JPH0790213B2 - Photoprocessing waste liquid processing equipment - Google Patents

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing device for evaporating a waste liquid (hereinafter, abbreviated as a photographic processing waste liquid or a waste liquid) generated during development processing of a photographic light-sensitive material by an automatic photographic developing machine, and in particular, The present invention relates to a processing apparatus for photographic processing waste liquid, which is suitable for processing by being disposed in or near an automatic developing machine. [Prior Art] Generally, photographic processing of a silver halide photographic light-sensitive material is developed, fixed, washed with water in the case of a black-and-white light-sensitive material, and color-developed, bleach-fixed (or bleach-fixed) in the case of a color light-sensitive material. ,
A combination of steps using a treatment liquid having one or more functions such as washing and stabilizing is performed. In a photographic process for processing a large amount of a light-sensitive material, a component consumed by the process is replenished, while a component concentrated by elution or evaporation in the process solution by the process (for example, a bromide ion in a developing solution and a fixing solution). By removing (such as silver complex salt) and keeping the components of the processing liquid constant, the replenishing liquid is replenished with the replenishing liquid for replenishment. A part of the processing liquid is discarded for the purpose of removing the thickened component in the above. In recent years, the replenisher is changing to a system in which the amount of replenishment is drastically reduced, including wash water, which is the replenisher for washing, for pollution and economic reasons. It is guided by a waste liquid pipe, diluted with waste liquid of washing water, cooling water of an automatic processor, etc., and placed in a sewer or the like. However, due to the strengthening of pollution control in recent years, it is possible to dispose of washing water and cooling water in sewers and rivers, but other photographic processing solutions [eg developing solution, fixing solution, color developing solution, bleach-fixing solution] (Or bleaching solution, fixing solution), stabilizing solution, etc.] is practically impossible. For this reason, each photo processing company has a waste liquid processing company paying a recovery fee to collect the waste liquid and installing a pollution processing facility. 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 the cost is extremely high. Moreover, the pollution treatment equipment has a very large initial investment (initial cost), and it is a vast area to install. There are drawbacks such as requiring Therefore, it is generally collected by a waste liquid collection company and secondarily and thirdly treated to be harmless, but the collection cost of waste liquid is not only increasing year by year due to the rise in the collection cost, but the collection efficiency is poor in minilabs etc. There is a problem that the waste liquid fills the store. To solve these problems, it has been studied to heat the photoprocessing waste liquid to evaporate it to dryness or solidify it by heating the photoprocessing waste liquid in a minilab, etc. It is disclosed in Kaisho 60-70841 and the like. By the way, according to the research conducted by the inventors, when the photographic processing waste liquid is subjected to evaporation treatment, harmful or extremely malodorous gas such as sulfurous acid gas, hydrogen sulfide, and ammonia gas is generated. This is ammonium thiosulfate or sulfite (ammonium salt, which is often used as a bleach-fix solution for photographic processing solutions.
It was found that the sodium salt or potassium salt) is generated by splitting due to high temperature. Further, during the evaporation process, the water and the like in the processed photographic waste liquid becomes vapor and is gasified, so that the volume expands and the pressure in the evaporation tank increases. For this reason, this pressure causes the harmful or odorous gas to escape from the evaporation processing apparatus to the outside of the apparatus, which is extremely unfavorable in the working environment. Therefore, in order to solve these problems, Japanese Utility Model Laid-Open No. 60-70841 discloses a method of providing an exhaust gas treatment section such as activated carbon in the exhaust pipe section of an evaporation treatment apparatus. However, this method has a serious drawback in that water vapor due to a large amount of water in the treatment waste liquid causes condensation or condensation in the exhaust gas treatment section, and the gas absorption treatment agent is covered with water, and the gas absorption capacity is lost instantaneously. However, it was still unusable for practical use. In order to solve these problems, the inventors of the present invention provide a cooling / condensing means for condensing vapor generated by evaporation when the photographic processing waste liquid is evaporated, and further process the condensate generated by condensation and non-condensed components. As for the above, a method and an apparatus for concentrating the photographic processing waste liquid, which is processed and discharged to the outside, was previously proposed. [Problems to be Solved by the Invention] However, according to the above proposal, the following problems have been found out. That is, the vapor generated by the evaporation process is condensed by the cooling condensing means, but if the cooling condensing efficiency is poor, the ratio of the vapor that is not condensed and is discharged to the outside of the device becomes high, and even if treated with activated carbon, for example,
