JPH01119383A - Treating apparatus for photograph treatment waste liquid - Google Patents

Abstract

PURPOSE:To prevent the development of offensive odors and increase the thermal efficiency so as to perform efficient evaporation and concentration, by providing this treating apparatus with a releasing means which accelerates the release of steam bubbles formed on surfaces of a heater and/or evaporator which are in contact with a waste liquid used in the treatment of photographs. CONSTITUTION:A waste liquid which has been used in the treatment of photographs and is stored in an evaporator 1 is heated by a heater 2, so that the waste liquid is evaporated and concentrated. The apparatus for treating the waste liquid is provided with a releasing means 70 accelerating the release of steam bubbles formed on surfaces of the heater 2 and/or the evaporator 1 which are in contact with the waste liquid. For example, the releasing means 70 is constituted such that is supplies air into the waste liquid in the evaporator 1 and stirs the waste liquid. As a result, the waste liquid which has been used for treating photographs is prevented from suffering thermal decomposition which is due to the presence of steam bubbles. Because of this, the development of offensive odors are prevented and the lowering in thermal efficiency is reduced, so that evaporation and concentration can be performed efficiently.

Description

[Detailed description of the invention]

(A) The present invention relates to a processing device for evaporating waste liquid (hereinafter referred to as photographic processing waste liquid or waste liquid) generated during the development process of photographic light-sensitive materials using an automatic photographic processor. ,especially,
The present invention relates to a processing apparatus for photographic processing waste liquid, which is suitable for being disposed in or near an automatic processor. (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 and fixing) in the case of color photographic materials. ,
A combination of processes using a treatment liquid having one or more functions such as water washing and stabilization is carried out. In photographic processing in which a large amount of light-sensitive material is processed, the components consumed during processing are replenished, while the components that are concentrated by elution or evaporation into the processing solution (
For example, methods are used to maintain the performance of the processing solution at a constant level by removing bromide and ions from the developing solution and silver complex salts from the fixing solution to keep the processing solution components constant. Therefore, replenisher is added to the processing solution,
A portion of the processing solution is discarded to remove thickening components during photographic processing. In recent years, systems have been changing to systems in which the amount of replenishment fluid, including washing water, which is used as a replenishment fluid for washing, has been drastically reduced due to pollution and economic reasons. The liquid is led out from the tank through a waste pipe, diluted with waste liquid from washing water, cooling water from automatic processors, etc., and then disposed of in a sewer or the like. However, due to stricter pollution regulations in recent years, it is possible to dispose of washing water and cooling water into sewers or rivers, but other photographic processing solutions [e.g. developer, fixer, color developer, bleach-fixer] (or bleaching solution, fixing solution), stabilizing 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 outsourcing to a waste liquid treatment company is
A considerable amount of space is required to store the waste liquid, and it is also extremely expensive.Furthermore, the initial cost of pollution treatment equipment is extremely large, and it takes a considerable amount of space to maintain. It has disadvantages such as requiring a large space. Therefore, waste liquid is generally collected by a waste liquid collection company and rendered harmless through secondary and tertiary processing.However, not only is the price of waste liquid collection increasing year by year due to rising collection costs, but collection efficiency is low in minilabs, etc., so it is difficult to do so. No one can come to collect the waste, causing problems such as waste liquid filling stores. In order to solve these problems, research has been conducted to heat 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. It is shown in JP-A No. 110-70841 and the like. By the way, when photographic processing waste liquid is evaporated, harmful or extremely malodorous gases such as sulfur dioxide gas, hydrogen sulfide, and ammonia gas are generated. This is due to the decomposition of specific acidic compounds, such as thiosulfate and sulfite, which are often used as fixers and bleach-fixers contained in waste photographic processing solutions. For this reason, various research and experiments were conducted to remove odor components, and it was found that when the photographic processing waste liquid is heated with a heating means and boils, large steam bubbles are generated, and the steam bubbles are overheated and evaporate. There are problems such as superheating of the processing waste liquid, overheating decomposition of the photographic processing waste liquid, generation of hydrogen sulfide and ammonia gas, and reduction of thermal efficiency. Therefore, if the separation of steam bubbles from the heating means that heats the photographic processing waste liquid is promoted, boiling will occur with small steam bubbles, and problems such as overthermal decomposition and a decrease in thermal efficiency will be avoided. It can be solved. Therefore, it has been found that the generation of odors such as hydrogen sulfide and ammonia gas generated as the concentration progresses can be significantly suppressed. (Object of the Invention) This invention was made in view of the above-mentioned conventional problems, and reduces overheating decomposition of photographic processing waste liquid and reduction in thermal efficiency.
