JPH0771665B2 - Evaporative concentration processing equipment for photographic processing waste liquid - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for evaporative concentration of a photographic processing waste liquid, and more particularly, to a waste liquid generated by development processing of a photographic light-sensitive material by an automatic processor, which is collected by a trader. The present invention relates to an apparatus for evaporative concentration of photographic processing waste liquid suitable for processing in or near an automatic processor.

(Background of the Invention) Generally, photographic processing of a silver halide photographic light-sensitive material is performed by developing, fixing, washing with water in the case of a black-and-white light-sensitive material, and color development, bleach-fixing (or bleach-fixing) in the case of a color light-sensitive material. ), Washing with water, stabilization, etc.

In a photographic process for processing a large amount of a light-sensitive material, while a component consumed by the process is replenished, a component that is concentrated by elution or evaporation in the process solution by the process (for example, a bromide ion in a developing solution, a fixing solution in a fixing solution). By removing the silver complex salt etc.) and keeping the components of the processing solution constant, a means to keep the performance of the processing solution constant is adopted. A part of the processing liquid is discarded to remove the chemical components.

In recent years, the development processing solution is changing to a system in which the amount of replenishment including washing water is greatly reduced due to pollution and economical reasons, but the photographic processing waste solution is led from the processing tank of the automatic processor by a waste solution pipe. It is diluted with waste water of washing water, cooling water of automatic developing machines, etc. and then disposed of in sewers.

However, in recent years, due to stricter pollution regulations, it is possible to dispose of wash water and cooling water in sewers and rivers, but other photographic processing solutions [eg, developing solution, fixing solution, color developing solution, bleach-fixing solution] (Or bleaching solution, fixing solution), stabilizing solution, etc.] is practically impossible. As a pollution processing method for reducing the pollution load of the photographic processing waste liquid, for example,
Activated sludge method (Japanese Patent Publication No. 51-7952, No. 51-12943, etc.),
Evaporation method (JP-A-49-89437, JP-B-56-33996, etc.),
Electrolytic oxidation method (JP-A Nos. 48-84462, 49-119457 and 4
9-119458, JP-B-53-43478, etc.), ion exchange method (JP-B-51-37704, JP-B-53-43271, JP-A-53-383)
Etc.), reverse osmosis method (JP-A-50-22463 etc.), chemical treatment method (JP-A-49-64257, JP-A-53-12152, JP-A-49-5883).
No. 3, No. 53-63763, No. 57-37395, No. 57-37396
No.) etc. are known, but they are not enough. Therefore,
Generally, waste liquid is collected by a waste liquid collection company, and is secondarily and thirdarily treated to be harmless, but the collection cost of waste liquid not only increases year by year due to soaring collection costs, but collection efficiency is poor at minilabs, etc. There is a problem that the waste liquid fills the store.

On the other hand, in order to solve these problems, it is possible to easily process the photographic waste liquid in a minilab, etc.
Studies have been conducted to heat the photographic processing waste liquid to evaporate the water content to dryness or solidification, and for example, it is shown in Japanese Utility Model Publication No. 60-70841. In the research of the inventors, when the photographic processing waste liquid is concentrated by evaporation, harmful or extremely malodorous gas such as sulfurous acid gas, hydrogen sulfide and ammonia gas is generated, which is used as a fixing solution or a bleach-fixing solution for the photographic processing solution. It was found that ammonium thiosulfate and sulfites (ammonium salt, sodium salt or potassium salt), which are often used, are generated by decomposition due to high temperature. Further, during evaporation processing, the water content in the photographic processing waste liquid becomes vapor and is gasified, so that the volume expands and the pressure in the evaporation tank increases. Therefore, this pressure causes the harmful or malodorous gas to leak out of the apparatus from the evaporation processing apparatus, which is extremely unfavorable in the working environment. Furthermore,
There is a problem in that a precipitate generated when the photographic processing waste liquid is evaporated and concentrated has a viscosity and is attached to a processing device or a taking-out means, so that it takes time to take it out.

