JPH0445886A - Method and apparatus for evaporating, concentrating and treating used photographic processing solution - Google Patents

Abstract

PURPOSE:To enable the discharge of a condensate into the sea, rivers, etc., by carrying out evaporation at <=70 deg.C and electrodialyzing the condensate with a DC power source in an electrodialytic cell fitted with the anode and cathode with a cation exchange membrane in-between. CONSTITUTION:An electrodialytic apparatus 61 is connected to a water tank 35 or 49 or other water tank 60 in which water produced by evaporation and condensation is poured from the tank 35 or 49 and stored and the water in the tank 60, 35 or 49 is circulated by a pump so that the water passes through the apparatus 61. When the water is electrodialyzed, it is preferably circulated in each of the chambers of the apparatus 61 divided with membranes, especially in the desalting chamber or this chamber and the cathode chamber. The water is preferably treated by contact with a cation or anion exchange resin, chelate resin or adsorbing resin or by reverse osmosis during electrodialysis.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method and apparatus for evaporating and concentrating photographic processing waste liquid. The present invention relates to a method and apparatus for evaporating and concentrating photographic processing waste liquid, which processes waste liquid that is not generated (abbreviated herein as photographic processing waste liquid or waste liquid).

[Prior Art] In general, photographic processing of silver halon saponide photographic light-sensitive materials includes development, fixing, washing, etc. in the case of black and white light-sensitive materials, and color development, bleach-fixing M (or bleaching, fixing, etc.) in the case of color light-sensitive materials. )
A combination of processes using a treatment liquid having one or more functions such as , water washing, and stabilization is performed.

Then, a photosensitive material of 1:1 is used for photographic processing.
3, the components consumed during processing are replenished into the tank processing solution, and on the other hand, components that are eluted into the tank processing solution during processing or become concentrated by evaporation, such as bromide ions in the developer solution and components in the fixer solution, are A method is used to maintain the performance of the processing solution at a constant level by removing substances (such as silver complex salts) and keeping the processing solution components constant. A portion of the tank processing solution is discarded to remove thickening components in the photographic processing described above.

The system is changing to a system in which the amount of replenishment, including washing water, which is used as a replenishment solution for washing, has been significantly reduced due to pollution and economic reasons. It is led through a pipe (discharge pipe), diluted with waste water from washing water, cooling water from automatic processing machines, etc., and then disposed of in sewers, etc.

However, due to the recent tightening of pollution control by the Water Pollution Control Law and the ordinances of each prefecture, photographic processing solutions [for example, developer, fixer, color developer, bleach-fixer (or bleach armpit,
fixing solution), stabilizer solution, etc.] has become virtually impossible to dispose of. For this reason, each photo processing company pays a collection fee to a specialized waste liquid processing company to collect the waste liquid, or installs pollution treatment equipment. However, the method of entrusting a waste liquid treatment company to a waste liquid treatment company requires a considerable amount of space to store the waste liquid, is extremely expensive, and requires an initial investment (initial cost 1) for pollution treatment equipment. ) is extremely large, and has the disadvantage of requiring a fairly vast area to maintain. The above-mentioned pollution treatment equipment has been used for a long time, such as activated sludge method (for example, Japanese Patent Publication No. 511-2943 and Japanese Patent Publication No. 5]-7952, etc.), evaporation method (Japanese Patent Publication No. 49-89437 and Japanese Patent Publication No. 56-79). 3
3996, etc.), electrolytic oxidation method (JP-A-Sho/18-8446)
No. 2, No. 49-119458, Special Publication No. 53-4347
August, JP 41119457, etc.), ion exchange method (
Japanese Patent Publication No. 51-37704, Japanese Patent Publication No. 53383, Japanese Patent Publication No. 53-43271, etc.), reverse osmosis method (4 ¥
22463 etc.), chemical treatment method (JP-A-496425)
No. 7, Special Publication No. 57-37396, Japanese Patent Publication No. 121-1983
No. 52, No. 49-588: ]: No. 11, No. 53-637 [
i3, Japanese Patent Publication No. 57-37395, etc.) are known, but they are still not sufficient.

On the other hand, due to constraints from water resources, rising water supply and drainage costs, the simplicity of automatic processor equipment, and the working environment around automatic processors, in recent years, stabilization treatments have been used to replace washing with water. Photographic processing using automatic developing machines (so-called waterless automatic developing machines), which do not require piping for water supply and drainage outside the machine, is rapidly becoming popular. In such processing, it is desired that cooling water for controlling the temperature of the processing liquid be omitted. In such photographic processing that does not substantially use rinsing water or cooling water, the photographic processing waste liquid from automatic processors is not diluted by water compared to the case where washing is used, so the pollution load h < extremely large. On the other hand, the amount of waste liquid is small (X# slightly). Therefore, due to the small amount of waste liquid, the piping outside the machine for supplying and waste liquid can be omitted, which eliminates the drawbacks of conventional automatic processors (for example, it is difficult to move after installation to install piping, and there is no space underfoot). It is extremely simple and easy to use as an office machine. A great advantage will be demonstrated.