An object of the present invention is to provide a processing device for photographic processing waste liquid that prevents the generation of bad odors. (Means for Solving the Problems) In order to solve the above-mentioned problems of the present invention, a photographic processing waste liquid processing apparatus is provided in which the photographic processing waste liquid stored in the evaporating means is heated by a heating means to evaporate and concentrate the photographic processing waste liquid. The present invention is characterized in that it includes a detachment means for promoting detachment of vapor bubbles generated on the surface of the heating means and/or evaporation means that comes into contact with the photographic processing waste liquid. In this way, when the photographic processing waste liquid is heated by the heating means and boiled, if the separation of the steam bubbles from the heating means for heating the photographic processing waste liquid is promoted, boiling will occur with small steam bubbles. This reduces the overheating of the steam bubbles,
The evaporating photographic processing waste liquid will no longer be overheated and decomposed due to superheating. Therefore, generation of hydrogen sulfide and ammonia gas can be suppressed, and thermal efficiency is improved. The removal means of this invention is configured to supply and stir gas into the photographic processing waste liquid within the evaporation means. in this case,
Air, nitrogen, etc. is supplied as a gas, and the supply amount is 2% or more of the amount of steam generated, preferably 10% or more and 100% or less, and more preferably 30 to 50% to reduce heat loss due to overheating of steam bubbles. This is preferable in terms of preventing the decrease. Further, by supplying the gas, the temperature of the photographic processing waste liquid in the evaporation means is set to be below the boiling point and above 80°C, more preferably at 10°C.
The temperature is preferably 0 to 90° C. Furthermore, the gas is preferably supplied near the surface of the heating means, and it is particularly preferable to supply the gas to a position below the heating means to ensure that vapor bubbles are removed. Preferably, the removal means of the present invention is configured to forcibly circulate and agitate the photographic processing waste liquid in the evaporation means, since vapor bubbles generated on the surface of the heating means can be removed quickly. , when the diffusion rate at this time is expressed as an increasing linear velocity, it is 0.05 to in/sec, more preferably 1 to
50 cm/sec, more preferably 2-20
cm/sec. In addition, Lm (expressed in SV value is 100 to 10.000 L/hr, more preferably 300 to 2000 L/hr. In this case, the temperature of the photographic processing waste liquid in the evaporation means is below the boiling point, 80 ° C. or above, and more preferably 100 to 90°C.Furthermore, the detachment means of the present invention can be configured to apply vibration to the heating means within the evaporation means.In this case,
Vibrate the heating means directly. Further, the detachment means is configured to vibrate the photographic processing waste liquid in the evaporating means with ultrasonic waves, thereby vibrating the photographic processing waste liquid and promoting the detachment of vapor bubbles generated in the heating means. . The frequency of the ultrasonic wave is preferably 10KHz to 100KH
z is used, more preferably 15KH2 to 50K)I
zh (used), and this frequency is arbitrarily set depending on the location where the ultrasonic generating means is provided, the temperature and concentration of the photographic processing waste liquid, etc., and the intensity of the ultrasonic wave is 1 to 300 dB, more preferably 2 to 200 dB. In this invention, it is preferable to use a detachment means in combination, and it is particularly preferable to use a combination of air or gas blowing and circulation of concentrated photographic processing waste liquid. In this case, ceramic (e.g. A 1
20 s % T i O2, Z r Ox , S n
It is preferable to coat with a coating material such as metal, metal oxide, etc., as it has corrosion resistance and heat resistance.In this case, the coating material is 0.
Particles on the order of 1 μm or larger are used and coated using various thermal spray techniques. As this coating method, it is preferable to use an electrolytic plating method or a brush coating method. As this electrolytic plating method, a lump of metal is plated on the surface by an electrolytic plating method. As the metal, N1%Cr or the like is used. Furthermore, non-electrolytically purchased particles such as activated carbon and alumina may be plated on the surface by a decomposition plating method or the like. Furthermore, as a brush coating method, various particles such as alumina, silica alumina, carbon, metal powder, etc. are dispersed in a suitable solvent such as Teflon or other organic polymer adhesive, and then applied to the surface, for example. Adhere firmly using heating method, etc. Further, the uneven processing of the present invention may be performed by blasting or sandblasting. These treatments include filing or sandpapering the surface sufficiently to make it uneven, or removing the grain. The roughness is processed by rough polishing. The deeper and finer the scratches, the higher the effect of vapor bubble release.It is preferable that this uneven processing is porous so that the bubbles can be removed quickly.For example, if the thickness is lμI? 1. Machining a 10mm groove at or above 41st place. The above-mentioned various thermal spraying methods, electrolytic plating methods, and brush coating methods are used for this porous uneven processing. Furthermore, in this invention, instead of surface processing as described above,
It is also possible to attach a member processed by similar means to the surface. For example, as a processed material, sintered metal using metal particles, metal mesh, etc. can be attached to the surface of the heating means or evaporation means, and the surface is Becomes porous. In this invention, the heating means that comes into contact with the photographic processing waste liquid is
It may be a nichrome wire, or it may be heated by a molded heater such as a cartridge heater, quartz heater, Teflon heater, bar heater or panel heater, or by microwave. may be brought into direct contact with the photo-processing waste liquid, and an electric current may be passed through the photographic processing waste liquid using the conductive material, and the photo-processing waste liquid may be heated. This conductive material is single crystal 51, polycrystalline Si, Ta2Nv