Therefore, in order to solve these problems, the inventors of the present invention have conducted various researches and experiments and found that the electrophotographic material is brought into direct contact with a conductive material and an electric current is passed through the electroconductive material to remove the photoprocessing waste solution. It was found that when heated, it is possible to suppress the generation of odors that occur during evaporative concentration due to the effect of catalytic action or electric current, and moreover, the composition changes to a non-viscous precipitate by evaporative concentration.

(Object of the Invention) The present invention has been made in view of the above-mentioned conventional problems, and a first object of the present invention is to evaporate a photographic processing waste liquid for reducing harmful or malodorous components generated by evaporative concentration of the photographic processing waste liquid. An object is to provide a concentration processing device. A second object of the present invention is to provide an evaporative concentration processing apparatus for photographic processing waste liquid which changes the composition of the precipitate to reduce the viscosity and facilitates removal from the processing apparatus.

(Means for Solving Problems) In order to solve the above-mentioned problems, the photographic processing waste liquid is heated to evaporate and condense to precipitate solutes in the photographic processing waste liquid. At
A conductive material is brought into direct contact with the photographic processing waste liquid, and a current is passed through the conductive material to heat the photographic processing waste liquid.

The effect of the present invention is to prevent precipitation of ammonia gas and sulfurous acid gas caused by heating and evaporating ammonium thiosulfate and ammonium sulfite or their respective sodium salts and potassium salts present in the photographic processing waste liquid, and to prevent precipitation. It is to change the composition of the product so that it can be taken out easily.

The inventors of the present invention firstly heat and evaporate and concentrate the photographic processing waste liquid, the concentrated heavy liquid falls to the lower part, and the upper part becomes a dilute waste liquid, and odor and gas generation due to thermal decomposition are significantly suppressed. However, as a result of further studying the above method, when the conductive material was brought into direct contact with the photographic processing waste liquid, the surface of the conductive material was partially heated to cause a catalytic action, or the photographic processing waste liquid was discharged from the conductive material. It was found that when an electric current flows through it, special ions gather and react in this area, the generation of odor and gas due to thermal decomposition is suppressed, and the composition of the precipitate changes to a non-viscous one. This is because, for example, when ammonia gas decomposes into nitrogen and water, or thiosulfuric acid decomposes to sulfuric acid and sulfurous acid gas does not occur, and when precipitation occurs by evaporative concentration, thiosulfuric acid has been concentrated and precipitated until now. However, it is thought that it is decomposed into sulfuric acid and precipitates. As a result, the odor at the time of evaporative concentration can be reduced, and the precipitate does not adhere to the processing device, which facilitates removal.

As the conductive material of the present invention, for example, the following materials are used.

(1) Nickel chrome For example, nickel 50 to 80%, chromium 10 to 30%, manganese 3% or less, carbon 1% or less, silicon 0.5% or less, and the balance iron.

(2) Iron Chromium For example, chromium is 15 to 30%, aluminum is 2 to 6%, manganese is 2% or less, carbon is 0.5% or less, and the rest is iron.

The following are more preferably used as the conductive material of the present invention.

(1) Single crystal silicon (Si) (2) Polycrystalline silicon (Si) (3) Tantalum nitride (Ta ₂ N) (4) Tantalum-silica (Ta-SiO ₂ ) (5) Zirconium nitride (ZrN) (6) Titanium nitride (TiN) (7) Chromium-silicon-oxygen (Cr-Si-O) (8) SiC may be used alone, or SiC-Zr, SiC-Cr, SiC-H.
It may be f, SiC-Ti, SiC-W, SiC-Nb, SiC-Ta, or SiC-La.

(9) Compound of boron (B) and La, Cr, Ti, Na, Ta, W, V (10) Carbon may be used alone, carbon and halogen,
A compound with Si, Ge or H may be used.

(11) Platinum (Pt) (12) Molybdenum alone or a compound of molybdenum and Si may be used.

Furthermore, each of (1) to (12) may be used alone, or any one of them may be selected and used in combination or mixed.

