JPH0342088A - Treatment of waste photographic solution - Google Patents

Abstract

PURPOSE:To simply concentrate a waste photographic soln. without generating an offensive odor or corroding an apparatus by cooling the waste photographic soln. to deposit the solute and by concentrating the resulting dilute supernatant by evaporation. CONSTITUTION:A waste developing soln. 11 stored in a waste soln. tank 5 is cooled with a cooler 101 to deposit the solute and to leave a dilute secondary waste soln. as supernatant. The deposited solute is discharged and recovered by opening a cock 102 and the secondary waste soln. is poured into a waste soln. tank 7 by a pump 10. The waste soln. 110 in the tank 7 is stuck to travelling endless belts 14 and air heated with a radiator 22 is blown on the belts 14 with a fan 24 to rapidly evaporate water in the waste developing soln. sticking to the belts 14. The waste photographic soln. can simply be concentrated without generating an offensive odor or corroding the apparatus.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for treating waste liquid generated during the development of photographic light-sensitive materials using an automatic photographic processing machine, and in particular to a method for reducing the volume of the waste liquid for transportation or other purposes. Concerning a method for facilitating the handling of

(Prior Art) Conventionally, waste liquid resulting from the development process of silver halide photosensitive materials is washed with a large amount of water or countercurrently conserved in color labs, for example, in large color labs, medium color labs, and small color labs. Either the liquid was diluted with a chemical and then discharged, or the waste liquid was separated, the chemical solution was collected or treated with activated carbon, and the washing water was discharged as is.

On the other hand, in color minilabs, it has been proposed to use a device that collects waste liquid and heats it to a high temperature to evaporate it. However, the method of heating and concentrating has problems such as dissipation into the atmosphere and severe corrosion of the equipment.

In order to avoid such problems, even if a method is used in which the waste liquid is cooled and the solutes are precipitated and separated by filtration, the secondary waste liquid in the solution state after treatment also contains a considerable amount of solutes. The problem was that it could not be disposed of as is.

Storing or transporting the dilute secondary waste liquid as described above is undesirable because it requires storage space and transportation costs because the amount of solutes contained is small and most of it is water. Various chemical treatments can be used as a method, but there are problems in that the treatment liquid contains few solutes and COD contributing components are dilute, making chemical management troublesome and requiring operations by skilled technicians. Even if adsorption treatment using activated carbon or the like is used, the volatile components in the waste liquid are hydrophilic, making it inefficient and costly. Furthermore, since the treatment liquid is dilute, it is not suitable for electrolytic treatment, and decomposition equipment for biodegradation is expensive, making it unsuitable for general use. Therefore, there has been a demand for a treatment method that further concentrates the secondary waste liquid by appropriate means and facilitates handling such as transportation.

(Problems to be Solved by the Invention) The present invention is a method for treating waste liquid generated during the development process of photographic light-sensitive materials, by obtaining a dilute secondary waste liquid that has been subjected to a dilution treatment, and further, by effectively utilizing the secondary waste liquid. It provides a method for concentrating.

(Means for Solving the Problems) In concentrating the photographic waste liquid, the present inventor cools the photographic waste liquid in the first stage, precipitates the solute, and further processes the dilute supernatant obtained by precipitating the solute in the second stage. By evaporating and concentrating, the waste liquid can be easily evaporated without producing any odor or corroding the equipment.
The present invention was completed based on the discovery that it can be reduced in size.

That is, the present invention comprises (a) a step of cooling the photographic processing waste liquid to precipitate and separate dissolved substances from the waste liquid to obtain a secondary waste liquid with a reduced amount of dissolved components; (11) evaporating and concentrating the secondary waste liquid. The present invention provides a method for treating photographic processing waste liquid, which comprises the steps of:

The photographic processing waste liquid treated by the method of the present invention will be explained below.

