JPS63147593A - 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 at least a water soluble polymer. CONSTITUTION:The waste photographic processing liquid contg. thiosulfuric acid ions, silver ions, etc., is heated, evaporated and concentrated in the state of maintaining pH at 3.0-11.0 in the presence of at least the water soluble polymer such as polyvinyl pyrolidone and PVA. More specifically, the amine and ammonia odors of the residual liquid can be suppressed and the generation of gaseous H2S and S is suppressed if the above-mentioned water soluble polymer exists. As a result, the malodors are efficiently suppressed without entailing cost increase and without requiring 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 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 has been significantly reduced.

However, even with such low replenishment and waterless washing method photographic processing, even relatively small-scale processing can be performed, for example, about 10 sentences per day when processing X-ray photosensitive materials, and 1 day when processing photosensitive materials for printing plate making.
Approximately 30 liters of waste liquid is generated per day, and approximately 50 liters of waste liquid is generated per day from the processing of color photosensitive materials, which poses a problem.

The present inventor has developed a method for producing high concentrations (e.g. BOO20,000) in small amounts.
-30,000ppm, NHa" 20,000~4
We discovered that the evaporation method is an excellent method for efficiently treating photographic processing waste liquid (approximately 0,000 ppm) and have made various proposals (Patent Application Nos. 80-259QQ1 to 259).
No. 010, Patent Application No. 132098-1981, Patent Application No. 1981-
185099, patent application No. 185100, etc.)
.

However, in this heating-evaporation method, sulfur dioxide gas, hydrogen sulfide gas, sulfur gas, etc.
One problem was that a bad odor was generated due to ammonia gas, amine gas, etc., and unless this problem was solved, the process could not be completed.

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 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 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 this highly concentrated malodorous 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.

On the other hand, techniques are known in which evaporated gas is irradiated with ultraviolet rays or distilled liquid is subjected to ozone oxidation treatment, but these techniques have drawbacks such as high equipment cost and complicated maintenance.

[Object of the Invention] An object of the present invention is to solve the drawbacks of the prior art and provide a method that can efficiently suppress bad odors without increasing costs or requiring complicated work.

[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 is characterized in that the photographic processing waste liquid is heated, evaporated, and concentrated in the presence of at least a water-soluble polymer (hereinafter referred to as the water-soluble polymer of the present invention).

In a preferred embodiment of the present invention, the water-soluble polymer is a polyvinylpyrrolidone compound, polyvinyl alcohol, gelatin, a cellulose compound, isobutylene maleic anhydride copolymer, and the photographic processing waste liquid is a thiosulfate ion (e.g. ammonium sulfate), silver ions in addition to thiosulfate ions, and p)l of photographic processing waste liquid.
3.0~! 1.0, preferably 4.0 to 10.0, and heat, evaporate, and concentrate.

The processing apparatus for photographic processing waste liquid according to the present invention has a means for supplying photographic processing waste liquid, a 71 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. The apparatus for treating photographic processing waste liquid that undergoes evaporation and e-condensation is characterized by having means for supplying a water-soluble polymer to the photographic processing waste liquid.

[Operations] The present invention is based on a technical 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.

In other words, since the photographic processing waste liquid contains amines and ammonium salts, if the p)l of the distillate increases, it will generate amine odor or ammonia odor, and if the waste liquid contains periosulfate ions, it will be heated. It decomposes at high temperatures and generates +2S gas, and finally sulfurizes and generates S gas, producing a bad odor.

The present inventors have conducted intensive studies to suppress such bad odors, and have found that if the water-soluble polymer of the present invention is present during heating, the amine odor and ammonia odor of the distillate can be suppressed, and H2
It was discovered that the generation of S and S gas can be suppressed.

[Example] Hereinafter, one example of the present invention will be described with reference to the accompanying drawings in the case of a method for suppressing bad odor.

FIG. 1 is a conceptual diagram showing an example of a method for suppressing bad odors.

In the figure, l is a supply means for photographic processing waste liquid, IA is a waste liquid supply pipe used for the supply means 1, 2 is a preheater for preheating the photographic processing waste liquid before heating, 3 is an evaporation tank, and 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 a gas cooler for cooling the steam.

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. It is a means for supplying a water-soluble polymer to the water-soluble polymer tank In, the water-soluble polymer pump 11. It consists of a water-soluble polymer supply pipe 12 and the like. B is a means for supplying a pH adjuster to the photographic processing waste liquid, for example, pH adjuster tank 1.
3. p) I regulator pump 14. pHrA adjusting bone supply tube +5H:17) Consists of 0-ra pHC, etc. C
is a means for supplying sulfite ions or a compound that releases sulfite to the photographic processing waste, for example, the sulfite tank 16.
, a sulfurous acid pump 17, a sulfurous acid supply pipe 18, 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 and evaporation is performed in the presence of the water-soluble polymer of the present invention. During this time, the p)I of the waste liquid [concentrated liquid] is 3.0 to 11.0.
is preferably maintained at 4.0 to 8, more preferably 4.0 to 8.
．． 0, more preferably 5.0 to 7.0. Note that, if necessary, the waste liquid may contain sulfite ions and/or a compound capable of releasing sulfite ions, which will be described later. Heating temperature is controlled by temperature controller TC
will be adjusted accordingly.