The conductive material of the present invention is composed of the above-mentioned resistance material or semiconductor material, and at least a part thereof is not coated. In addition, the shape is the resistivity of the conductive material,
Various types are adopted depending on the physical properties and the like, and for example, a linear type may be used. In this case, the coil may be wound in a single or multiple turns, or in various other shapes.

In addition, one or a large number of rod-shaped conductive materials may be arranged and used, or one or a plurality of plate-shaped conductive materials may be used, or the plate-shaped material may be used by rolling. Good.

These conductive materials are dipped vertically or horizontally in the photoprocessing waste liquid.

Further, a conductive material made of, for example, a semiconductor material may be put in the electrode of the net-like container, and the electrode may be put in a rod shape in the conductive material so that an electric current may flow. Alternatively, a plurality of roll-shaped electrodes may be used, and a conductive material may be inserted between the electrodes to flow an electric current. Further, a plurality of plate-shaped electrodes may be arranged at predetermined intervals, and the conductive material may be interposed between the electrodes. May be disposed, or electrodes may be provided at both ends of the conductive material so that a current may flow.

Then, these conductive materials may be entirely immersed in the photographic processing waste liquid, or approximately half or a small amount thereof may be immersed.
It is arbitrarily selected depending on the shape and physical properties of the conductive material.

The resistance of the conductive material of this invention is preferably 0.01 Ω to 1000
In the range of Ω, more preferably in the range of 0.01Ω to 100Ω,
More preferably, it is set in the range of 0.1Ω to 100Ω.
This conductive material has a current amount of
As described above, it is determined by the physical properties and morphology of the conductive material. As the power source, an AC power source or a DC power source is used by providing a rectifier. Further, the current-voltage regulator adjusts the applied current-voltage value according to the conductive material used.

The amount of current flowing from this conductive material into the photographic processing waste liquid is preferably in the range of 1 mA / to 100 A /, more preferably 10 mA /
It is set in the range of 10A /. Also, the temperature to be heated by this conductive material depends on the type of photographic processing waste liquid, the reduced pressure state, etc. and cannot be determined in any way, but generally 30 ° C to 120 ° C is good, energy cost, waste liquid processing speed, etc. Considering the above, 40 ° C to 80 ° C is preferable, and 50 ° C to 70 ° C is more preferable.

Further, since the present invention spontaneously precipitates in the lower part of the evaporation tank, as a preferred example, by continuously taking out the precipitate from the lower part of the evaporation tank, the photographic processing waste liquid can be automatically supplied from the upper part, A continuous evaporation process can be performed semipermanently.

As a method for continuously taking out the precipitate, an endless belt may be used, or a rotating spiral tube may be used, and any method may be used.

In general, it is desirable to remove the precipitate at the bottom of the evaporator by a batch method after processing a certain amount of photographic processing waste liquid. Further, since the temperature of the lower part of the evaporator is low, even if the precipitate is taken out during operation, there is no danger, and there is no offensive odor or harmful gas, and it is possible to operate extremely safely.

As a preferred application example of the present invention, it is suitable for processing a photographic processing waste liquid generated during the development processing of a photographic light-sensitive material by an automatic processor in or near the automatic processor. Here, the automatic processor, the evaporative concentration processing device, and the photographic processing waste liquid will be described.

(1) Automatic Developing Machine and Evaporative Concentration Processing Apparatus In FIG. 1, an automatic developing machine is indicated by reference numeral 100, and an evaporative concentration processing apparatus is indicated by reference numeral 1. The illustrated automatic processor 100
Is a system in which a roll-shaped photographic light-sensitive material F is continuously guided to a color developing tank CD, a bleach-fixing tank BF, and a stabilization processing tank SD for photographic processing, dried D, and then wound up. Reference numeral 101 is a replenisher tank, in which the sensor 102 detects the amount of photographic processing of the photographic photosensitive material F, and the replenisher is replenished in each processing tank by the control device 103 according to the detection information.

When the replenisher is replenished in each photographic processing tank, it is discharged from the processing tank as overflow waste liquid and collected in the stock tank 104. As a means for transferring the overflowed photographic processing waste liquid to the stock tank 104, a simple method is to drop it naturally through a guide tube. In some cases, forced transfer may be performed using a pump or the like.