However, on the other hand, the waste liquid has an extremely high pollution load, and it is completely impossible to dispose of it not only in rivers but also in sewers in view of pollution regulations. Furthermore, such photographic processing (processing that virtually does not involve washing with water)
Even though the amount of waste liquid is small, even in relatively small-scale processing,
For example, the processing time for X-ray photosensitive materials is 10 days per day, the processing time for photosensitive materials for printing plate making is 30 times a day, and the processing for color photosensitive materials is about 50 times a day.
In recent years, this has become an increasingly big problem.

A recent technique aimed at facilitating the treatment of photographic processing waste liquid is the low-temperature evaporation method (Japanese Patent Application Laid-open No. 63287588
No.), waste liquid pH controller 1-roll method (Japanese Patent Application Laid-open No. 631439
91), hot air heating evaporation method (Japanese Patent Application Laid-Open No. 6:I-40779)
No. 5), reduced pressure heating evaporation method (JP-A-63-151301), sludge removal method (JP-A No. 143683)
, a steam treatment method (Japanese Unexamined Patent Publication No. 62-201442), and a condensate treatment method (Japanese Unexamined Patent Publication No. 52-201442).

Various methods have been proposed for preventing odors, reusing distilled liquid as a processing liquid, etc. However, the current situation is that condensate cannot pass the regulatory values in areas with strict pollution regulations and cannot be discharged into sewers.

〔the purpose〕

Therefore, an object of the present invention is to clear the pollution regulation values in areas with strict pollution regulations and to enable discharge of condensate into general rivers, the sea, etc.

[Means for Solving the Problems] The processing method of the present invention which achieves the above-mentioned object is to heat the photographic processing waste liquid to evaporate and concentrate it, and then cool and condense the resulting vapor to obtain a condensate. In the evaporation concentration treatment method, the evaporation temperature is set to 70°C or less, the condensate is placed in an electrodialysis tank with an anode and a cathode separated by a cation exchange membrane, and electrodialysis is performed using a DC power source, and the current density of the electrode is is 10 A/dm' or less.

The processing apparatus of the present invention, which achieves efficient distribution, heats and evaporates photographic processing waste liquid at an evaporation temperature of 70'C or lower, and cools and condenses the resulting vapor to obtain a condensate. The condensate is placed in an evaporation concentration treatment device and an electrodialysis tank with an anode and a cathode separated by a cation exchange membrane, and electrodialysis is performed using a DC power source, and the current density of the electrode is set to IO.
The present invention is characterized by having an electrodialysis device with a fl value of A/dm' or less.

A preferred embodiment of the invention has a current concentration of 5 A/, Q
-Be below.

[Effect]

Pollution regulation values include BOD, COD, toxic substances, heavy metals, etc., as well as p++, total nitrogen, iodine consumption, total phosphorus, suspended solids, etc., and all of these must be cleared before use. However, with the conventional method, it is not possible to clear the regulation value in areas with strict regulations.

To be more specific, distilled liquid (condensate) cannot be directly poured into areas with strict pollution regulations. In particular, the concentration of
The problem is the pH value.

For this purpose, there is a technique for treating distillation condensate disclosed in Japanese Patent Application Laid-Open No. 62-201442. However, simply using these methods would be very costly and impractical.However, the present invention is a technology that is inexpensive in cost and highly practical.

To put this point in concrete terms, Japan's Water Pollution Control Law stipulates that nitrogen content (ammonia) must be 120 ppm or less (in closed waters).
On the other hand, in other countries, Sweden has a 30ppm regulation, and other countries are becoming stricter in their ammonia regulations.

However, one of the features of the present invention is the evaporation temperature h) 70
If the temperature is below ℃, the main component will be regulated components or ammonia nitrogen, which can be removed by electrodialysis treatment, which is the most advantageous option when considering all aspects such as waste liquid treatment cost, drainage performance, and maintenance. be.

[Specific structure of the invention] The present invention will be explained in detail below.

The photographic processing waste liquid to be treated in the present invention may be of any kind, preferably one discharged from an automatic processor.

Further, it is preferable that the processing apparatus according to the present invention is built into an automatic processor or disposed nearby and provided with waste liquid processing piping.