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, COD, and SS, it can be discharged into rivers or reused as necessary. It is. The gas from which the distillate is separated does not have a bad odor and does not contain any problematic components.
Can be discharged outside the system.

On the other hand, the volume of the waste liquid in the evaporation tank decreases as the heating and evaporation time elapses, causing it to become condensed. The heater 4 for heating is stopped by the operation of a timer, for example, and the heating is completed. B. The distilled concentrate is discharged outside the system.

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

In the present invention, "heating and evaporating in the presence of a water-soluble polymer" means performing heating evaporation while the water-soluble polymer is present in the waste liquid or concentrated liquid before heating.

The water-soluble polymer used in the present invention is 30 to 10.0
A polymerization degree of 00 is preferable, more preferably 100.
Polymerization degree of ~5,000, particularly preferably 2
It has a degree of polymerization of 00 to 3,000.

The amount of the water-soluble polymer of the present invention is preferably 0.0
1-300 grams/statement, more preferably 0.05-10
0 grams/statement, most preferably 0.1-80 grams/9
．． It is.

The water-soluble polymer of the present invention is preferably a compound having an OH group or a CO group, more preferably the following (1) to (
5) can be mentioned.

(1) Polyvinylpyrrolidone compound (2) Polyvinyl alcohol (3) Gelatin (4) Cellulose compound (5) Isobutylene maleic anhydride copolymer The above polyvinylpyrrolidone compound (1) used in the present invention has a molecular structure in which A polymer having a pyrrolidone core unit, which may be a homopolymer of vinylpyrrolidone alone or a copolymer with other copolymerizable monomers, but must be water-soluble as a single polymer. It is.

Typical examples of other monomers that can be copolymerized with the vinyl pyrrolidone include vinyl esters, acrylic esters, methacrylic esters, acrylic acid, methacrylic acid, and styrene. Examples of vinyl esters include vinyl acetate and propionic esters. Examples include vinyl acid, vinyl acetate, etc.
Examples of acrylic esters include methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, etc. In the case of copolymers of these, the copolymerization ratio is 5 to 1 to vinylpyrrolidone.
It is preferably used in a range of 0.00 mol%.

Further, the average molecular weight of the vinylpyrrolidone polymer is not particularly limited, but is preferably 500 to 800,000, more preferably 2,000 to 400. ooo There is.

The average molecular weight of a polymer can be determined by a conventional method, for example, as follows.

Accurately weigh 1.000 g of the polymer sample, 1OOI11
After preparing a 1% aqueous solution by adding distilled water to a volumetric flask, the viscosity of the aqueous solution and water as a solvent is measured. An Ubbelohde capillary viscometer was used to measure the viscosity. The viscometer containing the measurement solution was suspended in a thermostat and held at 20°C ± 0.01°C for 30 minutes, the time required for the solution to flow between the two gauges was measured, and the average value of several measurements was determined. , the relative viscosity was calculated from the relationship shown in the following equation.

From the relative viscosity, the value is determined according to Fikentscher's equation % (see Edit), and the average molecular weight is determined from the value using the usual method.

Typical examples of the vinyl pyrrolidone polymer used in the present invention are shown below, but the invention is not limited thereto.

Exemplary compound (1) Polyvinylpyrrolidone (average molecular weight approximately 40,00
0) (2) Polyvinylpyrrolidone (average molecular weight approximately s, ooo
) (3) Polyvinylpyrrolidone (average molecular weight approximately ie, oo
o) (4) Vinylpyrrolidone-vinyl acetate copolymer (copolymerization molar ratio 7:3) (average molecular weight 4,000) (5) Vinylpyrrolidone-methyl acrylate copolymer (copolymerization molar ratio 7:3) ( Average molecular weight 1,00
0) (6) Vinylpyrrolidone-ethyl acrylate copolymer (copolymerization molar ratio 7:3) (average molecular weight 25.0
00) (7) Vinylpyrrolidone-butyl acrylate copolymer (copolymerization molar ratio 7:3) (average molecular weight 7,00
0) (8) Vinylpyrrolidone-2-ethylhexyl acrylate copolymer (copolymerization molar ratio 7:3) (average molecular weight 1
8.000) (9) Vinylpyrrolidone-styrene copolymer (copolymerization molar ratio l: 3) (average molecular weight 20,000) The polyvinyl alcohol of (2) above used in the present invention includes fully saponified products and partially saponified products. Any of these can be used. During production, when the acetyl groups in polyvinyl acetate molecules are changed to hydroxyl groups in the saponification process, the product that has undergone almost complete saponification is called the "completely saponified product," and the product that has been stopped midway and only a few acetyl groups remain. "Partially saponified products"
It is.