The evaporative concentration processing apparatus 1 includes an evaporating pot 2 for storing a photographic processing waste liquid,
Conductive material 3 which heats the photographic processing waste liquid and sends an electric current therethrough,
It is composed of a discharging means 5 for discharging a precipitate 4 generated as the photographic processing waste liquid evaporates and concentrates, a vapor cooling means 6, a pressure reducing means 7 and the like. The precipitate 4 discharged from the discharging means 5 is stored in the precipitation storage container 8, and the condensate depressurized by the depressurizing means 7 is stored in the condensate storage tank 9.
A gas adsorbing means 10 such as a filter or an adsorbent can be added to the aggregate liquid storage tank 9. Conductive material 3
The above-mentioned resistance material and semiconductor material are used as the above, and they are arranged so as to be entirely immersed in the upper portion of the photographic processing waste liquid in the evaporation tank 2. The conductive material 3 is connected to the voltage / current regulator 90 via wiring, and the voltage / current regulator 90 is connected to the voltage / current regulator 90.
Is connected to a commercial power source 91, and is controlled by the control device 103 so as to obtain a predetermined amount of heat according to the conductive material 3. The conductive material 3 heats the photographic processing waste liquid, and an electric current flows in the liquid because the conductive material 3 is in direct contact with the photographic processing waste liquid. As a result, a catalytic action and a special reaction occur to reduce the odor during evaporative concentration. Moreover, since the composition of the precipitate 4 changes and the viscosity becomes smaller, the adhesion of the precipitate 4 in the evaporation pot 2 is reduced, and the precipitate 4 is easily taken out. If a commercial power source is used as the power source for the electric material 3,
It is preferable because there is no need to prepare a special power source.

As the discharging means 5, a known discharging device using a rotary screw pump or a concentrated solution of the photographic processing waste liquid is introduced into a container having one or more of a liquid absorbing resin and a solidifying agent from the bottom of the evaporator 2 through a valve. It can be designed in various ways such as being naturally dropped and solidified.

The amount and temperature of the photoprocessing waste liquid in the stock tank 104 is detected by the sensor 105, the information is stored in the control device 103, and when it is detected that the photoprocessing waste liquid in the stock tank 104 is full, Replenishment of the replenisher is prohibited so that the photoprocessing waste liquid is not discharged, or the pump 106 is driven to supply the photoprocessing waste liquid from the stock tank 104 to the evaporation tank 2. In order to prevent malfunction, it is preferable that the stock tank 104 has a sufficient capacity, or a plurality of stock tanks or spare tanks are provided. Further, in a system in which the photographic processing liquid is not collectively processed but is separately processed according to the type of the photographic processing waste liquid, the liquid temperature and the like are detected for each stock tank 104.

The temperature detection of the photographic processing waste liquid in the stock tank 104 is important as information of the photographic processing waste liquid for the operation control of the evaporative concentration processing apparatus 1 described later, particularly for controlling the heating temperature.

The supply of the photographic processing waste liquid from the stock tank 104 to the evaporative concentration processing apparatus 1 includes a method in which a fixed amount is supplied once and a method in which a fixed amount or a variable amount is continuously supplied. In the former case, the supply from the stock tank 104 to the evaporative concentration processing apparatus 1 is controlled according to the reduction amount of the photographic processing waste liquid in the stock tank 104 by the sensor 105 and / or the detection information of the photographic processing waste liquid in the evaporation tank 2 by the sensor 11. . In this case, the control may be performed according to the detection information by the flow meter provided in the waste liquid supply pipe from the stock tank 104 to the evaporative concentration processing apparatus 1.

In the case of a system that supplies a fixed amount or a variable amount continuously,
Temperature of supplied photographic processing waste liquid The amount of supplied photographic processing waste liquid is adjusted according to the temperature of the conductive material 3 or the evaporator 2 of the evaporative concentration processing apparatus 1. Further, the amount of the photoprocessing waste liquid to be supplied is always kept constant, and the amount of the photoprocessing waste liquid in the evaporative concentration processing apparatus 1 is detected by the sensor 11, and the heating temperature of the conductive material 3 is controlled to increase or decrease by the amount, or The heating time may be controlled to increase or decrease.