Ta-SiO2, ZrO2, ZrN, TiN, Cr-
5i-0, SiC%5iC-Zr, 5ic-Cr, 5i
C-Hf, 5IC-Ti, StC-Mo, Si
C-W, S t C-Nb, S i
C-Ta, S i C-La% B,
B-Mo% B-La. B-Cr, B-Tr, B-Na, B-Ta
, W. B-W, B-V, C% C-halogen, C-3i. C-Ge, C-H, Pt, Mo% Mo-3t
, Mo5i2. CaO1MgO, Y2 0s,
It is composed of at least one composition selected from La 2 (Cr04), and can suppress the generation of odor that occurs during evaporation and concentration due to catalytic action, the influence of electric current, etc. It is also preferable to use the composition as a resistance material in a car as a heater insulated against photographic processing waste liquid, and furthermore, a ceramic heater or the like is used. The heating means is disposed so as to be wholly or partially immersed in the photographic processing waste liquid, and thus evaporation of the photographic processing waste liquid is caused by heating by the evaporating means. This is preferable because it can improve waste liquid treatment efficiency (processing speed), and this heating temperature is! 20
The temperature is preferably about 130°C. This evaporation means may be in any form, and may be a cube, a cylinder, a polygonal prism including a square prism, a cone, a polygonal pyramid including a square pyramid, or a combination of some of these. However, it is preferable that the photographic processing waste liquid be vertically long so that the temperature difference between the vicinity of the heating means and the bottom of the photographic processing waste liquid is large. It is preferable to make the space as wide as possible. The material of the evaporation means may be any heat-resistant material such as heat-resistant glass, titanium, stainless steel, carbon steel, heat-resistant plastic, etc. However, from the viewpoint of safety and corrosion resistance, stainless steel (preferably 5US304 and 5US316, particularly preferably 5US316) and titanium. The evaporation means is preferably equipped with a heating means for heating the photographic processing waste liquid to about 120 to 130°C, and this may be installed inside the waste liquid, but it may be installed outside the evaporation means and evaporated through the wall of the evaporation means. It is also preferable to heat the waste liquid in the means, and the heating means may be installed at any position as long as it can heat the waste liquid of the evaporation means.
As described in Japanese Patent Application No. 61-288328, a heating means is installed to heat the upper part of the photographic processing waste liquid in the evaporating means, and the temperature of the photographic processing waste liquid near the heating means and the bottom part of the photographic processing waste liquid is It is preferable to create a difference in temperature, and it is preferable to install the heating means so that this temperature difference is 5° C. or more, in order to further enhance the effects of the present invention. This invention has a condensing means for cooling and condensing the evaporated vapor, and the condensing means can employ all kinds of heat exchange means.
(1) Shell and tube type (multi-tube type, cannula type), (
2) Two-plate tube type, (3) Coil type, (4) Spiral type, (5
) plate type, (6) fin tube type, (7) trombone type, and (8) air cooling type. It is also possible to use heat exchange type reboiler technology.
) vertical thermosiphon type, (2) horizontal thermosiphon type, (3) overflow tube bundle type (kettle type), (4) forced circulation type, (5) interpolation type, etc. may be adopted. Furthermore, condenser type heat exchange technology may be adopted, and may be any of (1) direct condenser type, (2) built-in tower type, (3) tower top type, (4) separation type, etc. . Moreover, it is also possible to use a cooler, and the type of cooler is also arbitrary. It is also advantageous to employ an air-cooled heat exchanger, which may be either (1) forced draft type or (2) blown draft type. In a preferred embodiment, the condensing means is configured as a heat sink device in which a heat sink (air cooling fan) is installed in a steam exhaust pipe for discharging evaporated steam, and has means for supplying water onto the heat sink. That's what I'm doing. In this case, water is preferably supplied onto the shower from above the heat sink device onto the heat sink. For example, water may be supplied onto the heat sink from a tap water tap via a valve or a solenoid valve as necessary, and in this case, the means for supplying books may be a tap tap, a water supply pipe, etc. However, it is preferable that the stored water is supplied onto the heat sink through various metering pumps or non-metering pumps as described above, and in particular, it is preferable that the reservoir water is supplied onto the heat sink through the various metering pumps or non-metering pumps as described above. The water in the tank is supplied to the heat sink via a pump in a shower-like manner, and is then collected in the water tank at the bottom, so that the water is circulated. In this case, by installing a liquid level sensor in the reservoir water tank and sending out a signal when the liquid level drops below a certain level, you will be able to know that the reservoir water has run out and supply water again. It's good. The condensing means is constructed as a heat sink device in which a heat sink (air cooling fan) is installed in a steam exhaust pipe that discharges evaporated steam, and when the condensing means has a means for supplying water onto the heat sink, It is preferable to have an air-cooling fan at the same time, and in particular, in this case, the air-cooling fan is installed in the device where the air passes through the heat sink device and is discharged to the outside of the evaporation concentration processing device of the present invention. It is preferable to do so because condensation in the electrical components in the evaporation concentration processing apparatus of the present invention can be prevented. The condensate obtained by cooling and concentrating the evaporated vapor is stored in a tank for storing the condensate (distillate tank). It is preferable to install the reservoir tank on a pull-out pedestal to improve workability. Furthermore, the structure of the evaporating means, heating means, and condensing means of this invention is disclosed in Japanese Patent Application No. 62-694 filed earlier by this applicant.