The degree of progress of the fermentation reaction is called the "degree of saponification" and is expressed as "mol%".
It is expressed as

These relationships are shown in the following scheme.

Partially saponified product Here, n, a+ or degree of polymerization, -x I 00 indicates degree of saponification I◆.

In the present invention, modified polyvinyl alcohol, particularly strong acid-modified polyvinyl alcohol, weakly acid-modified polyvinyl alcohol, partially acetalized polyvinyl alcohol, etc. may be used instead of or together with polyvinyl alcohol.

The polyvinyl alcohol of the present invention is also available from Ichisaka Products, for example PVA105. PVA2 [13゜P
VA204. PVA205. PVA405 (Kuraray "A"), Gohsenol NL-05, Gohsenol GL-03, Gohsenol AL-02, Gohselan (
Nippon Gosei Kagaku Kogyo Co., Ltd. (tA), Denka Popal -0
2. Denka Poval B-0:l (manufactured by Kikagaku Kogyo Co., Ltd.), C-25, C-20, C-201, C-1
7, A, yC-10, C-05, HA-23, MA-1
7, MA-5, PA-24, PA-20, PA-III
, PA-15, PA-10, PA-O5 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

Among the above-mentioned modified polyvinyl alcohols, examples of strongly acidic polyvinyl alcohols include polyvinyl alcohols modified with arylic acid or vinyl sulfonic acid copolymerization (10% or more Y), and examples of weakly acid-modified polyvinyl alcohols include carboxyl group-modified polyvinyl alcohols. Examples include polyvinyl alcohol, polyvinyl alcohol modified by copolymerization of acrylic acid and methacrylic acid (10% or less), and examples of partially acetalized polyvinyl alcohol include polyvinyl formal and polyvinyl butyral (however, the degree of acetalization is 15% or less, preferably 12% or less). can be given.

The above-mentioned modified polyvinyl alcohol can also be obtained from municipal products; an example of strong acid-modified polyvinyl alcohol is Gosselan (manufactured by Nippon Gosei Kagaku Co., Ltd.), and an example of weak acid-modified polyvinyl alcohol is L-506 (Kuraray). (manufactured by the company).

The above gelatin (3) used in the present invention is composed of a so-called polypeptide chain represented by the following general formula [A], and the chain is formed three-dimensionally.

General formula [A] I R'''R''' In the formula, R, R', R'', R''', R'''' are amino acid residues (for example, glycine, alanine, isoleucine, leucine, valine, phenylalanine, tyrosine, Tryptophan, serine, threonine, cystine, methionine, proline, oxyproline, lysine, oxylysine,
arginine, histidine, albaragic acid, glutamic acid, amide nitrogen). The dotted lines indicate connections between sub-valences, and Gin in a gel state is intertwined with these chains to form a network. As the temperature rises, the movement of the single cells of these micelles gradually increases, and this network structure forms.

Gelatin used in the present invention includes lime-treated gelatin, acid-treated gelatin, Bull, Soc, Sci
, Photo, Japan, No. 16. :10
Enzyme-treated gelatin as described in P. (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin derivatives include acid halides, acid anhydrides, isocyanates, bromoacetic acids, and alkanesultones.

Those obtained by reacting various compounds such as vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are used. A specific example is U.S. Pat. No. 2,614,928, 1:12.
, No. 945, No. 1, 18S, No. 1346, No. 3, 31
No. 2,553, Fukoku Patent No. 861,414, 1,0:
No. 13,189, No. 1.005,784, Special Publication No. 1973
-26845 etc.

Examples of the cellulose compound (4) used in the present invention include cellulose esters or ethers obtained by esterifying or etherifying the hydroxyl group of cellulose CJyOz(OH)3.

Cellulose ester is a derivative obtained by appropriately esterifying the three hydroxyl groups of cellulose with acids, such as nitric acid, sulfuric acid, acetic acid,
Propionic acid, acetic acid, other higher fatty acid esters, mixed esters of nitric acid, mixed esters of acetic acid, and the like are known.

Cellulose ether is a product obtained by etherifying the hydroxyl group of cellulose, and includes alkyl ethers such as methyl and ethyl, or benzyl ether. To produce cellulose ether, for example, the following method may be employed. That is, cellulose is made into alkali cellulose (mercerized), and as the reaction progresses, cellulose swells and decomposes, and partially becomes agglomerated to form a sticky paste. become. This can be purified to obtain cellulose ether.

Specific examples of the above cellulose compounds include carboxymethyl cellulose, hydroxyethyl cellulose,
Hydroxypropylcellulose, methylcellulose, ethylcellulose, ethylhydroxyethylcellulose,
Carboxymethylethylcellulose is mentioned.