The evaporative concentration processing apparatus 1 is controlled according to the difference between the amount of the supplied photographic processing waste liquid and the amount of the processed photographic processing waste liquid, or the amount of the remaining photographic processing waste liquid or the amount of the processed concentrated photographic processing waste liquid. Be done.

In the system of supplying a fixed amount of photographic processing waste liquid to the evaporation concentration processing device 1 at a time, the temperature of the supplied photographic processing waste liquid and the temperature of the conductive material 3 or the evaporation pot 2 are detected. For example, the operation of the evaporative concentration treatment apparatus 1 can be controlled by controlling the treatment time.

In addition, the supply, processing (evaporation, concentration), and discharge of the photographic processing waste liquid are controlled by various items as described above, and correspondingly, time, viscosity, pressure, liquid level, concentration, electric resistance, weight Various sensors 11 etc. that detect etc. are used,
Moreover, the mounting positions of the sensor 11 and the like are various.

Photographic processing waste liquid The photographic processing waste liquid which can be processed according to the present invention includes, as a representative example thereof, the waste liquid which appears during processing of a silver halide color photographic material. The processing effluent is not limited to this, and includes the effluent discharged when processing other silver halide color photographic materials.

(Embodiment) FIG. 2 is a schematic view of an embodiment showing the present invention more specifically. A conductive material 3 is provided inside the evaporation pot 2 of the evaporation concentration processing apparatus, and a commercial power source 91 is provided via a voltage / current regulator 90.
Connected with. An upper limit liquid level sensor 12 and a lower limit liquid level sensor 13 are provided above the conductive material 3 to prevent the evaporation tank 2 from emptying. Further, a waste liquid supply pipe 15 having a solenoid valve 14 is provided above the evaporation tank 2, and the solenoid valve 14
The photoprocessing waste liquid from the waste liquid storage tank 16 is evaporated by the operation of
Is supplied to. The waste liquid storage tank 16 is provided with a liquid level sensor 17 for detecting the remaining amount of the photographic processing waste liquid, and inputs the liquid amount information to the control device 103.

Further, a solenoid valve 18 for releasing the reduced pressure is provided on the upper portion of the evaporation tank 2, a steam discharge pipe 19 is connected to the upper portion of the evaporation tank 2, and a condenser 20 is provided on the steam discharge pipe 19. The water cooled by the refrigerator 21 is circulated. The condensate is introduced from the condenser 20 through the condensate introduction pipe 22 into the ejector 23 together with a part of the vapor, and then stored in the condensate auxiliary storage tank 24. The condensate in the condensate auxiliary storage tank 24 is circulated through the circulation pipe 26 by the operation of the pump 25. The condensed liquid overflowing from the condensed liquid auxiliary storage tank 24 is stored in the condensed liquid storage tank 27. Further, a discharge pipe 29 having an electromagnetic valve 28 is connected to the lower portion of the evaporation tank 2, and the operation of the electromagnetic valve 28 discharges the sediment 4 of the photographic processing waste liquid to a precipitation receiving tank 30 by concentration. There is.

An outline of the process of heating / evaporating using this device will be described. The photographic processing waste liquid stored in the waste liquid storage tank 16 is transferred to the evaporation tank 2 via the waste liquid supply pipe 15 and the upper limit liquid level sensor 12
Supplied until detected at. The photographic processing waste liquid in the evaporator 2 is heated and evaporated and concentrated by the conductive material 3, but when the liquid level is lowered until it is detected by the lower limit liquid level sensor 13, the waste liquid is again returned to the position of the upper limit liquid level sensor 12. Supplied. The vaporized vapor is sent to the condenser 20 via the vapor discharge pipe 19 and cooled, and then the condensate and the vapor are introduced from the condensate introduction pipe 22 to the ejector 23 and temporarily stored in the condensate auxiliary storage tank 24. . The stored condensate is further sent to the ejector 23 via the circulation pipe 26 by the drive of the pump 25, whereby the inside of the evaporation tank 2 is depressurized.