No. 35, No. 62-69436, and No. 62-6943
It is described in detail in the specification of No. 7. Next, as for typical examples of photographic processing waste liquids that can be processed according to the present invention, those described in Japanese Patent Application No. 194815/1987 previously filed by this applicant are used, and in particular, this The processing apparatus of the invention is effective for photographic processing waste liquid containing large amounts of thiosulfates, sulfites, and ammonium salts, and is particularly effective when containing organic acid ferric complex salts and thiosulfates. be. A preferred example of application of the present invention is the photo IA1! generated during the development process of photographic light-sensitive materials using an automatic processor. Suitable for processing waste liquid in or near an automatic processor. Here, automatic processors and photographic processing waste liquid will be explained. Automatic processor In FIG. 1, the automatic processor is designated by the reference numeral 100, and the one shown in the figure continuously passes a roll of photographic material F into a color development tank CD, a bleach-fix tank BF, and a stabilization processing tank sb. This method involves guiding the film through the process, photo-processing it, and winding it up after drying. 1o1 is a replenisher tank, which detects the amount of photographic processing of the photosensitive material F by a sensor 102, and replenishes each processing tank with replenisher by a control device 103 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 method for transferring overflowing photographic processing waste liquid to the stock tank 104 is to allow it to fall naturally through a guide pipe. There may also be cases where it is forcibly transferred using a pump or the like. Moreover, as mentioned above, each photographic processing tank CD, BF. Although there are differences in the components of the photographic processing waste liquids in sb, in the present invention, it is preferable to mix all the photographic processing waste liquids and process them all at once. (Example) Fig. 2 is a schematic diagram showing a processing apparatus for photographic processing waste liquid according to the present invention. In the figure, reference numeral 1 denotes an evaporation pot as an evaporation means, which is composed of a cylindrical upper part 1a with a large diameter and a cylindrical lower part 1b with a small diameter.Heating means 2 is arranged in the upper part 1a, and in the lower part 1b. is equipped with a ball valve 3. The evaporation pot 1 is provided with a liquid level sensor 4, and a sludge receiver 6 is placed on a support stand 5 disposed at the bottom of the evaporation pot 1, and this sludge receiver 6 is provided under the lower part 1b. A polypropylene bag 7 is fixed inside by an O-ring 8. In the upper part 1a of the evaporating pot 1,
A steam exhaust pipe 9 is provided, which passes through a heat exchanger 10 and a condensing means 11 to a distilled liquid inlet pipe 12.
connected to. In the condensing means 11, a large number of cooling heat sinks 13 are provided on the steam exhaust pipe 9, and a liquid level sensor 14 is further provided. 'a Cooling water introduction pipe 1 is installed at the bottom of the compression means 11.
5 is provided, and is connected via a cooling water circulation pump 16 to a shower vibe 17 having a large number of small holes. The air in the condensing means 11 is cooled by an air cooling fan 18.
Released outside the processing equipment. The accumulated liquid introduction pipe 12 is connected to the inside of the accumulated liquid tank 19, and the tip 12a of the accumulated liquid introduction pipe 12 is located below the level of the accumulated liquid in the accumulated liquid tank 19, and constitutes a bubbling mechanism 20. Furthermore, an activated carbon cartridge 21 that stores activated carbon is provided at the upper part of the reservoir tank 19. The accumulated liquid tank 19 also includes an air introduction pipe 2.