Among the cellulose compounds mentioned above, hydroxypropylcellulose represented by the following general formula (B) is preferable as the cellulose compound used in the present invention.

General formula [B] In the formula, R1-R6 are hydrogen atoms, -CH3,-(E2H5
, -C2HsOH, +CH2CH(CH3)-o+謹H
(m is an integer of 1 or more), -CH2COOH, -CH
2(:0OCH3, -CH2COOC2H5.

-C2HnOC2)1s, where n is a positive integer.

The above isobutylene-maleic anhydride copolymer (5) used in the present invention is represented by the following general formula [C].

General Formula [0] In the formula, n is a positive integer. The compounds of (1) to (5) above may be added to the waste liquid alone, or may be added in combination of two or more.

The water-soluble polymer of the present invention may be added to the waste liquid before being supplied to the evaporation tank 3, or it may be added from outside after being supplied to the evaporation tank, before or after the start of heating. Alternatively, the water-soluble polymer of the present invention may be placed in an evaporation tank and then photographic processing waste liquid may be supplied thereto.

When the water-soluble polymer of the present invention is supplied externally,
As shown in FIG. 1, the water may be supplied from the tank 10 by the pump 11, or the tank 10 may be provided above the evaporation tank 3 without using the pump X1, and the water may be supplied using head pressure.

When the water-soluble polymer of the present invention is a liquid, it can be added, for example, as shown in FIG. 1, but when it is a solid, the solid can be directly added to waste liquid or e! It may be added to the liquid ii, or it may be dissolved in a tank in advance and added as shown in FIG.

When using two or more types of water-soluble polymers of the present invention, it is preferable to provide a '41a tank for each additive compound if they are added externally from a tank as shown in Figure 1, but depending on the physical properties of the compounds. In some cases, one tank can be used in common.

In the present invention, the pH of the waste liquid (e-ray source) is preferably 4.
．． 0-10.0. By maintaining it more preferably in the range of 4.0 to 8.0, particularly preferably in the range of 5.0 to 7.0, malodor 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 ammonium sulfite and has a low pH,
is low (e.g. pH 7 to 3), and when a color developing solution is mixed, the pH of this mixed waste liquid is high (e.g. p) 11
4 to 6).

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

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, CI) a compound that imparts buffering properties to the waste liquid against pH fluctuations; There are compounds that can be used to control pH fluctuations during the process by external addition.

The above CI) compounds include, for example, (1) metal oxides, metal hydroxides, or metal salts such as Ca, Mg, A, Fe, and Zn, which release [OH-] by lowering the pH and buffer Compound (2) p) such as a carbonate solid (e.g. CaC03)
Compounds that dissolve and become alkaline due to a decrease in I (
3) Buffers such as organic acids (e.g. citric acid, etc.) and their salts (4) Buffers such as fin acids (e.g. boric acid, phosphoric acid, etc.) and their salts (5) Aminocarboxylic acids such as EDTA The chelating agent (B) includes 1-hydroxyethylidene-1,1-diphosphonic acid, and these can be used alone or in combination of two or more.

Further, as the compound (II) above, for example, (1) N
Hydroxides of alkali metals or alkaline earth metals such as aOH, KOH, Ca(OB)2, etc. (2) Carbonates (3) Silicates (e.g. sodium silicate, etc.) (4) Phosphates (5) Borate (6) Alkaline earth metal salts such as Ca salt and G 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, the above p)l regulator is added at the above C
In the case of the compound I), 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 the heating may be started after being supplied to the evaporation tank. In the case of the compound (n), it is of course supplied to the evaporation tank 3 from the outside.

When the pH adjuster is supplied from the outside, as shown in FIG. Alternatively, the tank 13 may be installed above the evaporation tank 3 and the water may be supplied using head pressure.

In the present invention, when the pHW regulator is a liquid, it can be added, for example, as shown in FIG. 1, but when it is a solid, the solid may be added directly to the waste liquid or C condensate, or
Alternatively, it may be dissolved in a tank in advance and added as shown in FIG.

When using two or more types of pHTA regulators in the present invention, it is preferable to provide a plurality of tanks for each additive compound when externally adding them from a tank as shown in FIG. 1, but depending on the physical properties of the compound, In some cases, one tank can be shared.

In the present invention, when a pH adjuster is externally added as shown in FIG. 1, the amount of addition can be controlled by a signal from a pH controller. When the pH decreases, the pump 14 can be turned on by a signal from the controller to supply the pH adjuster. In addition, when the pump 14 is of a stroke adjustable type, the stroke can also be automatically adjusted.

In the present invention, in order to effectively suppress bad odors, it is preferable to heat and evaporate the waste liquid in the presence of sulfite ions and a compound capable of releasing sulfite ions.

Among photographic processing waste solutions, color developing solutions and bleach-fix solutions contain sulfite ions, but bleach solutions do not contain sulfite ions, and even waste solutions that contain sulfite ions deteriorate over time. It decreases and disappears due to Particularly in the case of mixed waste liquid, the rate of decrease is fast and the waste liquid disappears after being stored for several days, so the method is effective even in such cases.