The ratio of odorous and harmful gases released to the outside of the device also increases. Furthermore, the condensate condensed by the cooling condensing means,
Even if it is treated with activated carbon, it may drop when it is discarded, or it may not be directly discharged to sewage due to the high pollution load. Further, sulfur-based malodorous gas is generated from the condensate, and activated carbon cannot be expected to have a sufficient effect on the reduction of iodine consumption. Therefore, the inventors of the present invention conducted various studies and experiments to reduce the pollution load of the condensate, and found that the precipitate generated by the heating of the heating means stayed in the vicinity of the heating means for a long time and continued to be heated. It was found that the precipitate was overheated and decomposed, resulting in a bad smell of sulfur and iodine consumption. Therefore, the heat treatment means for evaporating and condensing the photographic processing waste liquid prevents the precipitate from being decomposed by heat, and the precipitate obtained by evaporative concentration is separated and discharged as quickly as possible. It is possible to effectively prevent the sulfur-based odor of the condensate generated by evaporative concentration, and to greatly reduce the iodine consumption. The present invention has been made in view of the above conventional problems, and a first object of the present invention is to reduce the pollution load of the condensate obtained by cooling and condensing the vapor generated by the evaporative concentration of the photographic processing waste liquid at low cost. It is an object of the present invention to provide a processing apparatus for photographic processing waste liquid that can be reduced by. The second object of the present invention is to prevent the sulfur-based odor of the condensate obtained by cooling and condensing the vapor generated by the evaporative concentration treatment, further reduce the thermal decomposition of the precipitate, and significantly reduce the iodine consumption. An object of the present invention is to provide a processing device for processing waste liquid. [Means for Solving the Problems] In order to solve the problems of the present invention, in a photographic processing waste liquid processing apparatus in which a photographic processing waste liquid stored in an evaporation means is heated and evaporated and concentrated by a heating means, Means and / or evaporating means, a bubble separating means for promoting the separation of vapor bubbles generated on the surface in contact with the photographic processing waste liquid, and a precipitation separation for removing precipitates generated by evaporative concentration, and heating the heating means. The capacity is set to 20 W / cm ² or less, and a filter is used for the precipitation separating means, and the pore size of this filter is 1 to 200 μm. Therefore, the photographic processing waste liquid is heated by the heating means to evaporate and concentrate, and the precipitate generated thereby is separated and discharged by the precipitation separating means. Further, at this time, vapor bubbles formed on the surface of the heating means and / or the evaporating means in contact with the photographic processing waste liquid are promoted by the bubble removing means, so that the precipitate generated by the heating of the heating means is near the heating part. It can be prevented from staying for a long time and locally heated to be decomposed by overheating, suppress the generation of sulfur-based malodor, and reduce iodine consumption. Further, when the heating capacity for heating by the heating means is set to 20 W / cm ² or less, it is possible to reduce the overheat decomposition of the precipitate, more preferably 1 to 15 W / cm ² , and more preferably 2 to It is used in the range of 10 W / cm ² , and if the heating capacity is increased, overheating of the precipitate is likely to occur, and if it is lowered, heat cannot be transferred to the photographic processing waste liquid, so 2 W / cm ² or more is preferable. In the present invention, a filter such as a cylindrical film or a filter bag is used as the precipitation separating means, but a centrifugal separator, a cyclone or the like may be used. If a filter is used, the pore size is preferably 1-20
0 μm, the heating capacity for heating by the heating means is 20 W / c
Set it to m ² or less, and use a pore size of 1 to 20 as precipitation separation means.
By using a filter of 0 μm in combination, the thermal decomposition of the precipitate can be reduced, and the iodine consumption can be reduced more effectively. The pore size of the filter is more preferably 5 to 200 μm, most preferably 5 to 100 μm.