2 is provided and introduced into the waste liquid of the evaporator 1 via an air pump 23. Reference numeral 24 denotes a waste liquid supply tank, which is provided with a waste liquid introduction pipe 25 and is connected to the evaporator upper part 1a via a bellows pump 26 and a heat exchanger 10. The waste liquid supply tank 24 is further provided with a liquid level gauge 27. The upper part 1a of the evaporator 1 is further provided with a guide pipe 28, which is connected to the waste liquid supply tank 24 via a plunger disk 29, and the upper part 1a of the evaporator 1 is also provided with a temperature sensor 30. A supply pipe 70 is connected to the upper part 1a of the evaporating pot 1 at a position below the heating means 2, and air is introduced from the supply pipe 70. This air rises in the photographic processing waste liquid and agitates the surface of the heating means 2, causing vapor bubbles to separate. At this time,
The rising air causes the photographic processing waste to flow, making it easier to remove the vapor bubbles. Note that the position of the air supply pipe 0 is not limited to any particular position, and the air may be supplied directly to the heating means 2, for example. Further, the heating means 2 is composed of, for example, a heater, and the surface of this heater may be textured. In this case, the contact angle of the steam bubbles with the surface increases, and the early departure of the steam bubbles is promoted. be done. In this way, there is no longer a phenomenon in which steam bubbles are permanently attached to the surface of the heating means 2 and heated, so the surface temperature of the heating means rises and the thiosulfuric acid component in the photographic processing waste liquid is overheated and decomposed by heat. Decomposition and generation of hydrogen sulfide is reduced. Further, a decrease in thermal efficiency due to overheating of the water vapor bubbles is prevented. Next, an outline of the heating and evaporation process using this apparatus will be explained. Approximately 20 ft of overflow liquid from the automatic developing machine is stored in a waste liquid supply tank 24, and an activated carbon cartridge 21 filled with activated carbon, a accumulated liquid introduction pipe 12, and an air introduction pipe 22 are connected to the accumulated liquid tank 19. A polypropylene bag is installed in the sludge receiver 6 under the lower part 1b of the evaporation pot 1,
It is fixed to the lower part 1b of the evaporating pot 1 with two O-rings 8, and the condensing means 1! After supplying water inside, turn on the switch.
Then, the air pump 23 is activated, and the air in the accumulated liquid tank 19 is transferred to the evaporation pot via the air introduction pipe 22! be introduced within. Then, the air cooling fan 18 and the cooling water circulation pump 16 operate in this order, and the stored water passes through the cooling water introduction pipe 15 onto the shower vibe 1 or onto the heat sink 13 of the steam exhaust pipe 9 housed in the condensing means 11. The condensate is supplied to the condensing means 11, and is collected again at the bottom of the condensing means 11. The bellows pump 26 is activated, and the waste liquid in the waste liquid supply tank 24 passes through the waste liquid introduction pipe 25, passes through the heat exchange means 10, and is then sent into the evaporation pot 1. When the amount of waste liquid in the evaporator pot 1 increases and the liquid level is detected by the liquid level sensor 4 for, for example, 3 seconds or more, the operation of the bellows pump 26 is stopped, and at the same time, the heating means 2 is switched on, and the heating evaporation is started. will be started. The vapor is evaporated and concentrated by heating and evaporation, but air is introduced through the supply pipe 70, and this agitation causes the vapor bubbles to leave the heating means 2 at an early stage, and since the bubbles are thin, thermal decomposition is reduced, and the vapor is concentrated by evaporation. It is possible to significantly reduce the amount of odorous gases present in the generated steam, and even as the concentration progresses, the generation of hydrogen sulfide and sulfur-based odors is reduced. As a result of this process, the amount of waste liquid in the evaporator pot 1 decreases, the liquid level drops, and when the liquid level sensor 4 no longer detects the liquid level for more than 3 seconds, the bellows pump 26 is switched off again. enters,
The operation of supplying the waste liquid in the waste liquid supply tank 24 into the evaporation pot 1 is repeated. The steam evaporated from the evaporation pot 1 passes through the steam exhaust pipe 9, and after exchanging heat with the waste liquid in the heat exchanger 10, it passes through the condensing means 11, where a part of it is condensed and becomes a condensate liquid. . This condensate, along with the remaining gas in the steam, passes through the reservoir liquid inlet pipe 12 and is sent into the reservoir tank 19, and is discharged from the tip 12a below the surface of the reservoir liquid, and the condensed water is stored in the reservoir tank 19. Ru. At this time, the gas released from below the surface of the reservoir liquid rises in the reservoir liquid, causing bubbling, and this bubbling causes gases such as hydrogen sulfide melted in the reservoir liquid to be expelled from the liquid. When the air pump 23 is operated, the gas is returned from the accumulated liquid tank 19 to the photographic processing waste liquid located at the lower part of the evaporator 1 through the air introduction pipe 22. Incidentally, the accumulated liquid tank 19 is communicated with the atmosphere via an activated carbon cartridge 21 filled with activated carbon to prevent odor from being released into the atmosphere. When the liquid level sensor 27 detects that there is no more waste liquid in the waste liquid supply tank 24, the bellows pump 26 stops operating, the heating means 2 is turned off, and two hours later the cooling water circulation pump 16. The air cooling fan 18 stops, the lamp lights up,
A buzzer sounds to notify that the evaporation and concentration process has been completed, and the air pump 23 stops. Now, open Ball Pal 3 and use the evaporation pot! After the sludge inside is dropped into the polypropylene bag 7, the O-ring 8 is removed and taken out. In addition, during the evaporation concentration process, when the liquid level sensor 14 detects that the water in the condensing means 11 has run out, a lamp lights up and a buzzer sounds, indicating that the stored water has run out. Let me know. Further, during the evaporation concentration process, if the temperature sensor 30 detects that the liquid level in the evaporator 1 has abnormally decreased for some reason and the temperature in the evaporator 1 has risen to 120°C due to dry heating, the lamp lights up, a warning buzzer sounds, and the heating means 2 is turned off. From then on, the evaporation concentration process is interrupted by the series of operations described above. FIG. 3 shows a circulation system 71 located near the heating means 2 of the evaporation pot 1.