The photographic processing waste liquid is mainly composed of photographic processing liquid components. In addition, photographic processing waste liquid also contains reaction products such as oxidized products of developing agents, sulfates, and halides produced during photographic processing, and components such as large amounts of gelatin and surfactants dissolved from photosensitive materials. It is.

Photographic processing solutions include color processing solutions, black and white processing solutions, reducing fluids used in plate-making operations, and development processing tank cleaning solutions. Ru.

Many color paper developers contain alkylene glycols and benzyl alcohols along with color developing agents, sulfites, hydroxylamine salts, carbonates, water softeners, and the like. On the other hand, developer solutions for color negatives, developer solutions for color positives, and some developer solutions for color paper do not substantially contain these alcohols. Alternatively, it is preferable to apply it to a waste liquid containing 1% by weight or less.

Color developers typically contain aromatic primary amine color developing agents. It is mainly p-phenylenediamine derivatives, typical examples being N,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-methyl-4-(N-ethyl-N-(β- hydroxyethyl)amino)aniline, N-ethyl-N-(β-
Methanesulfonamidoethyl)-3-methyl-4-aminoaniline.

Further, these p-phenylenediamine derivatives are salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The content of the aromatic-grade amine developing agent ranges from about 0.5 g to about 10 g per 11 developer solution.

Color developers contain various hydroxylamines as preservatives. Hydroxylamines can be substituted or unsubstituted, and in the case of substituted hydroxylamines, the nitrogen atom of hydroxylamines is substituted with a lower alkyl group, especially two alkyl groups (for example, carbon number 1 to 3). Hydroxylamines substituted with

Hydroxylamine content is 0 per 11 color developer
~5g.

In addition, the black and white developer contains l-phenyl-3-pyrazolidone, 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone, N-methyl-p-aminophenol and its sulfate, hydroquinone and its sulfone. Contains salts, etc.

Color and black and white developers usually contain sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts as preservatives. , their content is Og~5g/l.

Other preservatives include N and N for color and black and white developers.
Combinations of dialkyl-substituted hydroxylamines and alkanols such as triethanolamine are also used.

Color and black and white developers have a pH of 9-12.

Various buffers are used to maintain the above pH.

Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-a-ξ-no-2-methyl-1,3-propanediol salt, valine salt, proline salt,
Trishydrocyamitsumethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are highly soluble and have a high pH of 9.0 or higher.
These buffering agents are often used because they have the advantage of having excellent buffering ability in the t+ region, having no adverse effects on photographic performance (fogging, etc.) even when added to the developer, and being inexpensive.

The amount of the buffer added to the developer is usually 0.1 mol/l to 1
Mol/l.

In addition, it is added to the developer as an anti-settling agent for calcium and magnesium, or to improve the stability of the developer. Contains various cattle rate agents.

Typical examples are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, nitrilo-N,N,N-1 methylenephosphonic acid,
Ethylenediamine-N,N.

N', N'-tetramethylenephosphonic acid, 1. 3-Sia [no 2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, 2-phosphonobutane-1,2゜4-tricarboxylic acid,
1-hydroxyethylidene-1,1-diphosphonic acid and the like.

Two or more of these chelating agents may be used in combination, if necessary.

The developer contains various development accelerators. As the development accelerator, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides,
These include 1-phenyl-3-pyrazolidones, hydrazines, meso ion type compounds, thione type compounds, imidazoles and the like.

Furthermore, although the developer often contains bromide ions for the purpose of preventing fogging, a developer that does not contain bromide ions may be used for photosensitive materials containing silver chloride as a main ingredient.

In addition, a compound that provides chlorine ions, such as NaCl or KCl, may be contained as an inorganic antifoggant. Further, various organic antifoggants may be included as required. Examples of the organic antifoggants include adenines, benzimidazoles, benztriazoles, and tetrazoles.

The content of these antifoggants is 0.0 per 11 parts of the developer.
It is 10g to 2g.

These antifoggants include those that are eluted from the photosensitive material during processing and accumulate in the developer.

