JPS63151301A - Apparatus for evaporation and concentration treatment of waste photographic treatment liquid - Google Patents

Abstract

PURPOSE:To reduce the harmful for malodorous component generated by evaporation, by concentrating a waste photographic treatment liquid by vacuum evaporation. CONSTITUTION:The waste liquid overflowing from an automatic developing machine 100 is collected in a stock tank 104 and subsequently supplied to an evaporation apparatus 1. The evaporation apparatus 1 is constituted of an evaporation vessel 2, a heating means 3, a discharge means 5 for a precipitate 4, a condenser 6 and a pressure reducing device 7. The waste liquid generated in the treatment of a silver halide color photographic material is the treatment object. When concn. treatment is performed under reduced pressure using the evaporation apparatus 1, the quantity of ammonia gas generated by evaporation is reduced and the generation of a malodor is also eliminated. For example, under pressure of 760mmHg, the quantity of ammonia generated is 230ppm to emit a foul odor but, under pressure of 230mmHg, the generation quantity of ammonia is reduced to 10ppm and foul odor is nearly all lost.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an apparatus for evaporating and concentrating photographic processing waste liquid. This invention relates to an apparatus for evaporating and concentrating photographic processing waste liquid, which is suitable for processing in or near an automatic processing machine without recovering it.

(Background of the Invention) In general, photographic processing of silver halide photographic materials includes development, fixing, washing, etc. in the case of black and white materials, and color development, bleach-fixing (or bleaching, fixing, etc.) in the case of color photographic materials. )
, washing with water, stabilization, etc.

In photographic processing, in which a large amount of light-sensitive material is processed, components consumed during processing are replenished, while components that are concentrated by elution or evaporation into the processing solution (for example, bromide ions in the developer, bromide ions in the fixer, etc.) are replenished. A method is adopted to maintain the performance of the processing solution at a constant level by removing silver complex salts (silver complex salts, etc.) and keeping the processing solution components constant. A portion of the processing solution is discarded in order to remove the thickening components in the photographic processing described above.

In recent years, systems have been changing to systems in which the amount of replenishment of developing processing solutions, including washing water, has been significantly reduced due to pollution and economic reasons. It is diluted with waste water from washing water, cooling water from automatic processors, etc., and disposed of in sewers, etc.

However, due to stricter pollution regulations in recent years, it is now possible to dispose of washing water and cooling water into sewers or rivers; (or bleaching solution, fixing solution), stabilizing solution, etc.] has become virtually impossible to dispose of. Examples of pollution treatment methods that reduce the pollution load of photographic processing waste liquid include:
Activated sludge method (Special Publication No. 51-7952, No. 51-129)
．． 43, etc.), evaporation method (JP-A-49-89437, JP-B-56-33996, etc.), electrolytic oxidation method (JP-A-48
No. -84462, No. 49-119457, No. 49-1
19458, Japanese Patent Publication No. 53-43478, etc.), ion exchange method (Japanese Patent Publication No. 51-37704, Japanese Patent Publication No. 53-4327, etc.)
1, JP-A-53-383, etc.), reverse osmosis method (JP-A-53-383, etc.), reverse osmosis method (JP-A-53-383, etc.)
0-22463, etc.), chemical treatment method (Japanese Patent Application Laid-open No. 49-6
No. 4257, No. 53-12152, No. 49-5883
No. 3, No. 53-63763, Special Publication No. 57-37395
No. 57-37396-+, etc.) are known, but they are still not sufficient. Therefore, waste liquid is generally collected by a waste liquid collection company and rendered harmless through secondary and tertiary processing, but not only does the price of waste liquid collection increase year by year due to rising collection costs, but collection efficiency is low in minilabs, etc.
It is difficult to get people to come and collect the liquid, causing problems such as waste liquid filling the store.

On the other hand, in order to solve these problems, research has been conducted on heating the photographic processing waste liquid to evaporate the water to dryness or solidify it, with the aim of making it easier to process the photographic processing waste liquid even in minilabs. , Utsukai Showa 60-70841
It is shown in the number etc. According to research conducted by the inventors, when photographic processing waste liquid is evaporated, harmful or extremely malodorous gases such as sulfur dioxide gas, hydrogen sulfide, and ammonia gas are generated.