The above-mentioned "heating and evaporating in the presence of sulfite ions" means that if the waste liquid received in the evaporation tank contains 1ifE acid ions, it may or may not be added newly, but If the waste liquid does not contain sulfite ions, or if the sulfite ions in the waste liquid disappear due to storage or disappear during the heating process, it is preferable to add new sulfite ions to the waste liquid. This involves heating and evaporating the substance while it is present. Sulfite ions and compounds capable of releasing sulfite ions may be present in the waste liquid in the evaporation tank in advance, or may be added continuously or intermittently during the heating evaporation process.

Alternatively, it may be made to exist in the stored waste liquid, and the waste liquid may be continuously or intermittently replenished into the evaporation tank.

The amount of sulfite ions (SO3'') present in the evaporator is preferably from 5X 10-' to 4 gram ions/situation, more preferably from IX 10-3 to 2 gram ions/situation, most preferably from 5X 10-3 to 2 gram ions/situation. 0.5 gram ion/statement.

The above-mentioned "compound that can release two sulfite ions (S03)" is a compound that can be hydrolyzed in an evaporation tank or heated and
It is a compound that releases by decomposition etc.

Specifically, the following compounds may be mentioned.

First, 2SO3, Na2SO3, 0IH4)2SO3,
NaH8O3゜KHSO3, Na2S2O5+, Ni2
Examples include inorganic sulfites such as 3205, 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 [I] or [II] can be mentioned, and at least one compound selected from these can be used.

General formula [I] R2-C-OH 5O3)1 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 8 carbon atoms, preferably 1 to 4 carbon atoms. 4 represents an alkyl group, and X represents an alkali metal or ammonium group.

One of the preferable carbonyl bisulfite adducts represented by the general formula [I] is one in which R1 is a hydrogen atom and R2 is an alkyl group having carbons a1 to a4, and the other is one in which R1 and Each R2 is an alkyl group having 1 to 4 carbon atoms.

General formula [II] In the formula, R3 and R4 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably 1 to 2 carbon atoms, X represents an alkali metal or an ammonium group, and n is 0-8
, 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, n is 1 to 4, and the other - is 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 orthosulfite adduct represented by the above general formula [I] or [II] are shown below, but the invention is not limited thereto.

Exemplary bisulfite adduct of general formula [I] I-(1) Acetaldehyde sodium bisulfite I-(
2) Propionaldehyde sodium bisulfite I-(3
) Butyraldehyde sodium bisulfite I-(4) Acetone sodium bisulfite I-(5) Butanone sodium bisulfite I-(6) Pentanone sodium bisulfite Illustrative bisulfite adduct of general formula [II] n-(1) Sodium succinic aldehyde bisbisulfite IT-(2) Sodium glutaraldehyde bisbisulfite 1l-(3) β-Methylglutaraldehyde sodium bisbisulfite n-(4) Sodium dialdehyde maleate bisbisulfite n-(5) 2.4-bentanedione Sodium bisulfite The above bisulfite adducts may be used alone or
More than one species may be used in combination.

As a compound other than the above, it can be decomposed by heating to 503
In addition to the above compounds, examples of compounds that release 2- include compounds represented by the following general formula I[1].

General formula [01 In the above formula, R5 and R6 each represent a hydrogen atom, an alkyl group that may have a substituent, an acyl group that may have a substituent, or a carbamoyl group that may have a substituent. represents, also R5.
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 a methyl group, an ethyl group, Examples of the n-substituted alkyl group include a butyl group, and examples of the n-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 an f1 substituent is preferably an acyl group or carbamoyl group which may have an aliphatic group or an aromatic group as a substituent.2 For example, an unsubstituted acetyl group, etc. In addition to acyl groups,
Examples of substituents include substituted acyl groups such as an aminoacetyl group (also known as glycyl group) having an amino group, and in addition to unsubstituted carbamoyl groups, those having substituents include, for example, N-methylcarbamoyl group, N,N Substituted carbamoyl groups such as -dimethylcarbamoyl group and N,N-tetramethylenecarbamoyl group are mentioned.

Examples of the ring formed by linking R5r and R6 include a morpholine ring, a piperazine ring, and a pyrrolidine ring. Preferred as R5 and R6 are a hydrogen atom, a methyl group, and an ethyl group, and a hydrogen atom is particularly preferred.

Xll X2 and X3 represent a hydrogen atom or an alkyl group which may have a substituent.

In Xl-X3, the alkyl group which may have an l substituent is preferably a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i- Propyl group, n-butyl group.

In addition to unsubstituted alkyl groups such as 1so-butyl group and 5ee-butyl group, hydroxymethyl group having a hydroxy group, carboxy group, etc. as a substituent, 3-hydroxyethyl group, 2-hydroxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-hydroxy-4-
Examples include substituted alkyl groups such as carboxybutyl group.