Moreover, various surfactants such as alkylphosphonic acid, arylphosphonic acid, fatty acid carboxylic acid, aromatic carboxylic acid, etc. may be contained as necessary.

In photographic processing, development is usually followed by bleaching, and sometimes bleaching is carried out simultaneously with fixing - bath bleach-fixing (Brix). The method of the present invention can also be applied to such treated waste liquid. The bleaching solution contains iron (I[
l) or Co(III) EDTA, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-cyamino-propane tetranosate, phosphonocarboxylate, as well as persulfates, quinones, and the like. In addition, it may contain appropriate rehalogenating agents such as alkali bromide and ammonium bromide, sulfates, carbonates, and nitrates. The fixing solution and bleach-fixing solution may contain thiosulfate (sodium salt, ammonium salt), acetate, borate, ammonium or potassium alum sulfite.

Due to its nature, the method of the present invention can be carried out in small-scale photo processing facilities such as small-scale photo labs called mini-labs, microfilm processing in office documentation, printing, plate making, color copiers, etc. Are suitable.

That is, the method of the present invention can be applied to the following waste liquids.

i) Printing plate factory: black and white, color developing solution, fixing solution, bleaching solution, these photographic processing waste solutions also contain various other waste solutions such as etching solution, reducing solution 1, organic solvents, tank cleaning solution, etc. % or less may be included.

ii) Color laboratory: black and white/color developer, fixer,
Bleach solutions, bleach-fix solutions, image stabilization baths, and other processing bath effluents.

In particular, it is suitable for small-scale labs called mini-labs and satellite labs.

Preferred embodiments include: (1) Collecting and treating the effluent from the above multi-towers and allowing the washing water to flow through as is; (2) If using a multi-stage countercurrent water-saving washing method or using a stabilization bath that also serves as washing, This is a method in which all discharged liquids are mixed and treated.

iii) Offices and stores: Offices that perform documentation using microfilm printer processors and reader printers such as Mikle 1200 (product name, manufactured by Fuji Photo Film Co., Ltd.), printers that print copies of drawings from drawings, etc. Fluid discharged from design offices using Prosensor, processors at stores where color copies are made, instant prints are taken at stores, etc.

In treating such a concentrated photographic waste liquid, the first step in the method of the present invention is to cool the waste liquid and precipitate and separate the above-mentioned dissolved substances to obtain a dilute secondary waste liquid.

In the present invention, cooling the photographic processing waste liquid to precipitate and separate the dissolved matter of the waste liquid usually means 15 to 22°C.
The photographic processing waste solution was cooled to -10 to 10°C to remove the sulfite and f! DTA, iron salts, hypo, sulfates, etc.
As the temperature of the waste liquid decreases due to cooling, the solubility of each substance decreases (the conductivity of the solution decreases from 30 mmho to 0.1 to 0.
．． 4ξ rumeau, that is, 1/100 to 11,500), the portion other than the portion corresponding to the amount dissolved at that temperature precipitates and becomes a solid component, which is precipitated and separated, reducing the amount of dissolved components in the supernatant.

If the supernatant liquid is frozen by cooling the cooling temperature to below -10°C, the supernatant liquid becomes sherbet-like, making it difficult to separate the precipitate. Moreover, when it is 100 or more, the solubility decreases little, so precipitation is small and the effect is not improved.

The cooling temperature is also related to the cooling time required for the melt to precipitate, but if the cooling time is within 30 minutes, it is preferably -5 to 0°C, and if the cooling time can take more than 30 minutes, 1° to 5°C is preferred.

Examples of cooling methods and devices include a system in which a refrigerant is operated through a pipe to cool the outer wall of the cooling sedimentation tank, or a cooling pipe is installed inside the cooling sedimentation tank. It is preferable to use a device that cools the outer wall of the cooling sedimentation tank. It is preferable to use a device that adds Na and S to the part where the photographic waste liquid is introduced into the cooling section. Silver ion (A1) reacts with N
Since the reaction of a, S + 2Ag"-8gas occurs, precipitation occurs quickly at low temperatures, improving separation efficiency.