It has been found that this is caused by the decomposition of ammonium thiosulfate and sulfites (anthonium salt, sodium salt, or potassium salt), which are often used as fixing solutions and bleach-fixing solutions in photographic processing solutions, due to high temperatures. Further, during the evaporation process, moisture and the like in the photographic processing waste liquid becomes vapor and gasifies, thereby expanding the volume and increasing the pressure in the evaporation pot. Therefore, due to this pressure, the harmful or malodorous gas leaks out of the evaporation treatment apparatus to the outside of the apparatus, resulting in an extremely unfavorable working environment.

Therefore, in order to solve these problems,
No. 1 discloses a method of providing an exhaust gas treatment section such as activated carbon in the exhaust pipe section of an evaporation treatment device. However, this method has the serious drawback that water vapor from a large amount of moisture in the photographic processing waste liquid condenses or condenses in the exhaust gas treatment section, covering the gas absorption treatment agent with moisture and causing it to instantly lose its gas absorption ability. As a result, it has not yet been put to practical use.

In order to solve these problems, the present applicant et al. installed a heat exchange means to condense the vapor generated by evaporation when evaporating photographic processing waste liquid, and further treated the condensed water generated by condensation and removed non-condensed components. We have previously proposed a method and apparatus for treating photographic processing waste liquid, which is also treated and discharged to the outside.

However, it has been found that the above proposal has the following problems. That is, the steam generated by the evaporation process is condensed by the heat exchange means, but since the pressure in the evaporation pot increases during the evaporation process, the steam is not efficiently guided to the heat exchange means and leaks out of the apparatus. This includes particularly foul-smelling and harmful gases such as hydrogen sulfide, which is unfavorable from the social and working environment. Furthermore, the non-condensed components that have passed through the heat exchange means are treated with activated carbon, etc. and then released to the outside, but it is difficult to sufficiently remove foul-smelling gases, and activated carbon quickly loses its ability. Because it is stored away, there is a high risk of it being released outside. Furthermore, when photographic processing waste liquid is heated and processed by evaporation and concentration, ammonia gas, sulfur dioxide gas, etc. are generated due to the evaporation of the photographic processing waste liquid containing thiosulfate and ammonium thiosulfate.
For example, when an automatic developing machine is installed indoors such as an office, odor gas generated by processing waste liquid from photographic processing becomes a problem. For this reason, there is a need for a device that can process photographic processing waste liquid in or near an automatic processor without generating odor gas, without having to be collected by a vendor.

(Object of the Invention) The present invention has been made in view of the conventional problems mentioned in 2.The first object of the present invention is to reduce harmful or malodorous components generated by evaporation treatment of photographic processing waste liquid. An object of the present invention is to provide an apparatus for evaporating and concentrating photographic processing waste liquid. A second object of the present invention is to provide an apparatus for evaporating and concentrating photographic processing waste liquid that has good thermal efficiency, good evaporation efficiency, and reduced energy costs. Third aspect of the present invention
The object of the present invention is to provide an apparatus for evaporating and concentrating photographic processing waste liquid, which has a significantly high degree of concentration of the residue that is concentrated to dryness by evaporation, has a low moisture content in the waste (slatch), and is easy to handle.

(Means for Solving the Problems) In order to solve the above problems, the photographic processing waste liquid evaporation concentration processing apparatus of the present invention includes an evaporation pot, a pressure reducing means for reducing the pressure of the evaporation pot, and a pressure reducing means for reducing the pressure of the evaporation pot. The apparatus is characterized by comprising a heating means for heating the photographic processing waste liquid.

The effect of the present invention is to concentrate while preventing ammonia gas, sulfur dioxide gas, hydrogen sulfide, etc. that are generated by heating and evaporating ammonium thiosulfate and ammonium sulfite, or their respective sodium salts and potassium salts, which are present in photographic processing waste liquid. However, these compounds can be obtained by evaporation treatment that allows them to be concentrated, sludge or precipitated.