The photographic processing waste liquid is circulated from the bottom to the top by driving the pump 72 of this circulation system 71. As a result, the photographic processing waste liquid can agitate the surface of the heating means 2, and vapor bubbles can be quickly removed. In FIG. 4, the heating means 2 of the evaporating pot 1 is provided on the outer periphery of the lower part 1b of the evaporating pot 1, and is heated from the outside. Then, an ultrasonic transmitter 73 is provided at a lower position near the heating means 2, and this operation vibrates the photographic processing waste liquid and causes vapor bubbles generated on the inner wall of the lower part 1b of the evaporation pot 1 where the heating means 2 is located. I'm trying to force them to leave early. In FIG. 5, a heating means 2 is provided in the photographic processing waste liquid from the upper part 1a of the evaporating pot 1, and this heating means 2 itself is forcibly vibrated by a vibrator 74, which is a mechanical means. The vibration of the heating means 2 forcibly removes vapor bubbles generated on the surface. The frequency of vibration at this time can be set arbitrarily. FIG. 6 shows the combination of gas blowing and circulation of photographic processing waste liquid. That is, a circulation pump 75 is provided, and when the circulation pump 5 is driven, the photographic processing waste liquid concentrated from the lower part 1b of the evaporator 1 is circulated through a pipe 76, and the evaporator 1 at the position where the heating means 2 is provided is circulated. I try to spray it towards the inner wall. In addition, by driving the air pump 23,
Gas from the accumulated liquid introduction pipe 12 is blown into the interior of the evaporating means 2 from a position below it. [Experiment Example 1] MPS processing system automatic processor for paper RP-800
(manufactured by Konica Corporation), and after printing a commercially available color photographic paper (manufactured by Konica Corporation), continuous processing was performed using the following processing steps and processing solution. Standard processing step (1) Color development 40°C 3 minutes (2) tll
[Inner fixation 38°C 1 minute 30 seconds (3) Stabilization treatment 25°C to 35°C 3 minutes (4) Drying 75
℃～100℃ Approximately 2 minutes Processing liquid composition [Color development tank liquid] Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide
1.3g sodium chloride
0.2g potassium carbonate
24.0g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.5g optical brightener (4,4
°-diaminostilbendisulfonic acid derivative)
1.0g hydroxylamine sulfate 3
．． 0g 1-hydroxyethylindene-1,1-niphosphonic 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 solution 11, and the pH was adjusted to 10.2 with potassium hydroxide and sulfuric acid.
Set to 0. [Color developer replenisher] Ethylene glycol 20mj! Potassium sulfite 3.0g Potassium carbonate
24.0g hydroxyamine sulfate 4.0g 3-methyl-4-amino-N-
Ethyl-N-(β-methanesulfonamide ethyl)aniline sulfate 1.5g Optical brightener (4,4
'-diaminostilbendisulfonic acid derivative)
2.5g 1-hydroxyethylindene-1.1
- Niphosphonic acid 0.5g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride hexahydrate o, 8g 1.2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0
．． Add 3g of water to make 11, and make p with potassium hydroxide and sulfuric acid.
Let it be H10,70. [Bleach-fix tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100. mf ammonium sulfite (40% solution) 27.5m! Add water to bring the total volume to tJ2, and add potassium carbonate or glacial acetic acid to p
Adjust to H7.1. [Innocence fixer replenisher A] Ferric ammonium ethylenediaminetetraacetate dihydrate 260.0g Potassium carbonate 42.0g Add water to make the total amount IJ! shall be. 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 250.0 mn (70%
Solution) Ammonium sulfite 25.0ml (40%
Solution) Ethylenediaminetetraacetic acid 17.0g Glacial acetic acid
Add 85.0mj2 water and bring to a boil. 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 coethylene glycol 1.0g 2-methyl-4-isothiazolin-3-one
0.20g 1-hydroxyethylidene-1,
1-Niphosphonic acid (60% aqueous solution 1.0g ammonia water (amthonium hydroxide 25% aqueous solution) 2.0g in water
ft and adjusted to pH 7.0 with 50% sulfuric acid. Fill an automatic processor with the above-mentioned color developing tank liquid, bleach-fixing tank liquid and stabilizing tank liquid, and while processing the commercially available color photographic vapor sample, mix the above-mentioned color developing replenisher, bleach-fixing replenisher A and B and stabilize. A running test was performed while replenishing the replenisher through the bellows pump. The amount of replenishment is 190 mL per 1 liter of color paper to the color developing tank, 50 mL each of bleach-fixing replenisher A and B to the bleach-fixing tank, and 50 ml of each of bleach-fixing replenishers A and B to the stabilizing tank. 250m
λ supplemented. The stabilization tanks of the automatic developing machine are the first to third tanks in the direction of the flow of the sample, and the final tank is replenished, and the overflow liquid from the final tank is allowed to flow into the oak at the previous stage. Furthermore, a multi-tank countercurrent system was adopted in which this overflow liquid also flows into the preceding tank. Continuous processing was performed until the total amount of replenishment of the water washing alternative stabilizing solution became three times the capacity of the stabilizing tank. In addition, after each color negative film GX-100 (manufactured by Konica Corporation) was exposed to light using a conventional method, the following development processing was performed using an automatic developing machine that was a modified version of the negative film processor NFS-FP34 (manufactured by Konica Corporation). The treatment was carried out continuously under the following conditions. From waterless washing stability (2nd tank) to waterless washing stability (1st tank),
The countercurrent method (two-stage countercurrent) is used, and the bleach-fixing process is similarly carried out from bleach-fixing (second tank) to bleach-fixing (first tank).