Is the range. In the present invention, it is preferable to evaporate and concentrate by the evaporating means, and to take out the precipitate produced thereby from the lower part of the evaporating means and return it to the upper part because the taking out and circulation of the precipitate are easy. Further, in the present invention, a waste liquid supply tank is provided after the precipitation separating means, and the waste liquid supply tank is circulated to the evaporation means via the waste liquid supply tank. In the present invention, the heating means may be a nichrome wire, a heater formed by machining such as a cartridge heater, a quartz heater, a Teflon heater, a rod heater or a panel heater, or a microwave. Further, a conductive material may be brought into direct contact with the photographic processing waste liquid, and an electric current may be caused to flow in the photographic processing waste liquid by the conductive material and the photographic processing waste liquid may be heated. The heating means is disposed so as to be wholly immersed in the photographic processing waste liquid, or is partially disposed so as to be disposed, and thus the evaporation of the photographic processing waste liquid may be caused by heating by the evaporation means. The waste liquid treatment efficiency (treatment speed) can be improved, which is preferable. This evaporation means may be of any form, a cube,
It may be a cylinder, a polygonal note including a square note, a cone, a polygonal note including a square pyramid, or a combination of some of these, but the temperature of the photographic processing waste liquid in the vicinity of the heating means and at the bottom. The length is preferably long so that the difference becomes large, and further, it is preferable to make the space above the surface of the waste liquid in the evaporation means as wide as possible in order to minimize blowout accidents due to bumping. 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., but in view of safety and corrosion resistance, stainless steel (preferably SUS304 and SUS3
16, particularly preferably SUS316) and titanium are preferred. The bubble removing means of the present invention is configured to supply and stir the gas into the photographic waste liquid in the evaporation means. in this case,
Air, nitrogen, etc. are supplied as gas, and the supply amount is 2% or more of the steam generation amount, preferably 10% or more and 100% or less, and more preferably 30 to 50% in the range due to overheating of steam bubbles. It is preferable in terms of preventing loss reduction. Further, by supplying gas, the temperature of the photographic processing waste liquid in the evaporation means is below the boiling point, 80 ° C or higher, more preferably 100 to 9
The temperature is preferably 0 ° C. Further, the gas supply position is preferably near the surface of the heating means, and it is particularly preferable to supply the gas to a position below the heating means because vapor bubbles can be reliably released. The bubble removing means of the present invention is configured to forcibly circulate and agitate the photographic processing waste liquid in the evaporating means, so that vapor bubbles generated on the surface of the heating means can be quickly removed. preferable. Expressing the diffusion velocity at this time as an ascending linear velocity, 0.05 to 1 m / sec, more preferably 1 to 50 cm
/ sec, more preferably 2 to 20 cm / sec. Also, LH
Expressed as an SV value, 100 to 10,000 L / hr, more preferably 3
It is from 00 to 2000 L / hr. Further, the bubble removing means of the present invention can be configured to vibrate the heating means in the evaporation means. In this case, the heating means is directly vibrated. Further, the bubble removing 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 removal of vapor bubbles generated in the heating means. it can. The frequency of ultrasonic waves is preferably 10 KHz to 100 KHz, more preferably 15 KHz to 50 KHz, and this frequency is arbitrarily set depending on the place where the ultrasonic wave generating means is provided, the temperature and concentration of the photographic processing waste liquid, etc. The intensity of the ultrasonic waves is 1 to 300 dB, more preferably 2 to 200 dB. In the present invention, it is preferable to use the bubble removing means in combination, and it is particularly preferable to use the blowing of air or gas together with the circulation of the concentrated photographic processing waste liquid. Further, the heating means and the evaporation means of the present invention can be processed to have irregularities. In this case, a ceramic (eg Al
₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ etc.), metal, metal oxide, etc.
It is preferable because it has corrosion resistance and heat resistance. In this case, particles having a size of 0.1 μm or more are used as the coating material, and coating is performed by using various thermal spraying techniques. As the coating method, it is preferable to use an electrolytic plating method or a brush coating method. As this electrolytic plating method, a lumpy metal is plated on the surface by electrolytic plating. Ni, Cr or the like is used as the metal. In addition, particles of non-electrolyte such as activated carbon or 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, and metal powder are suitable,
For example, it is dispersed in a solvent such as Teflon or other organic polymer adhesive and applied to the surface, and then firmly bonded by using, for example, a heating method. Further, the concavo-convex processing of the present invention may be processing performed by blast processing or sand blast processing. In these treatments, the surface is sufficiently sanded with a file or sandpaper to make the surface uneven, or the surface is roughened by rough polishing. The deeper and finer the flaw, the higher the effect of removing vapor bubbles. The concavo-convex process is preferably a porous concavo-convex process so that bubbles can be released at an early stage. For example, the process is performed with a thickness of 1 μm unit or more and less than 10 mm. As the porous irregularity processing, the above-mentioned thermal spraying, electrolytic plating method, and brush coating method are used. Further, the present invention, instead of surface treatment as described above,