The automatic developing machine mentioned above may be of any type or model.
For example, there is a method in which a roll-shaped photographic material is continuously guided through a color developing tank CD, a bleach-fixing tank BP, and a washing alternative stabilizing tank sb for photographic processing, and then rolled up after drying (automatic development). The machines include a color developing tank CD that guides the photographic material through a jaw treater, a bleach tank weight 4, and a fixing tank x.
There are various types including a water washing alternative stabilizing tank sb, a second stabilizing tank, etc. ).

The automatic processor has a general system and a replenisher tank, and a sensor detects the amount of photographic processing of the photographic light-sensitive material, and a control device replenishes each processing tank with the replenisher according to the detected information.

Note that the method of photographic processing, the structure of the photographic processing tank, and the method of replenishing the replenisher are not limited.
-14834, 48-34/148, 57-1
No. 32146 and No. 58-18631, patent application No. 1983-
No. 119840, same 5! ]-120658 and the like, the present invention can be applied to other systems or configurations, including the so-called waterless washing system shown in Japanese Patent No. 120658.

Representative examples of photographic processing waste liquids that can be processed according to the present invention are detailed in, for example, Japanese Patent Application No. 60-2541003. However, although Japanese Patent Application No. 60-259003 mainly describes photographic processing liquids for photographic materials to be processed or color materials, photographic processing waste liquids can be used to process silver halide photographic materials using photographic processing liquids. The overflow liquid that comes out when processing is used. The effects of the present invention are especially good when containing thiosulfate ions, and thiosulfate ions are contained at 20g/! It is more effective when it contains Q or more.

Collection of photographic processing waste liquid When the replenisher is replenished into the jll in each process, the overflow waste liquid is discharged from the processing tank and collected in a stock tank. In a typical automatic processor, the amount that overflows from the top of the processing tank due to replenishment of the replenisher is treated as photographic processing waste.

Providing a plurality of stock tanks, providing a plurality of evaporation concentration processing devices of the present invention, and using one or more of them as stock tanks (for example, alternately using them as stock tanks and processing devices), etc. The present invention also encompasses. By using a stock tank and processing a certain amount at a time, the components of the photographic processing waste liquid can be made uniform, and the stock tanks are useful as buffers from the photographic processing tank to the processing equipment.

A simple way to transfer overflow photographic processing waste to a stock tank is to let it fall naturally through a guide tube, but it is also possible to place a heat exchanger somewhere in the middle to collect the thermal energy held by the photographic processing waste. Alternatively, a means is provided to preheat the photographic processing waste liquid or evaporate water before it is sent to the stock tank by using the thermal energy of an automatic processor or an evaporative concentration processing device described below. Alternatively, it may be forcibly transferred using a pump or the like.

In addition, since there are differences in the components of the photographic processing waste liquid in each photographic processing tank CD, BF, and Sb, all the photographic processing waste liquid is not treated at once, but is divided into each photographic processing tank or into two or three or more groups. The present invention also includes a case where a stock tank is prepared for each waste liquid in the treatment tank and the waste liquid is treated separately. In particular, from the point of view of silver recovery, waste liquid from color developing tank CD and bleach-fixing tank B are
It is advantageous to separate F and the waste liquid from the washing alternative stabilization tank sb.

In the present invention, it is preferable to treat a photographic processing waste liquid that is a mixture of a photographic processing waste liquid from negative film processing and a photographic processing waste liquid from paper processing.

Alternatively, piping may be provided to a waste liquid tank in an existing automatic developing machine or the like, and the waste liquid may be forcibly transferred to the tank by a pump. Furthermore, the waste liquid tank of the automatic processor itself can be used as a stock tank. In this case, it is preferable to detect the weight of the stock tank and operate a pump to forcibly transfer the waste liquid through piping. Flow 1- to waste liquid tank
It is also preferable to float the liquid to detect a liquid level above a certain level and then operate the pump because it is easy to install in an existing automatic developing machine.

In addition, the photographic processing waste liquid subjected to the distillation and concentration treatment according to the present invention may have a pH value of pl+3.5 to 7.
In particular, it is preferable to perform the evaporation treatment at a pH of 4.5 to 6.5 in order to achieve the object of the present invention more effectively. Furthermore, the use of various antifoaming agents (eg, silicone compounds, etc.) is extremely advantageous in that it is possible to suppress foaming during evaporation processing due to the activator present in the photographic processing solution or eluted from the photographic material.

Processing Apparatus of the Present Invention The distillation concentration process used in the present invention refers to the distillation process of photographic processing waste liquid, and it is possible to apply one of the so-called rectification operations. Batch distillation (including simple distillation and batch rectification)
However, continuous distillation may also be used, and a continuous equilibrium distillation method for continuous rectification can also be used.