A counter current method was used to flow into the tank). In addition, the amount of processing liquid brought in from the front tank of a multi-tank is 0゜6 m
It was iL/dm'. Below are 9 color developing tank solutions showing the formulations of the tank solution and each replenisher; Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g! -Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.0g Hydroxyethyliminodiacetic acid 3.0g Magnesium chloride 0.3g Potassium bromide 1.2g Sodium hydroxide 3.48N-ethylene-N-β-
Hydroxyethyl-3-methyl-4-aminoaniline hydrochloride 4.6g Water was added to make the pH 11, and the pH was adjusted to 10.1 with sodium hydroxide.
Adjusted to. Color developer replenisher: Potassium carbonate 40g Sodium sulfite 3.0g Hydroxylamine sulfate 3.0g Diethylenetriaminepentaacetic acid 3.0g Potassium bromide
0.9g sodium hydroxide
3.4g N-ethylene-N-β-hydroxyethyl-3
-Methyl-4-aminoaniline hydrochloride 5.6g Add water to make 11, and add sodium hydroxide to pH 10.1.
Adjusted to. Bleach-fix tank solution and replenisher diethylenetriaminepentaacetic acid ferric ammonium salt 0.5M Hydroxyethyliminodiacetic acid 20g Ammonium thiosulfate (70% evening t/VOj 50ml Ammonium sulfite 15g 2-amino-5-mercapto-1,3 ,4-thiadiazole 1.0g ammonia water (28%) 11 with 20ml water
The pH was adjusted to 7.6 with acetic acid and aqueous ammonia. Anhydrous wash stable tank fluid and replenisher; 5-chloro-2-methyl-4-isothiazolin-3-one 0.01g2-methyl-4
-Isothiazolin-3-one Ethylene glycol diethylene triamine Pentaacetate Finished to IIL with ferric ammonium salt solution, pH 10 with ammonium and sulfuric acid,
Adjust to 0. Stable tank liquid and replenisher: Formalin (37% aqueous solution) Konidax (manufactured by Konica Corporation) Add water to make 11. Continuous processing was carried out until the tank replenishment amount of the color developer reached three times the capacity of the color developer tank. The color negative film and color vapor waste liquid were mixed at a ratio of 1:1 and used.

[Experiment 1]

Using the waste liquid, a comparative experiment was carried out using the photographic processing waste liquid processing apparatus shown in Fig. 2, in which the treatment was carried out by blowing air (temperature 26°C) from the lower position (lower 100 mm) and the case in which the treatment was carried out without blowing air. . Evaporation pot volume: Volume 4.2 ft Heat source used: Rod heater (W for 1 and 2) Example 2 Next, air (temperature 26°C) was heated to a lower position (100 m lower).
m), and when the treatment is performed by blowing from the upper position (upper 5).
A comparison experiment was conducted with a case where the air was blown from a depth of 0 mm). Evaporation pot volume: Volume 4.2It Heat source used: Rod heater (1.2KW) Air blowing amount
:251/min

[Experiment 2] A comparative experiment was conducted between a case where the evaporative concentration process was carried out using the circulation system shown in FIG. 3 and a case where the circulation system was not provided. Evaporation pot volume: Volume 4.21 Heat source used: Rod heater (1.2KW) Liquid circulation amount
:61/min

[Experiment 3] A comparative experiment was conducted between the case where the ultrasonic transmitter shown in FIG. 4 was provided and the evaporation concentration process was carried out, and the case where the ultrasonic transmitter was not provided. Evaporation pot volume: Volume 4.2 Heat source used: Rod heater (1.2KW) Waste liquid
:Comprehensive photographic processing waste liquid volume 2IL Ultrasonic transmitter: 300W
, 28KHz transmission

[Experiment 4] An experiment was conducted to compare the case where the evaporation concentration process was carried out by applying motion to the evaporation means using the mechanical means shown in FIG. 5, and the case where the motion was not applied. Evaporation pot volume: Volume 4.2ft Heat source used: Rod heater (1.2KW) Waste liquid
: Comprehensive photographic processing waste liquid volume 2j2 vibration : 50W,
60Hz (Effect of the invention) As described above, the photographic processing waste liquid processing apparatus of the present invention has the following features:
of vapor bubbles generated on the surfaces of the heating means and/or the evaporating means that come into contact with the photographic processing waste! Since the vapor bubbles generated on the surface of the heating means during evaporation and concentration are provided with a detachment means that promotes desorption, vapor bubbles generated on the surface of the heating means during evaporation and concentration can be forcibly and quickly detached. Therefore, the photographic processing waste liquid is not overheated and decomposed due to vapor bubbles, the generation of odor is suppressed, and the decrease in thermal efficiency is reduced, making it possible to carry out efficient ``evaporation concentration''.