That is, the present invention has the advantage that when the photographic processing waste liquid is pressurized, the amount of ammonia gas and sulfur dioxide gas that evaporate together with the water vapor is significantly reduced when the process is carried out under reduced pressure conditions, and the amount of hydrogen sulfide gas that begins to be generated during the concentration process is reduced. This is based on the very favorable discovery that it delays the onset of cancer. Therefore, the present invention is highly effective when the photographic processing waste liquid contains thiosulfate, which is a source of ammonia gas, sulfur dioxide gas, and hydrogen oxide, and is particularly effective when it contains ammonium thiosulfate. do.

Since the present invention includes a pressure reducing means, the temperature of the photographic processing waste liquid in the evaporator is lowered to 100° C. or less.

Therefore, not only does heating energy need to be low, but
Compared to conventional evaporation methods, less tar is generated in the evaporation concentrate, and deposits on the walls of the evaporator are also reduced.

The reduced pressure to obtain the effects of the present invention is preferably 610 mm.
Hg or less, more preferably 520 m
mHg or less, particularly preferably 230m
The goal is to keep it below mHg. In addition, there is no particular lower limit to the reduced pressure, but the cost of the equipment used to create a reduced pressure state
Hg or higher is preferable, and 10 mmHg or higher is preferable because a simple device can be used.

The temperature of photographic processing waste liquid varies depending on the type of waste liquid, the reduced pressure state, etc., and cannot be determined exactly, but it is generally 30°C.
C. to 100.degree. C. is preferable, and in consideration of energy costs, waste liquid processing speed, etc., 40.degree. C. to 80.degree. C. is preferable, and 50.degree. C. to 70.degree. C. is more preferable.

Further, as the pressure reducing means used in the present invention, a vacuum pump, an ejector, etc. are used.

When using an ejector, the water pumped into the ejector may be led directly from the tap, but
It is preferable to circulate the stored water using a pump because piping can be omitted. Furthermore, as a preferred embodiment, there is a method in which the vaporized ice is circulated by a pump and fed into the ejector.

Although the pressure reduction means and the evaporator may be directly connected to directly reduce the pressure in the evaporator, it is preferable that the pressure reducing means be provided in a steam exhaust pipe for guiding the steam generated by evaporation. Further, the steam produced by evaporation is guided to a heat exchange means for condensing through a steam discharge pipe, and the condensed water produced by condensation is guided to a condensed water storage tank by a condensed water discharge pipe, and the pressure reduction means is connected to a condensed water discharge pipe or a condensed water storage tank. The pressure may be reduced by providing it in a storage tank. Furthermore, in the case of a method in which the condensed water is circulated by a pump and sent into the ejector, a preferred embodiment is a method in which the steam discharge pipe and the ejector are directly connected and the steam is cooled by introducing the steam into the condensed water. Can be mentioned. in this case,
You can cool the condensed water by storing condensed water, installing a heat sink on the circulation vibrator that circulates the condensed water, using cooling water, or using a refrigerator to cool the condensed water directly or through the cooling water. Various means can be taken to cool the condensed water, such as cooling the condensed water or dissipating the heat by causing the condensed water to fall in the form of a shower.

Another preferred embodiment in which the condensed water is circulated by a pump and sent to the ejector is a method in which steam is condensed by a heat exchange means and then a part of the condensed water and steam is introduced to the ejector through a condensed water discharge pipe.

In addition, as a pressure reducing means, such as a vacuum pump outside the air distribution, those described in 86/87 Scientific Instruments Directory (edited and published by Tokyo Scientific Instruments Association), pages 537 to 610, can also be used. .

A preferred embodiment of the processing apparatus according to the present invention includes means for liquefying the vapor generated by evaporation and concentration, and means for recovering the liquefied vapor, and more preferably, a means for liquefying the vapor and/or vapor. It is important to have means for cooling the condensed water. It is also preferable to have means for recovering the concentrate obtained by the evaporative concentration.