It is also possible to attach a member processed by the same means to the surface. For example, as a processed material, a sintered metal using metal particles, a metal net, or the like is attached to the surface of the heating means or the evaporation means to make the surface porous. Next, as a typical example of the photographic processing waste liquid capable of performing the processing according to the present invention, those described in Japanese Patent Application No. 62-194615 filed by the applicant earlier are used,
Particularly, in the processing apparatus of the present invention, it is effective in the case of a photographic processing waste liquid containing a large amount of thiosulfate, phosphite and ammonium salt, and particularly in the case of containing ferric organic acid complex salt and thiosulfate. It is extremely effective. As a preferred application example of the present invention, it is suitable for processing a photographic processing waste liquid generated with the development processing of a photographic light-sensitive material by an automatic developing machine in the automatic developing machine or in the vicinity thereof. Here, the automatic processor and the photographic processing waste liquid will be described. Automatic developing machine In FIG. 1, the automatic developing machine is designated by reference numeral 100, and the one shown in the drawing continuously rolls the photographic light-sensitive material F into the color developing tank CD, the bleach-fixing tank BF, and the stabilizing processing tank Sb. It is a system in which it is photographed after being guided to, and dried and then wound up. Reference numeral 101 is a replenisher tank, and the sensor 102 detects the amount of photographic processing of the photographic photosensitive material F, and the replenisher is replenished to each processing tank by the controller 103 according to the detection information. When each photo processing tank is replenished with replenishing liquid, it is discharged as overflow waste liquid from the processing tank,
Collected in 104. As a means for transferring the overflowed photographic processing waste liquid to the stock tank 104, a simple method is to drop it naturally through a guide tube. In some cases, forced transfer may be performed using a pump or the like. Further, as described above, the components in the photographic processing waste liquid are different in each of the photographic processing tanks CD, BF, and Sb, but in the present invention, it is preferable to mix and process all the photographic processing waste liquids at once. [Embodiment] FIG. 2 is a schematic configuration diagram showing a photographic processing waste liquid processing apparatus of the present invention. In the figure, reference numeral 1 is an evaporation pot as an evaporation means, which is composed of a cylindrical upper portion 1a having a large diameter and a cylindrical lower portion 1b having a small diameter, and a heating means 2 is arranged on the upper portion 1a.
The heating means 2 is provided so as to be immersed in the photographic processing waste liquid, and is heated at a heating capacity of 20 W / cm ² or less to evaporate and concentrate. A circulation system 70 is provided between the lower part 1b and the upper part 1a of the evaporation tank 1.
Is provided. The circulation system 70 includes a pump 71 and a precipitation separating means 72. The pump 71 is driven to drive the lower part 1b of the evaporation tank 1.
The precipitate is taken out from the bottom of the evaporator, and the remaining liquid due to this separation is returned to the upper portion 1a of the evaporator 1. The precipitation separating means 72 is composed of a filter bag 72a, and this filter bag 72a is, for example, steel 72b having a hole diameter of 2 mm.
The liquid separated into the receiver 72c via the is returned to the evaporation tank 1. Further, a vapor discharge pipe 9 is provided in the upper portion 1a of the evaporation tank 1, and the vapor discharge pipe 9 is connected to a distillate introduction pipe 12 through a heat exchanger 10 and a condensing means 11. In the condensing means 11, a large number of cooling radiator plates 12 are attached to the steam discharge pipe 9.
Is provided, and a liquid level sensor 14 is further provided. A cooling water introducing pipe 15 is provided below the condensing means 11, and is connected via a cooling water circulation pump 16 to a shower pipe 17 having a large number of small holes. The air in the condensing means 11 is discharged to the outside of the processing device by the air cooling fan 18. The accumulated liquid introducing pipe 12 is connected to the inside of the accumulated liquid tank 19, but the tip 12a of the accumulated liquid introducing pipe 12 has the accumulated liquid tank 19
The bubbling mechanism 20 is formed below the liquid level surface of the. Further, an activated carbon cartridge 21 that stores activated carbon is provided above the liquid storage tank 19. The reservoir tank 19 is also provided with an air introduction pipe 22, which is introduced into the waste liquid of the evaporation tank 1 via an air pump 23. A waste liquid supply tank 24 is provided with a waste liquid introduction pipe 25, and is connected to the evaporator upper portion 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. A guide pipe 28 is further provided in the upper portion 1a of the evaporator 1 and is connected to a waste liquid supply tank 24 via a plunger disk 29. The upper portion 1a of the evaporator 1 is also provided with a temperature sensor 30. In the upper part 1a of the evaporator 1, a supply pipe 80 is provided at a position below the heating means 2.