The bleach-fix solution may be used alone as a waste solution, or it may be mixed with other processing solutions (for example, a color developer, a rinsing solution, or a stabilizing solution).

The pH at which the cooling method is effective for waste liquid separation is preferably p]!
pH 4-9, more preferably pH 6-8. Also, this cooling method is particularly effective for waste liquids with high salt concentrations.

The solid components precipitated by cooling may be collected as they are by scraping means, filtration means, etc., and treated as solid waste. The supernatant liquid is subjected to subsequent second stage treatment as a dilute secondary waste liquid.

In the present invention, in order to evaporate the secondary waste liquid in the second stage to obtain a concentrated liquid, the apparatus described in, for example, Japanese Patent Laid-Open Nos. 63-62587 and 63-62588 may be used. In this case, the evaporation temperature is 100°C or lower, preferably 70°C or lower, particularly preferably 10-45°C, and is usually carried out at normal pressure, but 0.01 to 1 atm, preferably 0.1 to 1 atm. It may be carried out at 1 atmosphere, particularly preferably from 0.5 to 1 atmosphere. Condensation temperature is 15°C or higher, preferably 15°C
-15°C, particularly preferably 0°C - 10°C.

The condensate obtained by such a device usually contains volatile components such as ammonia and sulfur dioxide gas in a concentration of 0.000001~0.
, ooi%, benzyl alcohol, glycol, etc. are 0.
000001 to 0.01%, but these may be disposed of as diluted waste liquid.

The remaining solids or concentrated liquids can be treated as solid waste or concentrated liquid waste.

When concentrating photographic waste liquid according to the method of the present invention in this way, the solute concentration in the photographic waste liquid is reduced to 10 to 30% by weight or less, preferably 1 to 10% by weight in the cooling step in the first stage.
The solid content to be precipitated is 0.3 based on the total volume.
Such a dilute secondary waste liquid, which is preferably ~1O%, is very efficiently concentrated by evaporation concentration in the second stage.

In the second stage of evaporation concentration process, the above secondary waste liquid is
By concentrating to about 30% (volume reduction rate), solid waste or concentrated waste liquid can be obtained.

By subjecting the concentrated waste liquid thus obtained to the first cooling step again, the photographic waste liquid can be concentrated even more effectively.

(Effects of the Invention) In the method of the present invention, a considerable portion of the dissolved matter is first removed by cooling, and then concentrated by evaporative concentration treatment, so that waste liquids with high initial concentration or high viscosity can be treated. solid waste and/or concentrated waste liquid,
It can be separated into a dilute concentrated liquid that can be discharged as is, which is advantageous in terms of cost and storage space when the concentrated waste liquid is collected and treated all at once. Furthermore, it also has the advantage of generating less noise and saving energy.

(Example) FIG. 1 shows an example of a processing apparatus used in the photographic waste liquid processing method of the present invention. An exhaust hole 3 and an intake hole 4 are provided on the right side of the main body case 2 of this waste liquid treatment device ml from above. A waste liquid precipitation tank 5 is installed on the left side of the main body case 2, and the waste liquid vibro from this waste liquid precipitation tank 5 is inserted into the main body case 2. A cooler 101 is arranged on the lower side inside the waste liquid precipitation tank 5,
A residue removing cock 102 is provided at the bottom end. Further, inside the waste liquid precipitation tank 5, the waste liquid vibro is covered with a filter 103. A waste liquid tank 7 is installed at the bottom of the main body case 2 so as to be located below the discharge hole of this waste liquid vibro.

The waste liquid vibro connecting this waste liquid tank 7 and the waste liquid tank 5 includes float switches F, ~F, and a pump drive circuit 9.
A suction pump 10 is provided which is controlled by. That is, until the float switch F is turned on by the photographic waste liquid surface in the waste liquid tank 7, the pump 10 operates to send the waste liquid 11 in the waste liquid tank 5 to the waste liquid tank 7, and the float switch F, By turning ON, the pump 10 stops operating.