In the present invention, it is desirable that the photographic processing waste liquid is supplied in accordance with the amount of evaporation, and specifically, the amount of evaporated and condensed water may be detected, or the fluctuation in the amount of liquid in the evaporation pot may be detected. Means for detecting the liquid amount include means for detecting the weight of the liquid, liquid level, etc. Among the means for detecting the liquid level, a means for detecting the liquid level in the evaporator is particularly preferable. .

The heating means of the present invention is a heating means disposed outside an evaporation pot that stores photographic processing waste liquid, or a heating means that is immersed in the photographic processing waste liquid stored in the evaporation pot. Examples of heating means placed outside include far-infrared heaters, hot air heaters, quartz tube heaters, pipe heaters, ceramic heaters, plate heaters, etc.
In particular, from the viewpoint of evaporation efficiency, a direct heating method that directly heats the waste liquid inside the evaporator is preferable.In this case, the heater is also made of a material whose surface will not be attacked by the photographic processing waste liquid (for example, 5US316, stainless steel, titanium steel, etc.). The heater is preferably covered by a Hastelloy C1 quartz tube, glass, etc.). Preferably, these heating means are provided with a means for preventing tangle by means of a temperature controller to prevent overheating.

In the present invention, as a preferred embodiment, a bag is provided in the evaporation pot, and the concentrated liquid sludge or precipitate is taken out and disposed of together with the bag, or a bag or a screw-in or one-touch polyethylene bottle is placed in the lower part of the evaporation chamber to evaporate the evaporation chamber. The liquid, sludge or precipitate can be removed and disposed of. These bags and bottles are preferably made of organic resin that can withstand temperatures of about 20°C to 90°C, such as 6-5 nylon,
6.6-Nylon, polyamide, vinyl chloride,
Polyethylene is used.

In a preferred embodiment of the invention, for example, condensed water can be passed through a gas treatment column and communicated with the outside air.

Thereby, even if a small amount of toxic gas is generated from the condensed water, it can be prevented from leaking to the outside. This is made possible by introducing outside air from the outside through a gas treatment column, in which an adsorbent or deodorizer such as activated carbon or zeolite may be used.

Furthermore, in order to reduce heating energy costs, the present invention preferably uses a large number of evaporation pots as shown in FIG. 4, and uses condensed water as a heat source for the other pots. This method utilizes latent heat of vaporization, which accounts for most of the heating energy, and is very preferable because it can significantly reduce heating energy costs. Furthermore, in order to reduce heating energy costs, the present invention uses Freon gas or the like as a heat medium to remove heat from condensed water and cool it using the same principle as coolers and refrigerators, as shown in Figure 3. It is preferable to use a method in which it is fed to an evaporator. In this case, the heat generated from the processing apparatus of the present invention is extremely reduced, and the apparatus can be installed in a sealed room, where conventional installation was not possible due to heat generation.

By the way, a small amount of harmful gas generated when photographic processing waste liquid is evaporated may be dissolved in the condensed water, and in some cases, components with a large pollution load may be mixed in. For example, as mentioned above, sulfur dioxide gas, ammonia, hydrogen sulfide gas, and organic solvents and organic acids such as ethylene glycol, acetic acid, diethylene glycol, and benzyl alcohol, which are gasified by azeotropy with water, flow out into the condensed water. There may be cases where

For this reason, the condensed water has a large pollution load value such as BOD and COD, and there may be cases where it is impossible to discharge it as it is into an external sewer or river. For this reason, in the present invention, an oxidizing agent or a pH adjuster is introduced into the condensed water, or, if necessary, a filtration means (particularly a filtration means containing activated carbon) placed downstream of the condensation section for evaporated steam is used.

In the present invention, ozone can be supplied into the filtration means or at a stage preceding the filtration means, for example, for the purpose of decomposing harmful gases. Catalytic incineration using platinum or palladium alloys is also used as another method, and is particularly effective for ammonia gas.

Further, as shown in FIG. 3, for example, by using an air feed pump and a gas barsha, the condensed water can be aerated to oxidize the reducing components of the condensed water.

In the processing apparatus of the present invention, it is effective when the photographic processing waste liquid is a photographic processing waste liquid and contains a large amount of thiosulfate, sulfite, and ammonium salt, and is particularly effective when it contains a large amount of organic acid ferric complex salt and thiosulfate. It is extremely effective when it is contained.