Obtaining pure water (with a significantly small amount of fractions other than water) through distillation can effectively supply water to the photographic processing solution. It is also advantageous to use suitable separating agents in the co-distillation and the extractive distillation. In the present invention, a treatment effect can also be obtained by so-called steam distillation. Note that the operating pressure may be any of high pressure distillation, atmospheric distillation, vacuum distillation, and molecular distillation.

In the present invention, preferred means for controlling the evaporation temperature to 70°C or less are as follows.

A A large amount of air is brought into contact with the heated waste liquid at normal pressure, and the preferable range of the amount of air is 6 to SOm'/IKW-hr.

B. Bringing heated air into contact with the waste liquid at normal pressure.

C. Evaporate by heating under reduced pressure.

D Heating and condensing using a heat pump under reduced pressure.

Among these, the above is most preferred, and the preferred degree of vacuum is] 0 to 100 mm 11g, more preferably 2
(] ~ 60 mm and 11 g. The above heat pump heating has the advantage that the temperature of the heated part is low, so no harmful components are generated (the floating matter becomes evaporation or cellulose).

In addition, concentration in the distillation concentration process in the present invention means to reduce the waste liquid volume to 2 times or less of the volume when it comes out from the photographic processing tank, preferably 1/4 or less, and more preferably 5 It is one-tenth or less, and optimally one-tenth or less.

First, an apparatus for evaporating and concentrating photographic processing waste liquid (first embodiment) used in the examples described later will be described in detail with reference to the sectional view of FIG.

A photographic processing waste liquid discharged from an automatic processor, etc., is injected and stored in a reduced pressure evaporation concentration column (hereinafter simply referred to as a column) 1 that can withstand reduced pressure. Connect it to reduce the pressure. It is known that under reduced pressure, which is lower than atmospheric pressure, boiling occurs below the boiling point of the substance, and this device is designed to perform this under reduced pressure. 2() to 7 under reduced pressure of 80 mmftg
It is preferable to operate at a boiling temperature of 0.06C or less, particularly 25 to 60C.

Next, a three-dimensionally arranged heating means 2 is provided in the column 1, and the lower part of the heating means 2 is immersed in the storage part 4 of the photographic processing waste liquid described in 2 above to heat the photographic processing waste liquid. The second part protrudes from the storage part of the photographic processing waste liquid and is in the air, and the photographic processing waste liquid is transferred to this part from the storage part by vacuum suction by opening the solenoid valve 6. Wash off the sludge that adheres to the heating pipe during the spraying process. This liquid supply is LC
(Reher sensor) to maintain the liquid level in the column.

By providing a cooling means 8A, a condensed water guide part, and a water receiver ←-18C in the second part of the column 1, the evaporated water can be converted into a condensate and stabilized under reduced pressure in the column. Contribute to the cause. On the other hand, the components that have been solidified to a high concentration by repeating the evaporation and condensation described in column 1 are
The sludge is scraped out from the bottom by the scraping forest 3,
The sludge is collected in a prepared container 12. In this embodiment, the heating means 2 is arranged three-dimensionally in both the liquid and the air. This is because the evaporation rate is higher than that of immersing the entire heating pipe in the waste liquid.

Roughly speaking, a cooling means 8A is provided at the bottom of the column 1, and is configured to capture water vapor coming up from the bottom, cool it, condense it, and recover it as water droplets. This is due to the generated steam causing the depressurization balance in this column 1 to collapse, resulting in the decompression device 7 (in this example, an ejector is used)
This has the effect of reducing the heavy load required to maintain a specified reduced pressure state. That is, column 1 is
The area where the internal pressure rises is immediately cooled and condensed to suppress the pressure.

The surface temperature of the heating means 2 is preferably at least 100°C, most preferably from 20°C to 60°C.

A heat radiating part of a heat pump is used as the heating means 2, and the cooling means 8B is provided in the cooling means 8A and the water recovery container 9.
This uses the heat absorption part of a heat pump.

First, a charge pipe 25 for charging the condenser of the bee 1 to pump constituting the heating means 2, a pre-heating section 37 for the supplied waste liquid is provided after the heating means 2, and a capillary serving as an expansion valve is installed after the heating means 2. The tube 26, the refrigerant compressor 2 disposed on the side 1 of the cooling means 8A, the air-cooled condenser 22 for air-cooling and condensing the refrigerant, and its fan 24 and fan motor 23 are placed outside the column 1. It's dark.

In addition, the capillary tube 26 passes through the condenser of the heating means 2 and is connected to the cooling means 8B in the water recovery container 9, and its extension serves as a cooling means 8A for refrigerant evaporation in the upper vapor condensing section 5 in the column 1. The air is connected to the compressor 21 and is returned to the compressor 21 outside the column 1.