On the other hand, as the concentration proceeds, the generated precipitate 4 is deposited in the evaporation tank 2 and replaced with the photographic processing waste liquid in the evaporation tank 2,
The liquid level sensor 17 in the waste liquid storage tank 16 detects that the waste liquid is exhausted, and the power of the conductive material 3 is turned off at the same time when a warning buzzer, a warning lamp or the like is notified. At the same time, the solenoid valve 28 is opened, whereby the precipitate 4 falls into the precipitation receiving tank 30.

Various shapes of the evaporator 2 of the processing apparatus of the present invention are shown in the specification of Japanese Patent Application No. 61-288328 previously filed by the applicant and FIGS. 2 to 8 of the drawings, and various precipitates are taken out. The method is also shown in FIGS. 9 to 12, and the method for continuously supplying the photographic processing waste liquid is also shown in FIG.

Another embodiment of the present invention is shown in FIGS.

In FIG. 3, the evaporating vessel 2 is decompressed by the ejector 23 and then introduced into the condensate auxiliary storage tank 24. Further, an air feed pump 31 and a gas purger 32 are provided, and the condensate is aerated to reduce the condensate. Oxidizes the ingredients. Further, the condensate liquid auxiliary storage tank 24 is provided with a gas adsorbent 33 for preventing the discharge of odorous gas from the viewpoint of safety, and further, the chemical liquid is supplied from the chemical liquid supply tank 35 to the photographic processing waste liquid in the evaporation tank 2. .

In this embodiment, the conductive material 3 is made of a nickel chrome wire in a coil shape and is connected to a power source (not shown) via a voltage / current regulator 90.

In FIG. 4, the photographic processing waste liquid is supplied to the bag 36 installed in the evaporation tank 2 by the operation of the diaphragm pump 37, and the inside of the evaporation tank 2 is depressurized by the operation of the vacuum pump 38 provided in the condensate storage tank 27. The condensate introduced from the evaporation tank 2 to the condensate storage tank 27 is cooled by the cooling fan 39 arranged in the cooling section of the steam discharge pipe 19.

FIG. 5 shows a pump 40 for the condensate auxiliary storage tank 24 and the condensate storage tank 27.
Driven by the pump 40, the condensate in the condensate supplementary storage tank 24 is sent to the condensate storage tank 27 with a small amount of high pressure.

As the conductive material 3 of the present invention, various materials are adopted according to the resistivity, physical properties, etc. of the conductive material. One example of this is shown in FIGS.
Shown in the figure.

FIGS. 6 to 8 use, for example, linear nickel chrome, FIGS. 6 and 7 are wound in a coil shape, and FIG. Are arranged vertically. Similarly, FIG. 8 shows the linear nickel chrome
It is arranged vertically with the layers rolled up.

FIG. 9 shows a rod-shaped electrode in which a conductive material 3 which is a semiconductor material is put in the electrode 3a of a net-like container and which is placed in the conductive material 3.
I am trying to send an electric current between 3b.

FIG. 10 shows the conductive material 3 formed in the shape of a bar and arranged in the horizontal direction at a large number with a predetermined interval. In FIG. 11, a plurality of plate-shaped materials are connected by a support frame 3c. hand,
It is arranged vertically.

Fig. 12 shows a plate-shaped material that is rolled and used.
FIG. 13 shows a structure in which a plurality of roll-shaped electrodes are used, and a conductive material 3 is inserted between the electrodes so that an electric current flows.
In FIG. 14, a plurality of plate electrodes are arranged at a predetermined interval, and the conductive material 3 is arranged between the electrodes.

Then, as shown in FIGS. 15 to 17, even if the conductive materials are completely immersed in the photographic processing waste liquid (FIG. 16), about half (FIG. 15) or a small amount of the conductive material (FIG. 17). May be dipped, and these are arbitrarily selected depending on the shape and physical properties of the conductive material 3.