As a preferred application example of the present invention, it is suitable for treating photographic processing waste liquid generated during the development of photographic light-sensitive materials by an automatic processor in or near the automatic processor. Here, an automatic developing machine, a total concentration processing apparatus, and a photographic processing waste liquid will be explained.

In FIG. 1, an automatic developing machine is designated by the numeral 100, and an evaporative concentration processing apparatus is designated by the numeral 1. Automatic developing machine 1 shown
00 is a roll-shaped photographic material F, a color development MCD,
It is of a type in which it is continuously guided to a bleach-fixing tank BF and a stabilizing processing tank SD for photographic processing, and after drying, it is rolled up. 1
Reference numeral 01 denotes a replenisher tank, in which a sensor 102 detects the photographic processing amount of the photographic light-sensitive material F, and a control device 103 replenishes each processing tank with replenisher according to the detected information.

When each photographic processing tank is replenished with the replenisher, it is discharged from the processing tank as an overflow waste liquid and collected in the stock tank 104. A simple way to prevent the overflowing photographic processing waste from being transferred to the stock tank 104 is to allow it to fall naturally through a guide pipe. In the case of forced transfer using a pump etc. φ) Possible - The evaporation concentration processing device 1 includes an evaporation pot 2 for storing photographic processing waste liquid,
A heating means 3, a discharge means 5 for discharging the precipitate 4 generated as the photographic processing waste liquid is evaporated and concentrated, and a steam cooling means 6.
and a pressure reducing means 7, etc. This discharge means 5
The precipitate 4 discharged from the tank is stored in a sediment storage container 8, and the condensed water whose pressure has been reduced by the pressure reducing means 7 is stored in a condensed water storage [9]. Gas adsorption means 10 such as a filter, an adsorbent, etc. can be added to this condensed water storage tank 9.

The heating means 3 includes one that heats the photographic processing waste liquid using one or a combination of two or more effective heat sources such as electricity, gas, solar heat, etc., and evaporates and concentrates the photographic processing waste liquid, The heating method was to collect the photographic processing waste liquid in the evaporating pot 2 and heat the whole, and this applicant developed it in 1981.
What is described in the specification attached to the patent application filed on November 18, 2017 is used. The heating means 3 may be placed at any position above the collected photographic processing waste liquid, inside the evaporator 2, or outside the evaporator 2.

The discharge means 5 is a known discharge device using a rotary screw pump, or a concentrated solution of photographic processing waste is discharged from the bottom of the evaporator 2 through a valve into a container containing one or more of a liquid-absorbing resin and a solidifying agent. Various designs can be made, such as those that allow it to fall naturally and solidify.

The amount and temperature of the photographic processing waste liquid in the stock tank 104 are detected by the sensor 105, and the information is stored in the control device 103, and when it is detected that the photographic processing waste liquid in the stock tank 104 is full, Replenishment of the replenisher is prohibited to prevent new photographic processing waste liquid from being discharged, or the pump 106 is driven to supply photographic processing waste liquid from the stock tank 104 to the evaporator 2. In order to prevent malfunctions, it is preferable to provide sufficient capacity for the stock tank 104 or to provide a plurality of stock tanks or reserve tanks. Further, in a system in which the photographic processing liquid is not processed all at once but is treated separately according to the type of photographic processing waste liquid, the liquid amount temperature and the like are detected for each stock tank 104.

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

The photographic processing waste liquid can be supplied from the stock tank 104 to the evaporation concentration processing apparatus 1 by a method in which a fixed amount is supplied at one time, or a method in which a fixed or variable amount is continuously supplied.

In the former case, the sensor 105 detects the stock tank 10.
The supply from the stock tank 104 to the evaporative concentration processing apparatus 1 is controlled according to the amount of decrease in the photographic processing waste liquid in the evaporator 4 and/or the detection information of the photographic processing waste liquid in the evaporator 2 by the sensor 11. In this case, control may be performed in accordance with information detected by a flow meter provided in the waste liquid supply pipe from the stock tank 104 to the evaporation concentration processing apparatus 1.