Hydrogen atoms are preferred as x, x2 and x3.

Among these are a methyl group, an ethyl group, and a hydroxy-substituted methyl group, and a hydrogen atom is particularly preferred.

X represents a hydrogen atom or an alkali metal (eg, sodium, potassium, etc.); the 0 layer represents an integer of 0 to 2, preferably 0 or 1, particularly preferably 0;

Specific examples of the compound represented by the above general formula [0] are shown below, but the invention is not limited thereto.

[Exemplary compounds] D-(1) N1(20H2SO3HD-(2)
NH2CH2CH2SO3HD-(10) NHzC
H-3O3H■ 2H5 D-(11) NHzCH-3lh)1C)+3 D-(12) NHzCH-3O3HCH2C00H D-(13) NHzCH-9O3HH20H D-(1B) NHzCH2C)l;+C:H2SO
3HD-(17) CH3-NHGH;C:HzSC
hHD-(21) pq-cn, so, HM-The above compounds may be added to the waste liquid alone or in combination of two or more.

When a compound capable of releasing the above 5032- is supplied from the outside, it may be supplied from the sulfurous acid tank 1B through the sulfurous acid pump 17, as shown in FIG. It may be installed above the tank 3 and supplied by head pressure.

When the compound capable of releasing 5032- is a liquid, it can be added, for example, as shown in FIG. 1, but when it is a solid, the solid can be added directly to the waste liquid or etfA liquid, Alternatively, it may be dissolved in a tank in advance and added as shown in FIG.

When using two or more compounds that can release the above 5032-, when adding them externally from a tank as shown in Figure 1,
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 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 chamber. In other words, by increasing the amount of heat applied per unit time, the thiosulfate is solidified before it decomposes and is not released to the outside, suppressing the odor. On the other hand, if the amount of heat applied is small, decomposition will be accelerated and the outflow of substances that cause bad odors will be activated.

An example of a method and a device for suppressing a bad odor has been described below in the margins, but 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. 81-132098
No., patent application No. 185099, patent application No. 61-185099, patent application No. 61-111
i5100 etc.).

(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 gin in the case of ammonium thiosulfate. Preferred types of waste solution include, for example, a mixed waste solution of a color developer and a bleach-fix solution or a stabilizer, or a waste solution of a bleach-fix solution alone, a fixer solution alone, or a stabilizer 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/4.

In addition, in the present invention, it is preferable to apply it to the treatment of small-volume waste liquids such as waterless automatic processors, etc. Here, small capacity is used as a concept for large-capacity factory waste liquids, etc. , for example, about li/D to 1000 degrees/D, although there is no particular numerical limitation.

(2) In the present invention, the method of supplying the waste liquid to the evaporation tank 3 includes a method of pumping it up from a waste liquid tank (not shown), a method of supplying it using hect 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. Concentration refers to reducing the volume of waste liquid after evaporation to 4 of the volume before evaporation.
It is to be reduced to one-fold or less, preferably one-fifth or less, and most preferably one-tenth. 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 evaporator LA3 is not particularly limited, but it may have a double structure of an outer tank (outer pot) and an inner tank (inner pot), and the inner tank may be formed with a removable bag made of resin, for example. is preferable,
Note that it is preferable that a heat insulating material (for example, a glass wool mat) be provided around the outer periphery of the evaporation tank 3, and that the upper part of the evaporation tank 3 be provided with a hinged opening/closing lid.

(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 electric heaters, nichrome wire heaters with built-in quartz tubes, ceramic heaters, etc., and it is preferable to install these inside the evaporator 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, 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,
Furthermore, a distillate containing ammonium salts such as ammonium sulfite can be obtained, and can be reused as fertilizer, etc., in addition to being used as a photographic processing solution in automatic processors (for example, as water for dissolving replenisher or washing water). .

(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 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 adsorption treatment provided at the end of the treatment.

[Experimental Example] The following experimental example was conducted using the photographic processing waste liquid shown below.

Processing process Processing temperature Processing time Color development 38℃ 3 minutes 15 seconds bleaching
White 38℃ constant for 3 minutes 15 seconds
Arrival: 38℃, 3 minutes and 15 seconds!
1g1 Stable 1st tank 32°C to 38°C 1 minute 1st stability 2nd tank 32°C to 38°C 1 minute 2nd stable
Dry for 1 minute at 38℃ 4
5°C to 65°C [Color developer] Potassium carbonate 30° Sodium hydrogen carbonate 2.5g Potassium sulfite
5g1-hydroxyethylidene-
1,1-diphosphonic acid (80%) 1.0g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride
0.8g 4-Amino-3-methyl-N=ethyl-N=(β-hydroxylethyl) Aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make one sentence, use potassium hydroxide or 20% sulfuric acid tep)l 1
Adjust to 0.0B.