Pulleys 12a and 12b are attached to the bottom of the waste liquid tank 7, and a mesh endless belt 14 is passed between the corresponding pulleys 13a and 13b provided in the main body case 2. There is. pulley 1
3a and 13b are connected to a motor M via V-belts 15a and 15b, and by driving the motor M, the endless belt 14 can be made to travel.

A duct 16 is provided above the pulleys 13a and 13b, and a fan 17 is provided within this duct 16. This fan 17 is connected to the motor M1 via V bell) 1B.
When the endless belt 14 is driven, air containing moisture evaporated from the endless belt 14 is sent to the exhaust hole 3 through the duct 16. A cooler 19 is attached to the other end of the duct 16 to cool the air sent by the fan 17. A water drop tray 20 is installed below the cooler 19 to receive the water cooled and liquefied by the cooler 19. A drain pipe 21 is attached to the tray 2o of this water drip tray, and the tray drains the water dripping onto the tray 2o to the outside of the main body case 2.

A radiator 22 is provided adjacent to the intake hole 4 provided on the side surface of the main body case 2, and an intake fan 2 is installed at the back of the radiator 22.
4 are provided. The cooler 19 and the radiator 22 are connected via a pipe 23 for refrigerant circulation. Furthermore, the pipe 23 is equipped with a compressor 25 for compressing the refrigerant circulating from the cooler 19, and a radiator 2.
Expansion valve 2 for rapidly expanding the refrigerant passing through 2
6 is connected. As a result, the compressed refrigerant having a high temperature flows through the radiator 22 and warms the outside air taken in from the intake hole 4. Further, when the refrigerant expands by opening the expansion valve 26 and passes through the cooler 19, it absorbs heat from its surroundings, so that the air discharged from the exhaust hole 3 is cooled.

According to the developing waste liquid treatment device I configured as described above,
The developer waste liquid 11 stored in the waste liquid tank 5 is stored in the cooler 1.
01, the solute precipitates and a dilute secondary waste liquid remains as a supernatant. The deposited precipitate is removed from the residue in conc. 1
It is discharged and collected by opening 02. The secondary waste liquid in the waste liquid precipitation tank 5 is transferred to the waste liquid tank 7 by a suction pump 10.
pumped to. As the amount of the secondary waste liquid 110 pumped up increases, the liquid level of the secondary waste liquid 110 in the waste liquid tank 7 rises. The liquid level is float switch F.

When detected, the operation of the suction pump 10 is stopped. Further, when the liquid level of the secondary waste liquid 110 falls, the float switch Fl becomes 0FFL, and the suction pump 1o is operated again via the pump drive circuit 9. Therefore, waste liquid tank 7
A predetermined amount of secondary waste liquid 110 is always stored.

By driving the motor M, the endless belt 14 runs while being partially immersed in the developer waste liquid. Therefore, the endless belt 14 to which the secondary waste liquid 110 has adhered is pulled out of the waste liquid tank 7 and exposed to the outside air. The endless belt 14 thus exposed to outside air is blown by the fan 24 into the endless belt 14 through the intake hole 4 and warmed by the radiator. When warmed air is blown onto the endless belt 14, the water in the developer waste adhering to the endless belt 14 rapidly evaporates. The humid air containing a large amount of moisture evaporated in this way is sent to the cooler 19 through the duct 16 by the fan 17. This air is cooled as it passes through the cooler 19, and the supersaturated water vapor is liquefied and dripped onto the tray 20. As a result, dry air after dehumidification is discharged from the exhaust hole 3. Therefore, there is no possibility of increasing the humidity around the developing waste liquid processing apparatus 1.

Further, since the water dripping onto the tray 20 is discharged to the outside of the main body case 2 through the drain pipe 21, it may be collected in a separately prepared container or simply poured into the drain pipe.