In the case of a method that continuously supplies a fixed amount or a variable amount,
The amount of the photographic processing waste liquid to be supplied is adjusted according to the temperature of the photographic processing waste liquid to be supplied and the temperature of the heating means 3 or the evaporating pot 2 of the evaporative concentration processing apparatus 1. In addition, the amount of photographic processing waste liquid to be supplied is always constant, the amount of photographic processing waste liquid in the evaporation concentration processing apparatus 1 is detected by the sensor 11, and the heating means 3
For example, the heating temperature by the heater may be controlled to increase or decrease, or the heating time may be controlled to increase or decrease.

The evaporation concentration processing device 1 is controlled according to the difference between the amount of photographic processing waste liquid supplied and the amount of processed photographic processing waste liquid, or the amount of remaining photographic processing waste liquid or the amount of processed and concentrated photographic processing waste liquid. It will be done.

In addition, in the case of a system in which a fixed amount of photographic processing waste liquid is supplied to the evaporation concentration processing apparatus 1 at a time, the temperature of the supplied photographic processing waste liquid and the temperature of the heating means 3 or the evaporating pot 2 must be detected. For example, the operation of the evaporation concentration treatment apparatus 1 can be controlled by controlling the treatment time.

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

Photographic processing waste liquid that can be processed according to the present invention is:
A typical example thereof is the waste liquid produced when processing silver halide color photographic materials, but the photographic processing waste liquid that can be treated according to the present invention is not limited to this, and other silver halide Also included are waste liquids produced during the processing of color photographic materials.

(Example) FIG. 2 is a schematic diagram of an example showing the present invention more specifically. In FIG. 2, a heating means 3 is provided inside the evaporation pot 2 of the evaporation concentration processing apparatus, and an upper limit liquid level sensor 12 and a lower limit liquid level sensor 3 are provided above the heating means 3. This prevents the evaporator from drying up.

Further, a waste liquid supply pipe 15 having a solenoid valve 14 is provided in the upper part of the evaporating pot 2, and when the solenoid valve 14 is operated, the waste liquid storage tank is
A photographic processing waste liquid is supplied from 6 to the evaporator 1. This waste liquid storage [16] is provided with a liquid level sensor 17 for detecting the remaining amount of photographic processing waste liquid, and the liquid level information is manually inputted to the control device 103.

In addition, a solenoid valve 18 for releasing pressure reduction is provided at the top of the evaporator pot 2.
Further, a steam exhaust pipe 19 is provided at the upper part of the evaporating pot 2.
A condenser 20 is provided in the steam exhaust pipe 19, and water cooled by a refrigerator 21 is circulated therein. From the condenser/condenser 20, condensed water is introduced into an ejector 23 along with a portion of steam through a condensed water introduction pipe 22, and then stored in a condensed water auxiliary storage tank 24. The condensed water in the condensed water auxiliary storage tank 24 is circulated through a circulation pipe 26 by operation of a pump 25. This condensed water auxiliary storage tank 24
The condensed water that overflows is stored in the condensed water storage tank 27. Further, a discharge pipe 29 having a solenoid valve 28 is connected to the lower part of the evaporation pot 2, and the operation of the solenoid valve 28 discharges the precipitate 4 resulting from the concentration of the photographic processing waste liquid to the precipitate receiver M2O.

To explain the outline of the heating and evaporation process using this device, the photographic processing waste liquid stored in the waste liquid storage tank 16 is sent to the evaporation pot 12 via the waste liquid supply pipe 15 until it is detected by the upper limit liquid level sensor 12. Supplied. The photographic processing waste liquid in the evaporating pot 2 is heated and evaporated by the heating means 3;
When the liquid level drops to the point where it is detected by the lower limit liquid level sensor 13, the waste liquid is supplied again to the position of the upper limit liquid level sensor 12. The evaporated steam is sent to a condenser 20 via a steam exhaust pipe 19 and cooled, and then condensed water and steam are introduced from a condensed water introduction pipe 22 to an ejector 23 and are temporarily stored in a condensed water auxiliary storage tank 24. . The stored condensed water is further sent to the ejector 23 via the circulation vibrator 26 by driving the pump 250, thereby reducing the pressure in the evaporating pot 2.