[Example] MPS processing system Using an automatic processor for paper RP-800 (manufactured by Konishi Roku Photo Industry Co., Ltd.), after printing commercially available color photo paper (manufactured by Konishi Roku Photo Industry Co., Ltd.), Continuous processing was performed using the processing steps and processing solutions.

Standard treatment process (1) Color development phenomenon 40 ℃ 3 minutes (2) Bleach fixing 38 ℃ 1 minute 30 seconds (3) Stabilization treatment 25 ℃ to 35 ℃ 3 minutes (4) Dry 75 ℃ to 100 ℃ 2 minutes Treatment liquid Composition [Color developer tank liquid] Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 1.3 g Sodium chloride 0.2 g Potassium carbonate 24.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline Sulfate 5.5g Optical brightener (4,4'-diaminostilbenzyl sulfonic acid derivative) 1.0g Hydroxyamine sulfate 3.0g 1-Hydroxyethylindene-1,1-diphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0 g Magnesium chloride hexahydrate 0.7g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Add water to make 1 and adjust pH to 10.20 with potassium hydroxide and sulfuric acid.
And

[Color development replenisher] Ethylene glycol 20 ml Potassium sulfite 3.0 g Potassium carbonate 24.0 g Hydroxyamine sulfate 4.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 6.0 g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.5g 1-Hydroxyethylindene-1,1-diphosphonic acid 0.5g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride hexahydrate 0.8g 1 2,2-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Add water to make 1 and adjust pH to 10.70 with potassium hydroxide and sulfuric acid.
And

[Bleaching and fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium dihydrate
60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.ml Ammonium sulfite (40% solution) 27.5ml Add water to bring the total volume to 1 and adjust to pH 7.1 with potassium carbonate or glacial acetic acid.

[Bleach-fix replenisher A] ethylenediaminetetraacetic acid ferric ammonium dihydrate
260.0g Potassium carbonate 42.0g Add water to bring the total volume to 1.

The pH of this solution is 6.7 ± 0.1 with acetic acid or aqueous ammonia.
And

[Bleach-fixing replenisher B] Ammonium thiosulfate 250.0 ml (70% solution) Ammonium sulfite 25.0 ml (40% solution) Ethylenediaminetetraacetic acid 17.0 g Glacial acetic acid 85.0 ml Add water to bring the total volume to 1.

The pH of this solution is 5.3 ± 0.1 with acetic acid or aqueous ammonia.
Is.

[Stabilizing tank replacement solution and replenisher] Ethylene glycol 1.0g 2-Methyl-4-isothiazolin-3-one 0.20g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) 1.0 g Ammonia water (25% ammonium hydroxide in water) 2.0 g Water to 1 and 50% sulfuric acid to pH 7.0.

An automatic processor is filled with the above-mentioned color development tank solution, bleach-fixing tank solution and stability tank solution, and while processing the commercially available color photographic paper sample, the above-mentioned color development replenishing solution and bleach-fixing replenishing solutions A and B and stable replenishment are carried out. A running test was performed while replenishing the liquid through a bellows pump. The replenishing amount is 190 ml per 1 m ² of color paper as the replenishing amount to the color developing tank, 50 ml of each of the bleach-fixing replenishing liquids A and B as the replenishing amount to the bleach-fixing tank, and the washing replacement stable replenisher as the replenishing amount to the stabilizing tank Was replenished with 250 ml. The stabilizing tank of the automatic processor is a stabilizing tank that is the first to third tanks in the direction of sample flow, replenishment is performed from the final tank, and the overflow liquid from the final tank is allowed to flow into the preceding tank. In addition, a multi-tank countercurrent system in which this overflow liquid is allowed to flow into the previous tank is also adopted.

Continuous treatment was carried out until the total replenishment amount of the washing substitute stabilizer became three times the capacity of the stable tank.

However, 400 g of potassium carbonate and 4 g of antifoaming agent FS Antifoam 025 (manufactured by Dow Corning) were previously added to the photographic processing waste liquid.
The surface tension of the photographic processing waste liquid is added from 19 dyne / cm to 26 d.
yne / cm.