Is connected and air is introduced from here. This air rises in the photographic processing waste liquid and agitates the surface of the heating means 2 to separate vapor bubbles. At this time, the photographic processing waste liquid flows due to the rise of air, which makes it easier to peel off by the steam method. The mounting position of the air supply pipe 80 is not limited,
There is no limitation, and for example, direct supply may be made toward the heating means 2. Further, the heating means 2 is composed of, for example, a heater, and the heater surface may be subjected to uneven processing. In this case, the contact angle of the vapor bubble with respect to the surface is increased, and the vapor bubble is promptly released. It As described above, since the phenomenon that vapor bubbles adhere to the surface of the heating means 2 forever and there is no heating occurs, the surface temperature of the heating means 2 rises and is overheated to decompose the thiosulfate component in the photographic processing waste liquid. The decomposition and generation of hydrogen sulfide is reduced. Further, it is possible to prevent a decrease in thermal efficiency due to overheating of steam bubbles. Next, an outline of the process of heating and evaporating using this apparatus will be described. About 20 overflow liquids from the automatic developing machine are stored in a waste liquid supply tank 24, and an activated carbon cartridge 21 filled with activated carbon, a reservoir liquid introducing pipe 12 and an air introducing pipe 22 are connected to the reservoir liquid tank 19. After supplying water into the condensing means 11, when the switch is turned on,
The air pump 23 operates and the air in the reservoir tank 19 is introduced into the evaporation tank 1 through the air introduction pipe 22. Then, the fan 18 for air cooling and the cooling water circulation pump 16 are operated in this order, and the accumulated water passes through the cooling water introduction pipe 15 and the shower pipe.
17 or a heat radiating plate of the steam discharge pipe 9 housed in the condensing means 11
It is circulated in such a manner that it is supplied to the upper part of 13 and accumulates again in the lower part of the condensing means 11. The bellows pump 26 operates, the waste liquid in the waste liquid supply tank 24 passes through the waste liquid introduction pipe 25, and after passing through the heat exchange means 10,
It is sent to the evaporation kettle 1. The amount of waste liquid increases in the evaporator 1
When the liquid surface level sensor 4 detects the liquid surface 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 turned on to start heating and evaporation. Although it is evaporated and concentrated by heating and evaporating, air is introduced from the supply pipe 70, and by this stirring, evaporating bubbles are separated from the heating means 2 at an early stage, and thermal decomposition is reduced because the bubbles are thin, and vapor generated by evaporating and condensing. The odorous gas present therein can be significantly reduced. Further, even if the concentration proceeds, the precipitate is taken out from the lower part 1b of the evaporation tank 1 by driving the pump 71, is supplied to the precipitation separating means 72, and is separated and discharged into a precipitate having a higher concentration here. . Then, the remaining liquid is returned to the evaporation tank 1 and such circulation is performed during the evaporation concentration process to sequentially take out the precipitate, so that it does not accumulate in the vicinity of the heating means 2. Therefore, the heating means 2 prevents the precipitate from being decomposed by heating, and reduces the generation of hydrogen sulfide or sulfur odor even if the concentration proceeds. By this process, the amount of waste liquid in the evaporation tank 1 is reduced,
When the liquid level decreases and the liquid level sensor 4 does not detect the liquid level for more than 3 seconds, the bellows pump is restarted.
The operation of turning on the switch 26 and supplying the waste liquid in the waste liquid supply tank 24 into the evaporator 1 is repeated. The vapor evaporated from the evaporator 1 passes through the vapor discharge pipe 9, and after this vapor exchanges heat with the waste liquid in the heat exchanger 10, the condensing means
When it passes through 11, a part of it is condensed into a condensate.
This condensate is sent together with the remaining gas in the vapor through the distillate introduction pipe 12 into the distillate tank 19, is discharged from the tip 12a below the distillate surface, and the condensed water is stored in the distillate tank 19. It At this time, bubbling is performed by the gas released from under the liquid surface rising in the liquid liquid, and the gas such as hydrogen sulfide that melts in the liquid liquid is expelled from the liquid by the bubbling. Is the operation of the air pump 23,
It is returned from the reservoir tank 19 via 22 to the photographic processing waste liquid located in the lower portion of the evaporation tank 1. The reservoir tank 19 communicates with the atmosphere via an activated carbon cartridge 21 filled with activated carbon to prevent odors from being released into the atmosphere. And the waste liquid supply tank 24
When the liquid level sensor 27 detects that the liquid inside has been exhausted, the operation of the bellows pump 26 stops,
The switch of the heating means 2 is turned off, and the cooling water circulation pump 16 and the air cooling fan 18 are stopped after 2 hours, the lamp is turned on, the buzzer sounds and the evaporative concentration process is completed, and the air pump 23 is turned on. Stop.