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of an automatic processor, and Figure 2 is a schematic diagram of an automatic processor. Figure J6 is a schematic configuration diagram showing an embodiment of the present invention. In the drawings, reference numeral 1 is an evaporation pot, 2 is a heating means, 11 is a condensing means, 19 is a reservoir tank, 24 is a waste liquid supply tank, 70 is a supply pipe, 1 is a circulation system, 72 is a pump, 73 is an ultrasonic wave The transmitter 74 is a vibrator. Figure 1 Procedural amendment sound March 7, 1988 1 Indication of the case Patent application No. 276413 of 1988 2 Name of the invention Processing device for photographic processing waste liquid 3 Person making the amendment Relationship to the case Patent applicant address Tokyo 1-26-2 Nishi-Shinjuku, Shinjuku-ku Name (1)
27) Konica Co., Ltd. (as of December 11, 1988 6. Subject of amendment: "Detailed description of the invention" in the specification)
Column 7 Contents of the amendment As shown in the attached sheet: (1) "Can do" on page 4, line 19 of the specification is corrected to "can do". (2) In the third line of page 10 of the same book, "metsuru" is corrected to "metsukiru". (3) In the same book, page 13, line 4, ``combined'' is corrected to ``combined''. (4) In the same book, page 17, line 14, "do" is corrected to "do". (5) In the same book, page 18, line 16, ``to be done'' is corrected to ``to be done''. (6) In the same book, page 18, line 17, ``to be done'' is corrected to ``to be done''. (7) “Bottom” in page 19, line 16 of the same book was changed to “bottom 1bJ
I am corrected. (8) In the same book, page 21, line 9, "from here" is corrected to "from here." (9) In the same book *page zt, lines 15 and 16, "without limitation," is corrected to "without limitation." (10) "Bubbling" on page 24, line 18 of the same book is corrected to "bubbling." (11) "r ball pal 3" on page 25, line 14 of the same book.
Ball valve 3" is corrected. (12) "Magnesium" in the third line of page 30 of the same book is corrected to "magnesium." (13) In the same book, page 31, line 20, “(60% aqueous solution”) is corrected to “(60% aqueous solution)”. (14) In the same book, page N32, line 9, “did” is corrected to “did”. (15) In the first line of page N33 of the same book, ``I went'' is corrected to ``I did it.'' (16) In the third line of page 34 of the same book, ``r-method did'' is corrected to ``r-method.'' (17) "2-Methyl-4-isothiazolin-3-one" on page 36, line 10 of the same book was replaced with "2-methyl-4-isothiazolin-3-one 0.01
Correct it as gJ. (18) "Ethylene glycol" on page 36, line 11 of the same book is corrected to "ethylene glycol 2.
0.03 mole”. (20) “Formalin (37%
(aqueous solution)" should be corrected to "formalin (37% aqueous solution) 3 mλ." (21) In the same book, page 36, line 18, "Konidax (manufactured by Konica Corporation)" is corrected to "Konidax (manufactured by Konica Corporation) 7mp". that's all

Claims (5)

[Claims] (1) In a processing device for photographic processing waste liquid stored in an evaporating means, which is heated by a heating means to evaporate and concentrate the photographic processing waste liquid, the waste liquid is generated on the surface of the heating means and/or the evaporating means that comes into contact with the photographic processing waste liquid. 1. A processing device for photographic processing waste liquid, characterized in that it is equipped with a separation means for promoting separation of vapor bubbles. (2) The photographic processing waste liquid processing apparatus according to claim 1, wherein the removing means is configured to supply and stir gas into the photographic processing waste liquid in the evaporating means. (3) The photographic processing waste liquid processing apparatus according to claim 1, wherein the removing means is configured to forcibly circulate and stir the photographic processing waste liquid within the evaporating means. (4) The photographic processing waste liquid processing apparatus according to claim 1, wherein the detachment means is configured to apply vibration to the heating means within the evaporation means. (5) The photographic processing waste liquid processing apparatus according to claim 1, wherein the removing means is configured to vibrate the photographic processing waste liquid in the evaporating means with ultrasonic waves.