[Experimental Example 1] Using the photographic processing waste liquid of the color paper, the photographic processing waste liquid evaporative concentration treatment apparatus shown in FIG. Concentrated. 1 /
12 The hydrogen sulfide concentration in the space above the condensate storage tank 27 immediately before the end of concentration was measured with a detector tube. Conductive material 3 is nickel chrome
It was set to 20Ω, placed in a quartz tube, completely covered, and immersed in the waste liquid so that no current would flow.

Further, the electromagnetic valve 28 under the evaporation tank 2 was opened, the precipitate 4 remaining in the evaporation tank 2 was measured, and the remaining amount% with respect to the capacity of the evaporation tank 2 is shown in the table.

[Experimental Example 2] In Experimental Example 1, semi-immersion was performed as shown in FIG.

[Experimental Example 3] In Experimental Example 1, the conductive material 3 was made of silicon single crystal as shown in FIG. 9 and was entirely immersed as shown in FIG.

[Experimental Example 4] In Experimental Example 3, semi-immersion was performed as shown in FIG.

[Experimental Example 5] In Experimental Example 1, graphite was used as the conductive material 3 to form a spiral shape, and the resistance was set to 20Ω.

[Experimental Example 6] In Experimental Example 5, semi-immersion was performed as shown in FIG.

Experimental Example 7 In Experimental Example 1, titanium electrodes were provided on both ends of the conductive material 3, and a current of 0.1 A was passed.

[Experimental Example 8] In Experimental Example 1, the platinum wire of the conductive material 3 was set to 20 ohms, and the whole was immersed as shown in FIG.

[Experimental Example 9] In Experimental Example 1, tantalum nitride as the conductive material 3 was set to 20 ohms, and the whole was immersed as shown in FIG.

[Experimental Example 10] In Experimental Example 1, the conductive material 3 was entirely immersed in iron and chromium.

As is clear from the table, according to the present invention, the concentration of hydrogen sulfide is significantly reduced, and at the time of removing the precipitate,
The amount of sediment remaining in the evaporator is small.

Further, the same experiment was conducted using the conductive material described in (1) to (12) above instead of the silicon single crystal of 20 ohms in Experimental Example 1. As a result, the same preferable result as shown in the above table was obtained.

(Effect of the Invention) As described above, according to the present invention, the conductive material is brought into direct contact with the photographic processing waste liquid, and the conductive material causes the electric current to flow in the photographic processing waste liquid while heating the photographic processing waste liquid. It is possible to suppress the odor generated during evaporative concentration due to the effect of the catalytic action or the electric current. In addition, the composition of the precipitate obtained by this concentration changes, the viscosity is reduced, adhesion of the precipitate to the processing apparatus is reduced, and the precipitate is easily taken out.

[Brief description of drawings]

FIG. 1 is a schematic view showing a state in which an evaporative concentration processing apparatus of the present invention is provided in an automatic developing machine, FIG. 2 is a schematic view showing a more concrete embodiment of the present invention, and FIGS. 3 to 5 Is a schematic view showing another embodiment, FIGS. 6 to 14 are schematic views of another embodiment of the conductive material, and FIGS. 15 to 17 are views showing the immersion state of the conductive material. In the drawings, reference numeral 2 is an evaporation pot, 3 is a conductive material, 5 is a discharging means
6 is a cooling means, and 7 is a decompression means.

Claims (2)

[Claims] 1. A method for evaporating and concentrating a photographic processing waste liquid by heating to evaporate and concentrate the solute in the photographic processing waste liquid, to directly contact a conductive material with the photographic processing waste liquid, An apparatus for evaporating and concentrating a photographic processing waste liquid, wherein an electric current is caused to flow through the photographic processing waste liquid by a conductive material and the photographic processing waste liquid is heated. 2. An evaporative concentration apparatus for photographic processing waste liquid according to claim 1, wherein at least a part of the conductive material is immersed in the photographic processing waste liquid and brought into direct contact therewith.