Here, the ball valve 3 is opened, the sludge in the evaporator 1 is dropped into a polypropylene bag, and then the O-ring 8 is removed and taken out. When the liquid level sensor 14 detects that the condensing means 11 has run out of water during the evaporative concentration process, the lamp is turned on and the buzzer sounds to notify that the water has run out. Further, during the evaporative concentration process, the liquid level in the evaporator 1 is abnormally lowered for some reason, and the temperature in the evaporator 1 is decreased by emptying.
When the temperature sensor 30 detects that the temperature has risen to 120 ° C,
After the lamp is turned on, the warning buzzer sounds, and the switch of the heating means 2 is turned off, the evaporative concentration process is interrupted by the series of operations described above. In FIG. 3, a circulation system 70 is provided in the vicinity of the heating means 2 of the evaporator 1 and a pump 71 of the circulation system 70 drives the photographic processing waste liquid to circulate from the bottom to the top. As a result, the photographic processing waste liquid agitates the surface of the heating means 2 so that the vapor bubbles can be removed early. FIG. 4 shows the heating means 2 of the evaporation pot 1 at the bottom of the evaporation pot 1.
It is designed to be heated from the outside in preparation for the outer circumference of 1b. An ultrasonic transmitter 73 is provided at a lower position in the vicinity of the heating means 2, and this operation vibrates the photographic processing waste liquid, thereby heating the heating means 2
The vapor bubbles generated on the inner wall of the lower portion 1b of the evaporator 1 where is located are quickly released. FIG. 5 shows that the heating means 2 is provided in the photographic processing waste liquid from the upper portion 1a of the evaporation pot 1, and the heating means 2 itself is a vibrator of mechanical means.
The vibration of the heating means 2, which is forcibly vibrated by 74, forcibly releases the vapor bubbles generated on the surface. The vibration frequency at this time can be set arbitrarily. FIG. 6 shows a combination of gas blowing and circulation of photographic processing waste liquid. That is, a circulation pump 75 is provided, and the photographic processing waste liquid concentrated by the circulation pump 75 from the lower portion 1b of the evaporator 1 is circulated through the pipe 76, and the evaporator 1 at the position where the heating means 2 is provided. It is sprayed toward the inner wall of the. Further, by driving the air pump 23, the gas from the accumulated liquid introducing pipe 12 is blown into the inside from a position below the evaporation means 2. 7 to 9 show still another embodiment of the precipitation separating means 72, and FIG. 7 uses a cylindrical filter 72d. FIG. 8 shows a support base 72e having a net-like large hole provided with a filter bag 72a. The filter bag 72a is a metal fitting 72.
It is removable with f. In FIG. 9, the lower container 72g and the upper container 72h are connected by the connecting portion 72i, the filter 72j is arranged in the upper container 72h, and the precipitate is taken out to the lower container 72g. When removing the precipitate, the pump 77 is driven to drain the liquid. The above-mentioned precipitation separating means and air bubble separating means may be used in combination, or any combination thereof may be used.

【Example】

MPS processing system Paper automatic developing machine RP-800 (made by Konica Corporation) is used to paint commercially available color photographic paper (made by Konica Corporation), and then continuous processing is performed using the following processing steps and processing solutions. I did. Standard processing process (1) Color development 40 ° C 3 minutes (2) Bleach fixing 38 ° C 1 minute 30 seconds (3) Stabilization 25 ° C to 35 ° C 3 minutes (4) Drying 75 ° C to 100 ° C About 2 minutes Treatment liquid Composition [Color developer tank liquid] Ethylene glycol 15 ml Calcium sulfite 2.0 g Potassium bromide 1.3 g Sodium chloride 0.2 g Potassium carbonate 24.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline Sulfate 5.
5g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0g Hydroxylamine sulfate 3.0g 1-Hydroxyethylindene-1,1-diphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride-6 Water salt 0.7g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Add water to make 1 and adjust pH to 10.20 with potassium hydroxide and sulfuric acid.
And [Color development replenisher] Ethylene glycol 20 ml Potassium sulfite 3.0 g Potassium carbonate 24.0 g Hydroxyamine sulfate 4.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 7.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.5g 1-Hydroxyethylindene-1,1-diphosphonic acid 0.5g Hydroxyethyliminodiacetic acid 5.0g Magnesium chloride hexahydrate 0.8g 1 2,2-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Add water to make 1 and adjust pH to 10.70 with potassium hydroxide and sulfuric acid.