The cold water in the water recovery container 9 is pumped through a water circulation pump (P-2).
) 33 to the ejector (preferably two or more in parallel) 7 of the decompression device, and the water drawn through the pipe 34 from the condensate recovery port 8C of the evaporation percentage condensation section 5 of the column 1'' is transferred to a water recovery container. At the same time, the pressure inside the column 1 is reduced.

Further, water overflowing from the water recovery container 9 is sent to a water tank 35 through a pipe 3b.

Next, another example (second example) of the evaporative concentration processing apparatus for photographic processing waste liquid used in the examples described later will be described using a front view shown in FIG.

Temperature controller with built-in heat source 41 (roll-type oil bath 4
2, a heat-resistant column 45 having an air pump 43 and a temperature sensor 44 is immersed, and the evaporation temperature of the photographic processing waste liquid in the column 45 is determined by the temperature of the oil path 42 and the amount of air introduced by the air pump 43. The structure allows for high and low temperature control by adjusting the temperature.

The evaporated steam is then cooled and concentrated by a coil-type cooling concentrator 48 having an inlet 46 and an outlet 47 for tap water, and is collected in a water tank 49.

Next, an embodiment of the electrodialysis treatment apparatus used in the present invention will be described with reference to FIG.

Directly to the additional water tank 35 or 49, or the water tank 35 or 49
An electrodialysis treatment device δ1 is installed in another water tank 60 for introducing and storing evaporated condensed water, and the evaporation condensed water in the water tank 6 [) (or 35 or 49) is passed through the electrodialysis treatment device 6X by a pump. This is a configuration that circulates between

When performing the electrodialysis treatment of the present invention, it is preferable to circulate the liquid in each chamber divided by the membrane of the electrodialyzer, and more preferably to constantly circulate the liquid in the demineralization chamber or in the demineralization chamber and the cathode chamber. It is.

It is also possible to use the condensate after treatment as a replenisher, or in this case, the relevant treatment liquid components are added.

Furthermore, during the electrodialysis treatment of the present invention, it is preferable to contact the cation exchange resin, anion exchange resin, or KIRE-1 with the resin or adsorption resin, or to perform reverse osmosis treatment. , contact treatment with an anion exchange resin is preferred.

A specific embodiment of the electrodialysis treatment apparatus 61 is shown in FIG. 3, in which 62 is a cathode, 63 is an anode,
64 is an anion exchange membrane or a simple diaphragm, 55 is a cation exchange membrane, 66 is a cathode chamber, 67 is a demineralization chamber, 68 is a concentration chamber,
69 is an anode chamber, 70 is an electrolyte solution circulation tank, 71 is a circulation pump, 72 is an electrolyte solution circulation pipe line (supply side), 173 is the same circulation pipeline (outflow side), 74 is condensed water, 75 is a circulation pump, 76 74 shows a circulation pipeline (supply side) for the condensed water 74, and 77 shows a circulation pipeline (outflow side) for the condensed water. Reference numeral 78 is a discharge line for breaking the two-way valve 79 for circulating or discharging condensed water, and is connected to the water tank 60 or the treated water tank 80.

The electrodialysis treatment apparatus of the present invention is not limited to the embodiment shown in FIG. 3, for example, as shown in FIG. Circulation lines 82 , 83 and pumps 84 . which bring the condensed water in the chambers 67 to 68 into contact with the anion exchange resin 81 .
85 may be provided.

In yet another embodiment, as shown in FIG.
7 and the concentration chamber 68 may be arranged in parallel alternately.

Further, an arrangement as shown in FIG. 6 is also preferable.

Incidentally, among the reference numerals shown in FIGS. 4, 5, and 6, the same reference numerals as those shown in FIG. 3 indicate the parts explained in FIG.

The electrodialysis tank included in the preferred electrodialysis treatment apparatus of the present invention may have a multi-stage structure as shown in FIG. 3, FIG. 4, or FIG. 6, most preferably two to three stages.

The current density in the present invention is preferably 0.1 to 10A.
/dm', more preferably 1 to 8 A #Im'.

The current concentration is preferably 0.1 to 5 A/l or less,
More preferably it is 0.5 to 4 A/u or less.

In the present invention, if the current density exceeds OA/c1m', the separation of ammonia, sulfite, etc. is poor.

If the current concentration exceeds 5 A/l, the separation of ammonia, sulfite, etc. will be poor.

The reason why it is undesirable to use less than 0.1 A/l or IA/dm' is because the device becomes larger.