Then, the liquid level sensor 17 in the waste liquid storage tank 16 detects that the waste liquid has run out, and at the same time, the heating means 3
can be cut. At the same time, the electromagnetic valve 28 opens, and the sediment 4 falls into the tank 30.

FIGS. 3 to 6 are diagrams showing other embodiments of the evaporation concentration processing apparatus of the present invention. In Fig. 3, the pressure of the evaporator pot 2 is reduced by the ejector 23, and then the condensed water is introduced into the auxiliary storage M24.
2, and by aerating the condensed water, the reducing components of the condensed water are oxidized. In addition, the condensed water auxiliary storage [24] is equipped with a gas adsorbent 33 that prevents the discharge of odor gas from the viewpoint of safety, and is further driven by a compressor 34.
Freon gas or the like is circulated as a heat medium to remove heat from the condensed water and cool it, and the heat is given to the evaporation pot 2 side. In addition, a chemical solution supply pipe 3 is provided for the photographic processing waste liquid in the evaporation pot 2.
A chemical solution is supplied from 5. In FIG. 4, a large number of evaporation pots 2 are prepared, and the bottom of the evaporation pot 2 on the left side in this figure is heated with heating means 3 such as a heater, and the condensed water in this evaporation pot 2 is transferred to the evaporation pot 2 disposed in the next stage. The heat source is guided to the bottom of the heat source via an ejector 23. In this way, by utilizing the latent heat of vaporization, heating energy costs can be significantly reduced.

In FIG. 5, photographic processing waste liquid is supplied to a bag 36 installed in the evaporator 2 by the operation of a diaphragm pump 37, and the pressure inside the evaporator 2 is reduced by the operation of a vacuum pump 38 provided in the condensed water storage tank 27. The condensed water led from the evaporation pot 2 to the condensed water storage tank 27 is cooled by a cooling fan 39 disposed in the cooling section of the steam exhaust pipe 19. Figure 6 shows the condensed water auxiliary storage tank 25.
and a condensed water storage tank 27 are connected via a pump 40, and when the pump 40 is driven, a minute amount of condensed water from the condensed water auxiliary storage [25] is sent to the condensed water storage [27] at high pressure.

[Experimental Example] After printing a commercially available color photographic paper, continuous processing was performed using the following processing steps and processing solution.

Standard processing steps (1) Color development 38℃ 3 minutes (2) Bleach fixing 38℃ 1 minute 30 seconds (3) Stabilization treatment
25℃~35℃ 3 minutes (4) Drying 75℃~1
00°C Approximately 2 minutes Processing liquid composition [Color developing tank liquid] Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide
1.3g sodium chloride
0.2g potassium carbonate 24
．． 0g 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 4.5g optical brightener (4,4
'-diaminostilbendisulfonic acid derivative)
1.0g hydroxylamine sulfate 3
．． 0g 1-hydroxyethylindene-1,1-diphosphonic acid 0.4g hydroxyethyliminodiacetic acid 5.0g magnesium chloride hexahydrate 0.7g 1,2-dihydroxybenzene-3
,5-Disulfonic acid disodium salt 0.2g water was added to make the pH 14, and the pH was adjusted to 10.2 with potassium hydroxide and sulfuric acid.
Set to 0.

[Color developer replenisher] Benzyl alcohol 20 mfl.

Ethylene glycol 20ml Potassium sulfite 3.0g Potassium carbonate
24.0 g and droxyamine sulfate 4.0 g 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 6.0 g optical brightener (4,4'
-diaminostilbendisulfonic acid derivative)
2.5g 1-hydroxyethylindene-1,1-
Niphosphonic acid 0.5gHydroxyethyliminodiacetic acid 5.0gMagnesium chloride hexahydrate 0.8g1.2-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.
Add 3g of water to bring the pH to 11, and adjust the pH to 11 with potassium hydroxide and sulfuric acid.
10,70.