Note that as the endless belt 14, a synthetic resin sheet with a mesh structure, cloth, or the like can be used as long as it is easily adhered to developer waste. Furthermore, in the illustrated embodiment, two endless belts 14 are arranged in parallel in order to increase the evaporation efficiency and to avoid increasing the size of the device itself, but the number of endless belts 14 is not necessarily limited to this. Concentration progresses and secondary waste liquid 110
When the liquid level of the pump decreases, the float switch F2 connected to the pump and valve drive circuit 105 is activated to open the valve B and the valve B2, and then the pump P is activated. When the liquid level drops to the level of float switch Fl, pump P1 stops, valve B2 closes, and then valve B1 closes.
closes.

Thereafter, the pump 10 is started, and when the liquid level rises to the level of the float switch F+, the pump 10 is stopped.

FIG. 2 shows a modification of the apparatus used in the method of the invention. The processing waste liquid discharged from the processing machine is stored in the cooler 101.
' into a precipitation tank 5'. Solutes are precipitated from the photographic processing waste liquid cooled by the cooler 101'.
The supernatant overflows and passes through the vibro' and is further transferred to the waste liquid precipitation tank 5. The secondary waste liquid 110 concentrated through the operations described in FIG. 1 is transferred again to the waste liquid precipitation tank 5'.

FIG. 3 shows a modification of the apparatus used in the method of the invention. The processing waste liquid discharged from the processing machine is stored in the cooler 105.
．． 106 and is cooled in the pipe to precipitate the solute. The supernatant liquid overflows from the upper surface of the waste liquid precipitation tank 5', passes through the vibro 1 to which the cooler 104 is attached, and is transferred to the waste liquid precipitation tank 51. The supernatant liquid passes through the vibro as an overflow from the upper surface of the 5″F and moves to the waste liquid tank 7.

The following processing was performed using the apparatus shown in FIG.

Example 1 A developing treatment waste liquid obtained by performing the automatic developing process of Example 1 of JP-A No. 60-195545 was converted into (Al developing waste liquid (
b) The bleach-fixing waste solution was divided into two types and stored. Tokukai Showa 6
Photosensitive material 1 described in Example 1 of Publication No. 0-195545
5i to give (a) 4.21 (bl 2.51).

(a) (First, 30% of 3all per waste liquid 11
The waste liquid after 0 reaction, which was transferred to the waste liquid precipitation tank while mixing the sodium sulfide solution, is guided to the waste liquid precipitation tank 5, which is adjusted to 0 to -6°C by the refrigerant of the refrigerator, and the temperature is reduced to below zero in 30 minutes. The precipitate S cooled to -3° C. was discharged from the valve 102, and the supernatant secondary waste liquid 110 was transferred to the waste liquid tank 7, where it was evaporated and concentrated. Evaporation concentration is JP-A-63
This was carried out using the apparatus described in JP-A-156501. The results are shown in Table 1.

No. table 1) Measured using manganese dioxide solution.

2) Since it is a concentrated liquid, the error in COD is large and the value is approximate.

From the table above, C0D42000/1 waste liquid 4.21
COD 110.000■/1 waste liquid 2.51, average C0
The concentrated waste liquid of 6.71 with D76.000/l is 5.6
i condensate and thick sediment plus waste liquid (slurry, including oil) approx. I can see that I was able to break up with my office lady. Therefore, by the method of the present invention, the amount of concentrated waste liquid to be sent to the waste liquid treatment site could be reduced to about 15%, and about 84% of the amount of dilute condensed waste liquid that could be directly discharged was obtained.

[Brief explanation of drawings]

FIG. 1 shows the processing apparatus used in the method of the present invention, and the second
FIG. 3 shows a modification thereof.

Claims (1)

[Claims] (a) a step of cooling the photographic processing waste liquid to precipitate and separate dissolved substances from the waste liquid to obtain a secondary waste liquid with a reduced amount of dissolved components; and (b) a step of evaporating and concentrating the secondary waste liquid. Characteristic method for processing photographic processing waste liquid.