The voltage may be within a range in which the current density or current density can be obtained.

The cation exchange membrane used in the electrodialysis treatment apparatus of the present invention is manufactured and commercially available by manufacturers such as Ionics, Toyo Soda, DuPont, and Asahi Glass. Anion exchange membranes are manufactured and commercially available by manufacturers such as Ionics.

The electrolytic cell body is preferably made of an electrically insulating material that can be used for a long time or can be used again, and is particularly made of synthetic resins such as polyevichloride, polyvinyl methacrylate, polyethylene, polypropylene, polyvinyl chloride, Polychlorinated ethylene, phenol-formaldehyde resin, etc. are preferably used. The power feeding anode 63 which provides a positive direct current voltage is made of, for example, a carbon material (for example, activated carbon, coke, lime, etc.), a graphite material (for example, carbon fiber, carbon cloth, graphite, etc.), or a carbon material. Composite materials (for example, carbon mixed with metal in powder form and sintered)
, activated carbon fiber nonwoven fabric (e.g. KE-1000 felt, Toyobo Co., Ltd.), or a material in which this is combined with platinum, platinum, palladium or nickel, as well as dimensionally stable electrodes (
Platinum group oxide coated titanium material. Titanium coated with butyric iridium coach ink. For example, there is the DSA ex-hand mesh. ), platinum coated 1g titanium material, nickel material, stainless steel material, iron construction, etc. Also, power feeding anode 63
The power feeding cathode 62 which faces the ion and applies a negative DC voltage is made of, for example, platinum, stainless steel, titanium, nickel, Hastelloy,
It is made of graphite, carbon material, mild steel, or a metal material coated with a platinum group metal. It is preferable to use a mesh-like electrode as the electrode.

Control The control of the photographic processing waste liquid processing apparatus of the present invention is mainly performed by (1) discharging the photographic processing waste liquid to the stock tank, (2) supplying the photographic processing waste liquid from the tank to the evaporation concentration processing apparatus, and (3) evaporation concentration. Operation of the Treatment Apparatus (4) It is preferable to automatically control each aspect of the treatment of the evaporation-concentrated waste liquid by the electrodialysis treatment apparatus of the present invention.

The processing device for photographic processing waste liquid preferably used in the present invention is used by being built into the automatic processing machine or placed near it, especially in a photographic processing facility where one or a small number of automatic processing machines are installed. . Preferably, the apparatus is configured to treat the photographic processing waste liquid completely or largely under automatic control.

Note that the above embodiments mainly explained the case where the overflow liquid from each treatment tank is discarded from the stock tank and is indirectly received into the evaporation concentration treatment equipment, or the overflow liquid from each treatment tank is directly received into the evaporation concentration treatment equipment without providing a stock tank etc. may be accepted.

[Effects of the Invention] According to the present invention, it is possible to clear the pollution regulation values in areas with strict pollution regulations, and to make it possible to discharge the condensed TM liquid into general rivers, the sea, etc.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 A distilled liquid (condensate) was obtained using the evaporation concentration processing apparatus of the first example shown in FIG. 1 and the second example shown in FIG. 2, and this condensate was shown in FIG. The treatment was performed using the electrodialysis treatment apparatus shown below. That is, in FIG. 6, the desalination chamber 67 is]
, OmmX 200mmX 200mm==400 m
, Q as standard, 2[] 0 +n m X 2 [
] The conditions for NO61 to NO6 were set by changing the area of Om m and changing the voltage. In Figure 6,
a = 1010111. b=3+nm, c
= 10 mm, d = 3 mm, e = ID mm, and the cathode 62 and anode 63 are 5 cm x 5 cm. Further, the cathode 62 is a titanium expanded mesh, and the anode 63 is a DSA expanded mesh.
The anion exchange membrane 64 was an anion exchange membrane manufactured by Ionics, and the cation exchange membrane 65 was a cation exchange IIM manufactured by Ionics. Also, during the process, the cathode chamber 66,
The liquid in each of the demineralization chamber 67 and the anode chamber 69 was circulated.

In the treatment using the apparatus shown in the second example, the oil bath temperature and air pump capacity were adjusted to adjust the waste liquid evaporation temperature.

The waste liquid used was a mixture (1:1) of the following color negative film processing waste liquid and vapor processing waste liquid.

Regarding the distillate when concentrated to 1712 times, Nl + 4 of the one with electrodialysis treatment and the one without electrodialysis treatment
The +ion concentration (+)I)to) was measured and the results are shown in Table 1.