[Color developer replenisher] Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite
7g sodium bromide
0.9g 1-hydroxyethylidene-1,1-diphosphonic acid (80%) 1.2g hydroxylamine! Acid acid 3.1g4-amino-
3-Methyltoethyl-N-(β-hydroxylethyl) Aniline sulfate 6.0g Potassium hydroxide 2g Add water to make one sentence, and adjust to pH 10 using potassium hydroxide or 20% sulfuric acid.
Adjust to 12.

[Bleach solution] Iron ammonium ethylenediaminetetraacetate 160g Disodium ethylenediaminetetraacetate 10g Ammonium bromide 15 (1g glacial acetic acid
Add 10mM water to make one sentence, and adjust the pH to 5.8 using aqueous ammonia or glacial acetic acid.

[Bleach replenisher] Iron ammonium ethylenediaminetetraacetate 170g Disodium ethylenediaminetetraacetate 12° ammonium bromide 178g glacial acetic acid
Add 211A water to make it 141, and 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 0.58 Sodium carbonate 10g Add water to make one sentence, and adjust to pH 7.0 using aqueous ammonia or glacial acetic acid. adjust.

[Qualitative replenisher] Ammonium thiosulfate 300g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Disodium ethylenediaminetetraacetate 0.8g Sodium carbonate 14g Add water to make 11, and adjust to pH 7.5 using aqueous ammonia or glacial acetic acid. .

[First stable solution and first stable replenisher] 5-chloro-2-methyl-4-isothiazolin-3-one 0.0232-isothiazolin-3-one 0.02° ethylene glycol 1.0 g The pH was adjusted to 11 with water, and the pH was adjusted to 7.0 with 20% sulfuric acid.

[Second Stable Solution and Second Stable Replenisher] Formalin (37% aqueous solution) 2+sJ1 Conidar 2x (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 5tJL water to make 1sL.

The color developing replenisher was added to the color developing bath in an amount of 13.5 m per IQO cm of color negative film, the bleaching replenisher was added in an amount of 5.5 m per 100 cm of color negative film, and the fixing replenisher was as follows. color negative film 100
The fixing bath is replenished with 8 mJlj per crn', and the first stable replenisher is added at 8 mJlj per 100 crn' of color negative film.
+lfL was added to the first stabilizing bath, and the second stabilizing replenisher was added to the second stabilizing bath at a concentration of 150 ml per 100 cm' of color negative film.
m! l flowed.

(Paper Processing) Next, Sakura Color SR Paper (manufactured by Konishiroku Photo Industry Co., Ltd.) was subjected to continuous processing using the first processing step and the processing solution after printing.

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℃ for about 2 minutes Processing solution composition [Color development tank solution] Benzyl alcohol 15+A ethylene glycol 15+A potassium sulfite 2.0g Potassium bromide
1.3g sodium chloride
0.28 potassium carbonate
24.0゜3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 4.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) ( Product name Keikoru PK-Conch (manufactured by Shin Nisso Kako Co., Ltd.) 1.0g Hydroxylamine sulfate 3.0g! -Hydroxyethylidene-1,
1- Niphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride Φ6 Water fM O, 7g 1.2-Hydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Add water to make one sentence, Adjust the pH to 10.20 with potassium hydroxide and sulfuric acid.

[Color developer replenisher] Benzyl alcohol 20+*1 Ethylene glycol 20+s Potassium sulfite 3.0g Potassium carbonate
30.0g Hydroxylamine T
I&M salt 4.0g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 6.0g Optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) ( (Product name: Keikol PK-Conc (manufactured by Nisso Kako Co., Ltd.)) 2.5g 1-Hydroxyethylidene-1,l-niphosphonic acid 0.5g Hydroxyethyliminodiacetic acid m5, Og Magnesium chloride hexahydrate 0.8g 1 .2-Hydroxybenzene-3,5-disulfonic acid-
Add 0.3g of disodium salt and water! ; Adjust to pH 10.70 with potassium hydroxide.

[Bleach-fix tank solution] Ethylenediaminetetraacetic acid ER2 Iron ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3, Q g Ammonium thiosulfate (70% solution) 100.0aJL
Ammonium sulfite (40% solution) 27.5m
Add M water to bring the total volume to lfL, and adjust to p) 17.1 with potassium carbonate or glacial acetic acid.

[Bleach-fixing replenisher A] Ferric ammonium ethylenediaminetetraacetate dihydrate 2B0.0g Potassium carbonate 42.0g Add water to bring the total volume to 11.

The p)I of this solution is 6.7±0.1.

[Bleach-fix replenisher B] Ammonium thiosulfate (70% solution) 500.0+
JL ammonium sulfite (40% solution) 250.
0tJL ethylenediaminetetraacetic acid 17.
0g ice vinegar m85.0 Add layered water to bring the total volume to one level.

The pH of this solution is 5.3±0.1.