And [Bleaching and fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium dihydrate
60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.ml Ammonium sulfite (40% solution) 27.5ml Add water to bring the total volume to 1 and adjust to pH 7.1 with potassium carbonate or glacial acetic acid. [Bleach-fix replenisher A] ethylenediaminetetraacetic acid ferric ammonium dihydrate
260.0g Potassium carbonate 42.0g Add water to bring the total volume to 1. The pH of this solution is 6.7 ± 0.1 with acetic acid or aqueous ammonia.
And [Bleach-fixing replenisher B] Ammonium thiosulfate (70% solution) 250.0 ml Ammonium sulfite (40% solution) 25.0 ml Ethylenediaminetetraacetic acid 17.0 g Glacial acetic acid 85.0 ml Add water to bring the total volume to 1. The pH of this solution is 5.3 ± 0.1 with acetic acid or aqueous ammonia.
Is. [Stabilizing tank replacement solution and replenisher] Ethylene glycol 1.0 g 2-Methyl-4-isoazolin-3-one 0.20 g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.0 g Ammonia water (water Ammonium oxide 25% aqueous solution) 2.0 g Water to 1 and 50% sulfuric acid to pH 7.0. An automatic developing machine was filled with the above-mentioned color developing tank solution, bleach-fixing tank solution and stability tank solution, and the above-mentioned color developing replenishing solution and bleach-fixing replenishing solutions A and B were stabilized while processing the commercially available color photographic paper sample. A running test was performed while replenishing the replenisher with a bellows pump. The amount of replenishment is 1 m ² of color paper as the amount of replenishment to each color development tank.
90 ml, bleach-fix replenisher as a replenisher for the bleach-fix tank
50 ml each of A and B, and 250 ml of a stable replenisher alternative to washing with water as a replenishing amount to the stabilizing tank were replenished. The stabilizing tank of the automatic processor is a stabilizing tank that is the first to third tanks in the direction of sample flow, replenishment is performed from the final tank, and overflow liquid from the final tank is allowed to flow into the preceding tank. Further, a multi-layer countercurrent system is adopted in which the overflow liquid is allowed to flow into the tank at the preceding stage. Continuous treatment was carried out until the total replenishment amount of the stabilizing solution as a substitute for washing was 3 times the capacity of the stable tank. In addition, after exposing each color negative film GX-100 (manufactured by Konica Corporation) by a conventional method, using an automatic processor modified from the negative film processor NPS-FP34 (manufactured by Konica Corporation) under the following development processing conditions. The treatment was carried out continuously. From anhydrous washing stable (second tank) to anhydrous washing stable (first tank),
Counter current method (two-stage countercurrent) is used, and bleach-fixing is also performed from bleach-fixing (second tank) to bleach-fixing (first).
(Counter current type). The amount of treatment liquid carried in from the previous tank of each tank was 0.6 ml / dm ² . The formulation of the tank liquid and each replenishing liquid is shown below. Color developing tank liquid; potassium carbonate 30 g sodium sulfite 2.0 g hydroxylamine sulfate 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.0 g hydroxyethyliminodiacetic acid 3.0 g magnesium chloride 0.3 g odor Potassium iodide 1.2 g Sodium hydroxide 3.4 g N-ethylene-N-β-hydroxyethyl-3-methyl-4-aminoaniline hydrochloride 4.6 g Water was added to make 1 and the pH was adjusted to 0.1 with sodium hydroxide. Color development replenisher; potassium carbonate 40 g sodium sulfite 3.0 g hydroxylamine sulfate 3.0 g diethylenetriaminepentaacetic acid 3.0 g potassium bromide 0.9 g sodium hydroxide 3.4 g N-ethylene-N-β-hydroxyethyl-3-methyl-4 -Aminoaniline hydrochloride 5.6 g Water was added to make 1 and the pH was adjusted to 10.1 with sodium hydroxide. Bleach-fixing tank solution and replenisher; diethylenetriaminepentaacetic acid ferric ammonium salt 0.5 mol hydroxyethyliminodiacetic acid 20 g ammonium thiosulfate (70% wt / VO) 250 ml ammonium sulfite 15 g 2-amino-5-mercapto-1,3 , 4-thiadiazole
1.0 g Ammonia water (28%) 20 ml Water was adjusted to 1 and the pH was adjusted to 7.6 with acetic acid and ammonia water. Anhydrous washing stability tank liquid and replenisher; 5-chloro-2-methyl-4-isothiazolin-3-one 0.01 g 2-Methyl-4-isothiazolin-3-one 0.01 g Ethylene glycol 2.0 g Diethylenetriamine ferric ammonium acetate Salt 0.03
Adjust to 1 with molar water and adjust to pH 10.0 with ammonium and sulfuric acid. Stabilization tank solution and replenisher solution; formalin (37% aqueous solution) 3 ml Conidax (Konica Corporation) 7 ml Add water to finish to 1. Continuous processing was performed until the tank replenishment amount of the color developing solution became three times the capacity of the color developing solution tank. The waste liquid of the color negative film and the color paper was mixed at a ratio of 1: 1 and used.