[Bleach-fix tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100. mJIL ammonium sulfite (40% solution) 27-5mj2 Add water to bring the total volume to 1, and adjust to pH 7.1 with potassium carbonate or glacial acetic acid.

[Bleach-fixing replenisher A] Ferric ammonium ethylenediaminetetraacetate dihydrate 260.0g Potassium carbonate 42.0g Add water to make a total volume of 11.

The pH of this solution was adjusted to 6.7 using acetic acid or aqueous ammonia.
Set to ±0.1.

[Bleach-fix replenisher B] Ammonium thiosulfate 500.0mJZ (70
% solution) Ammonium sulfite 250.0mJ2 (40
% solution) Ethylenediaminetetraacetic acid 17.0g Glacial acetic acid
85.0ml/l.

Add water to make the total amount In.

This solution has a pH of 5.3 using acetic acid or aqueous ammonia.
It is ±0.1.

[Water wash alternative stable tank fluid and replenisher] Ethylene glycol 1.0g 2-methyl-4-isothiazolin-3-one
0.20g 1-hydroxyethylidene-1,
1-niphosphonic acid (60% aqueous solution 1.0g ammonia water (ammonium hydroxide 25% aqueous solution) 2.0g I with water
k and adjusted to pH 7.0 with 50% sulfuric acid.

Fill an automatic processor with the above color developer tank solution, bleach-fix tank solution and stabilization tank solution, and add the above color developer replenisher and bleach-fix replenisher A every 3 minutes while processing the commercially available color photographic paper sample. A running test was conducted while replenishing B and stable replenisher through the bellows pump. The amount of replenishment is 190 mJZ per color paper to the color developing tank, 50 m1 each of bleach-fixing replenisher A and B to the bleach-fixing tank,
Add 250 ml of water washing alternative stabilizing replenisher to the stabilizing tank.
mu was supplemented. 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 flows into the previous stage. A multi-vessel countercurrent system was adopted in which this overflow liquid also flowed into the rice mill at the previous stage.

Continuous processing was performed until the total amount of replenishment of the water washing alternative stabilizing solution became three times the capacity of the stabilizing tank.

Photographic processing waste liquid 20I1. is a mixture of three types of overflow liquid obtained by the above processing. The treatment was carried out using the apparatus shown in FIG.

The evaporation concentration process was carried out by changing the voltage of the pump 25 of the ejector 23 and changing the reduced pressure state as shown in Table 1. The temperature of the photographic processing waste liquid in the evaporation pot 2 is shown in Table 1, the ammonia gas concentration was measured when the photographic processing waste liquid was concentrated to 1/2, and the odor was detected when the condensed water was kept at 30 ° C. The results are shown in Table 1. Further, evaporation concentration was performed for each of the samples in succession, and the concentration ratio was determined when the thiosulfate in the concentrated liquid in the evaporator 2 decomposed and sulfurized, and hydrogen sulfide began to appear in the condensed water.

Table 1 Odor test (5 people) O: Almost no odor. (4 out of 5 people) △: Slightly smelly. (3 out of 5 people) ×: The odor is terrible. (5 out of 5 people) As is clear from Table 1, when the pressure is reduced, the generation of ammonia gas is reduced, and the odor quickly disappears. As a result, odor generation is suppressed.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an automatic processor equipped with the evaporation concentration processing apparatus of the present invention, FIG. 2 is a schematic diagram showing a more specific embodiment of the present invention, and FIGS. 3 to 6 FIG. 2 is a schematic diagram showing another embodiment. In the drawing, reference numeral 2 is an evaporation pot, 3 is a heating means, 5 is a discharge means,
6 is a cooling means, and 7 is a pressure reducing means. Figure 2 Figure 3 Figure 6

Claims (2)

[Claims] (1) An apparatus for evaporating and concentrating photographic processing waste liquid, comprising an evaporator, a pressure reducing means for reducing the pressure of the evaporator, and a heating means for heating the photographic processing waste introduced into the evaporator. (2) The apparatus for evaporating and concentrating photographic processing waste liquid according to claim 1, further comprising a cooling means for cooling the vapor generated by the evaporation and concentration of the photographic processing waste liquid.