However, the desalination chamber (17) of the electrodialysis treatment apparatus shown in Fig. 6 contains condensed water (distilled liquid), the cathode chamber and the anode chamber are 100 m/[1r each, and the desalination chamber 67 is 2 (] 00 m). Father/1
N114'' ions (p p m ) in the demineralization chamber 67 were measured after 10 hours.

As is clear from Table 1, according to the present invention, NH,
``''The ion concentration is below the legal standard and can be discharged to the sewer.

Waste liquid (mixed waste liquid to be treated) Commercially available color negative films of HeShe100 and 4[)O manufactured by Konica, Fuji Film, and Kotak were processed according to the following processing process specifications and processing liquid specifications.

(The replenishment amount is the value per 100 cm'.) However, the fixing tank was a 2-tank countercurrent (45 seconds, 2 tanks), and the stabilizing tank was a 3-bath countercurrent (20 seconds, 3 tanks).

The composition of the treatment liquid used is as follows.

[Color developing tank liquid] Potassium carbonate Sodium bicarbonate Potassium sulfite Sodium bromide Potassium iodide Potassium arsenic Roxyamine sulfate Thorium chloride 2,5 g g 1,3 g 1,2+++ g 2,5 g o,8 g 4,8 g Potassium hydroxide 1 Add .2g water to make one sentence, and adjust FA to all 10.06 using potassium hydroxide or 50% sulfuric acid.

[Color developer replenisher] Potassium carbonate 40g Soluium bicarbonate 3g Potassium sulfite 7g Sodium bromide 0.5g Hydroxylamine sulfate 3.1g 4-amino-3-methyl-N=ethyl-N6, 0g Potassium hydroxide 2g Add water to make one part and adjust to all 10.12 using potassium hydroxide or 20% sulfuric acid.

Bleach tank liquid 1-3-propylenecyaminetetravinegar ferric ammonium 150g acetic acid (90% aqueous axillary) 50m ferric ammonium bromide
Add 150 ζ-poor water to make a mixture,
Adjust to all 4.4 using aqueous ammonia or glacial acetic acid.

[Bleach replenisher] All of the bleach tank solution was adjusted to 4.2 with acetic acid.

[Fixer tank liquid and replenisher] Ammonium thiosulfate 250g Ammonium sulfite 20g Example [Heco-7] (Ammonium salt) 2g Add water to make 1Ω, and adjust to all 6.8 using acetic acid and aqueous ammonia.

[Stable tank fluid and replenisher coformaldehy l=' (37% solution)]
m fL5-Chloro-2-methyl-4-inthiazolin-3-one [+. 05g Emulgen 8 1. 0 1
Add 1 m of formaldehyde and 2 g of sodium bisulfite adduct to make 1 m, and add aqueous ammonia and 50% sulfuric acid to pH 7.
Adjusted to 0.

On the other hand, Konica Color QA vapor manufactured by Konica ■ was treated using the following treatment steps and treatment liquid.

Processing process Temperature Time Replenishment amount Number of tanks (1) Color development 38℃ 30 seconds 200 m/m' 1 tank (2)
Bleach fixing 339C 25 seconds 100m. u/m'
1 tank (Note) 3 tank method is performed using counter current method.

Processing solution composition [color developing tank solution] Triethanolamine 10+u potassium sulfite sodium chloride potassium carbonate 0, 2 g 1, 5 g 32, 0 g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfamide ethyl ) - Aniline sulfate optical brightener (diaminostilhene type) Diethylhydroxylamine diethylenetriamine pentaacetic acid butyrobromide potassium 5,5 g 1,0 g 5,0 g 3,0 g 1,2-dihydroxybenzene-3,5-disulfone butylene - Sodium salt 0.2g Add water to make the total amount 1 sentence, and add 11□SO. ,tea
ll 10.15.

[Color development replenisher] The amount of 3 to methyl-4-amino-N-ethyl-N-(β-methanesulfoamide ethyl) to 1 n of aniline sulfur in the color development tank solution was adjusted to 7. [The pH value is set to 1 g/l and the pH value is set to 10.50 using potassium bromide.

[Bleach-fix tank solution and replenisher] Ethylenediaminetetoacetate ferric ammonium dihydrate 6 (] g ethylene thiamine diacetate) 3 g ammonium thiosulfate (70% solution) 14 o Il 1 m ammonium sulfite (40% solution) 27.5+++Q Add water to make the total volume one sentence, and adjust to pH 5.8 with potassium carbonate or ice vinegar.
Prepare to.

[Stable tank liquid and replenisher liquid] 1-hydroxyethylidene-1,1-diphosphonic acid griiici 30gg
ZnSO4・71120
0.7g optical brightener (diaminostilbene type)
1.0g Caisson WT <Note)
(1.5 g (Note) Manufactured by Rohm and Haas Co., Ltd. Continuous processing was performed until the total replenishment amount of each washing substitute stabilizing solution became three times the capacity of the stabilizing tank.