[Experiment 1] In the case of using the waste liquid described above, the processing apparatus for the photoprocessing waste liquid of FIG.
In contrast to the one using a filter bag having a pore size of 20 μm as the sedimentation separation means, the gas supply means for supplying gas shown in FIG. 2, the means for circulating the liquid shown in FIG. 3 and the one shown in FIG. An experiment was carried out by combining a device that gives a sound wave and a device that mechanically vibrates shown in FIG. Table 1 shows the measurement results of iodine consumption (unit: ppm) measured in this experiment. As is clear from this table, the combined use of the precipitation separation means and the bubble separation means enabled the iodine consumption to be greatly reduced.

[Experiment 2] Using the treatment apparatus shown in FIG. 2, the pore size of the filter bag of the sedimentation separation means was changed from 0.2 to 5000 μm as shown in the table below, and the gas supply shown in FIG. Experiments were carried out using the liquid circulation shown in FIG. In this treatment, iodine consumption was measured 1 hour after the operation and 12 hours after the operation. The measurement results are shown in Table-2. As is clear from this table, the combined use of a plurality of bubble separation means with the precipitation separation means enabled the iodine consumption to be further reduced.

[Experiment 3] Further, in the treatment apparatus shown in FIG. 2, the heating capacity was changed between the case where the precipitation separation means was not provided and the case where the filter bag was provided as the precipitation separation means and the pore size was 20 μm. Was done. In this experiment, the amount of iodine consumed after a predetermined operation was measured. The measurement results are shown in Table-3. As shown in this table, it is understood that the iodine consumption varies depending on the heating capacity, and 20 W / cm ² or less is preferable. [Effects of the Invention] As described above, the present invention relates to an apparatus for treating photographic processing waste liquid,
Since the heating means and / or the evaporating means are provided with a bubble separating means for promoting the separation of vapor bubbles generated on the surface in contact with the photographic processing waste liquid, and a precipitation separating means for removing a precipitate generated by evaporative concentration, Means for facilitating the desorption of vapor bubbles generated on the surface of the heating means and / or the evaporating means in contact with the photographic processing waste liquid by the defoaming means. It is possible to prevent heat-induced decomposition by heating, suppress generation of sulfur-based malodor, reduce iodine consumption, and reduce pollution load at low cost. Further, by setting the heating capacity for heating by the heating means to 20 W / cm ² or less, and using a filter for the precipitation separating means, and setting the pore size of this filter to 1 to 200 μm,
The thermal decomposition of the precipitate can be reduced, and the iodine consumption can be reduced more effectively.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an automatic processor, FIGS. 2 to 6 are schematic configuration diagrams showing an embodiment of the present invention, and FIGS. 7 to 9 are schematic diagrams of another embodiment of a precipitation separating means. is there. In the drawings, reference numeral 1 is an evaporation pot, 2 is heating means, 11 is condensation means,
19 is a sump tank, 24 is a waste liquid supply tank, 70 is a circulation system, 71
Is a pump, 72 is a precipitation separating means, 73 is an ultrasonic transmitter, and 74 is a vibrator.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Naoki Takabayashi, No. 1 Sakura-cho, Hino-shi, Tokyo Konica Co., Ltd. (56) References JP-A-63-236585 (JP, A)

Claims (1)

[Claims] 1. A processing apparatus for a photographic processing waste liquid, wherein a photographic processing waste liquid stored in an evaporation means is heated by a heating means to evaporate and concentrate the photographic processing waste liquid, the surface of the heating means and / or the evaporation means being in contact with the photographic processing waste liquid. Equipped with a bubble separating means for promoting the separation of the generated vapor bubbles and a precipitate separating means for removing a precipitate generated by evaporative concentration, and the heating capacity of the heating means is set to 20 W / cm ² or less, and the precipitate separation A filter is used as a means, and the pore size of this filter is 1 to 200
An apparatus for treating photographic waste liquid, which is characterized by having a size of μm.