[Water washing alternative stable tank fluid and replenisher] Ethylene glycol 1.0g 1-hydroxyethylidene-1,1-niphosphonic acid (80% 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-fix tank solution, and stability tank solution, and add the above color developer replenisher and bleach-fix replenisher A every 3 minutes while processing the Sakura Color SR paper sample. A running test was conducted while replenishing B and stable replenisher through a metering cup. The amount of replenishment is 1901 as the amount of replenishment to the color developing tank per rn' of color paper, the amount of replenishment to the bleach-fixing tank is 50 layers each of bleach-fixing replenisher A and B, and the amount of replenishment to the stabilization tank is 1901, as a substitute for washing. 250 doses of stable replenisher were added. In addition, the stabilization tanks of the automatic developing machine are the first to third tanks in the direction of the flow of the sample, 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 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 following processing.

Experimental Example 1 The photographic processing waste liquid of 51 is shown in Figure 1. was received and subjected to evaporation treatment.

10 g of the water-soluble polymer shown in Table 1 was added to the photographic processing waste liquid. In the table, PVA is polyvinyl alcohol,
PvP is polyvinylpyrrolidone.

The pH of the waste liquid from the evaporation tank was adjusted to 6 using H2SO4 and KOH before heating started.

The mixture was concentrated by evaporation until it became 500 ml, and the evaporated gas was cooled to obtain a distillate.

The concentrations of H2S gas and NH3 gas in the gas on the surface of the distillate were measured. The results are shown in Table 1.

As is clear from Table 1, it can be seen that the use of the water-soluble polymer of the present invention has an effect of suppressing bad odor. On the other hand, it can be seen that there is no bad odor effect in the case of no additives or in the case of polymers other than those of the present invention.

Experimental Example 2 In Experimental Example 1, a similar experiment was conducted using PVA with different degrees of polymerization. The results are shown in Table 2.

Table 2 As is clear from Table 2, the degree of polymerization is 30 among PVA.
10,000, it can be seen that the effect of suppressing bad odor is particularly excellent.

Experimental Example 3 The same results as in Experimental Example 2 were obtained when gelatin, hydroxyethyl cellulose, isobutylene maleic anhydride copolymer, and polyvinylpyrrolidone were used in place of PVA used in Experimental Example 2.

Experimental Example 4 When conducting the same experiment as Experimental Example 1, the p of the waste liquid before the start of evaporation is
When H was changed, a reduction effect of 112 sW degree in the upper part of the accumulated liquid was obtained compared to those of p113 to p11. +1
) + 5 or lower, the amount of H2S generated increased slightly, and at pH 4 or lower, it further increased.

On the other hand, the effect on ammonia odor was also obtained in the pH range of 3 to 11, but the ammonia in the upper part of the collected liquid increased slightly at pH 7 or lower, and further increased slightly at pn 8 or higher.

Experimental Example 5 When thiosulfate ions are removed from the waste liquid used in Experimental Example 1, H
It was found that the amount of 2S generated decreased. It has also been found that it is more effective to use a water-soluble polymer when it contains thiosulfuric acid. Furthermore, similar effects were obtained with silver ions as with thiosulfate ions.

[Effects of the Invention] According to the present invention, even if photographic processing waste liquid is evaporated, the amine odor and ammonia odor of the distillate can be suppressed, and the generation of H2S gas and S gas can be suppressed. Therefore, even if activated carbon treatment or the like is provided as a secondary treatment, the load of the secondary treatment is significantly reduced, the amount of adsorbent consumed is reduced, and the complexity required for replacing the adsorbent is eliminated.

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, which is an embodiment of the present invention. 1: Waste liquid supply means 2: Preheater 3: Evaporation tank 4: Heating means, heater 5: Steam exhaust pipe 6: Gas cooler 7: Gas cooler fan 8: Distillate tank 9: Circulation fan 10: Water-soluble polymer tank 11 2 Water-soluble polymer pump 12: Water-soluble polymer supply pipe 13: pH adjuster tank 14: pHyA adjustment agent pump Is: PTL adjuster supply pipe 16: Sulfur dioxide tank 17: Sulfur dioxide pump 18: Sulfur dioxide supply pipe

Claims (6)

[Claims] (1) A method for treating photographic processing waste liquid, which comprises heating, evaporating, and concentrating the photographic processing waste liquid in the presence of at least a water-soluble polymer. (2) The method for treating photographic processing waste liquid according to claim 1, wherein the water-soluble polymer is a polyvinylpyrrolidone compound, polyvinyl alcohol, gelatin, a cellulose compound, or an isobutylene maleic anhydride copolymer. (3) The method for treating photographic processing waste liquid according to claim 1 or 2, wherein the photographic processing waste liquid contains thiosulfate ions. (4) The method for treating photographic processing waste liquid according to claim 3, wherein the photographic processing waste liquid contains silver ions. (5) The photograph according to any one of claims 1 to 4, 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. (6) 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 a water-soluble polymer to the photographic processing waste liquid.