The overflow liquid generated by the above treatment, [
Color developer overflow solution]: [Bleach solution overflow solution] [Fixer overflow solution]: [Water wash alternative stabilizer overflow solution] = 3:3:3:5 Negative waste solution mixed at a ratio of 3:3:3:5 is photographed below. Processing waste liquid (A) is referred to as [color developing solution overflow solution]: [bleach fixing solution overflow solution], [washing substitute stabilizing solution overflow 0]
The vapor waste liquid mixed at a ratio of -M:]=3:3:5 is hereinafter referred to as photographic processing waste liquid (B). The above photographic processing waste liquid (A
) and (B) were mixed in 1.1 and used as a mixed waste liquid to be treated.

Example 2 In No. 2 of Example 1, before the waste liquid was evaporated and concentrated, the waste liquid PL+ was adjusted to 5.5 with sulfuric acid, and the catholyte and anolyte were also returned thereto for treatment. As a result, only the non-problematic desalination chamber liquid was discharged, and very good continuous operation was possible.

Example 3 In Example 1, the only difference was that the mixed waste liquid to be treated was replaced with the following, and the same results as in Example 1 were obtained.

That is, Konica R3T Clear Light Contact Film CRIIE manufactured by Konica Corporation was subjected to normal exposure and processed using the following processing solution and processing steps.

[Developer prescription] Hydroquinone 25g1-
Phenyl-4,4 dimethyl-3- birasoliton 0.4 g g 0.3 g 0.05 g Diol 10 g 0 g 0 g Sodium bromide 5-methylbenzotriazole 5-nitroindasole Diethylaminopropane-1,2- Potassium sulfite Potassium carbonate Hydroxyethylene Cyamine triacetate 1 ~ lium g Finished in one sentence with water.

pl+ was set to 10.2 with caustic soda.

[Fixer formulation] (Composition A) Ammonium thiosulfate (72.5v%: aqueous solution) 240
+n Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g citric acid 1~
Lium dihydrate 2g Acetic acid (90w%; aqueous solution) 1:]
, 66m composition) Pure water (ion exchange water) 17m exchanged sulfuric acid (50w% aqueous solution) 3.0
g Aluminum sulfate (text A, 03 conversion content is 8.1w%
When using a fixer, 20 g of an aqueous solution of the above were dissolved in 500 m of water in the order of composition A and composition A, and the fixing solution was used. The pl+ of this fixer is about 4.2.

[Development processing conditions] (Process) (Temperature) (Time) (Replenishment amount) Development 40°C 15 seconds 30+nu/4-cut fixing
35℃ 15 seconds 40+cu/4 washes with water Room temperature 15 seconds Running water Mix developing waste liquid and fixing waste liquid discharged under these processing conditions (1:1
), and an experiment similar to that for N002 in Example-1 was conducted, and similarly favorable results were obtained.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing a first embodiment of the evaporation concentration processing apparatus of the present invention, FIG. 2 is a front view similarly showing the second embodiment, and FIG.
Each of FIGS. 6 to 6 is a sectional view or a perspective view showing an embodiment of the electrodialysis treatment apparatus of the present invention.

Claims (1)

[Claims] 1. A method for evaporating and concentrating photographic processing waste liquid, in which a photographic processing waste liquid is heated and evaporated, and the resulting vapor is cooled and condensed to obtain a condensate, wherein the evaporation temperature is set at 70°C.
The condensate is placed in an electrodialysis tank in which an anode and a cathode are separated by a cation exchange membrane, and electrodialysis is performed using a DC power supply, and the current density of the electrode is 10 A/dm^2 or less. A method for evaporating and concentrating photographic processing waste liquid. 2. The method for evaporating and concentrating photographic processing waste liquid according to claim 1, wherein the current concentration is 5 A/l or less. 3. An apparatus for evaporating and concentrating photographic processing waste liquid by heating the photographic processing waste liquid at an evaporation temperature of 70 degrees Celsius or lower, cooling and condensing the resulting vapor to obtain a condensate liquid, and a device for evaporating and concentrating the photographic processing liquid liquid by heating and evaporating the photographic processing waste liquid at an evaporation temperature of 70° C. Photographic processing waste liquid characterized by having an electrodialysis device configured to place it in an electrodialysis tank partitioned with a cation exchange membrane and perform electrodialysis using a DC power supply, and to set the current density of the electrode to 10 A/dm^2 or less. Processing equipment. 4. The photographic processing waste liquid processing apparatus according to claim 3, wherein the current concentration is 5 A/l or less.