JPH0783867B2 - Evaporative concentration processing equipment for photographic processing waste liquid - Google Patents

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an evaporative concentration processing apparatus for evaporatively processing 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,
In particular, the present invention relates to an apparatus for evaporative concentration of photographic processing waste liquid, which is suitable for processing in an automatic processor or in the vicinity of the automatic processor. [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. ,
It is performed by combining steps using a treatment liquid having one or more functions such as washing and stabilizing. 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). (For example, silver complex salt) is removed to maintain the performance of the processing solution constant by keeping the composition of the processing solution constant, and the replenisher is replenished with the replenisher for the above replenishment.
A part of the processing liquid is discarded for the purpose of removing thickening components in photographic processing. 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 water of washing water, cooling water of an automatic processor, etc., and then disposed of in sewers 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 photographic processing company has a waste liquid processing company specialized in collecting the waste liquid for a recovery fee, and has installed 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. It has the drawback that it requires More specifically, as a pollution treatment method for reducing the pollution load of the photographic processing waste liquid, an activated sludge method (for example, JP-B-51-12943 and JP-B-51-7952) and an evaporation method (JP-A-4949) -89437 and 56-33996, etc.), electrolytic oxidation method (JP-A-48-84462, JP-A-49-119458)
No. 5, Japanese Patent Publication No. 53-43478, Japanese Patent Publication No. 49-119457, etc.), Ion exchange method (Japanese Patent Publication No. 51-37704, Japanese Patent Publication No. 53-383, Japanese Patent Publication No. 53-43271, etc.), Reverse osmosis method (JP-A-50-22463, etc.), chemical treatment method (JP-A-49-64257, JP-B-57-3)
7396, JP-A-53-12152, JP-A-49-58833, JP-A-53-63
No. 763, Japanese Examined Patent Publication No. 57-37395, etc.) are known, but they are still insufficient. On the other hand, due to restrictions on water resources, rising water supply and drainage costs, simplicity of automatic developing machine equipment, and the working environment around the automatic developing machine, in recent years, stabilization processing, which is an alternative to water washing, has been used. In particular, photographic processing by an automatic developing machine (so-called anhydrous washing automatic developing machine) that does not require piping for water supply / drainage for washing is becoming popular. In such a treatment, it is desired that the cooling water for controlling the temperature of the treatment liquid be omitted. In such photographic processing that does not substantially use rinsing water or cooling water, it is not diluted by water as compared with the case where there is photographic processing waste liquid from an automatic processor, so its pollution load is extremely large, while the amount of waste liquid is small. is there. Therefore, due to the small amount of the waste liquid, it is possible to omit the pipe outside the machine for supplying and discharging the waste liquid, and thus it is difficult to move the pipe after the installation in order to install the pipe in which the drawbacks of the conventional automatic developing machine can be considered. The space under the foot is small, the piping work at the time of installation is very expensive, the drawbacks such as the energy cost of hot water supply pressure are eliminated, and it is extremely compact and simple enough to be used as an office machine. Great advantages are demonstrated. However, on the other hand, the waste liquid has a very high pollution load, and it has become impossible to dispose of it not only in rivers but also in sewers in accordance with the pollution regulations. Furthermore, such photographic processing (using a large amount of running water,
Although the amount of waste liquid in the process (without washing) is small, for example, in a relatively small-scale color processing laboratory, the amount is about 10 per day. Therefore, it is generally collected by a waste liquid collection company and treated as a secondary and tertiary treatment to render it harmless, but not only the waste liquid collection price increases year by year due to soaring collection costs, but the collection efficiency is poor at minilabs, etc. We are unable to get them to collect the waste, which causes problems such as filling up the store with waste liquid. On the other hand, in order to easily process the photoprocessing waste liquid in order to solve these problems even in a minilab or the like, research has been conducted on heating the photoprocessing waste liquid to evaporate the water to dryness or solidify. , No. 60-70841, etc. According to the research conducted by the inventors, when the photographic processing waste liquid is subjected to the evaporation treatment, harmful or extremely malodorous gas such as sulfurous acid gas, hydrogen sulfide and ammonia gas is generated. It has been found that this is caused by decomposition of ammonium thiosulfate or zinc salt (ammonium salt, sodium salt or potassium salt), which is often used as a fixing solution or a bleach-fixing solution of a photographic processing solution, due to high temperature. Further, during evaporation processing, the water content in the photographic processing waste liquid becomes vapor and is gasified, so that the volume expands and the pressure in the evaporation tank increases. Therefore, this pressure causes the harmful or malodorous gas to leak out of the evaporation processing 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 unit such as activated carbon in an exhaust pipe of an evaporation treatment apparatus. However, this method uses water vapor due to a large amount of water in the photographic processing waste liquid to cause dew condensation or condensation in the exhaust gas processing section, and the water covers the gas absorption processing agent.
It has a serious drawback that it instantaneously loses its gas absorption capacity, and it has not yet been put to practical use. [Problems to be Solved by the Invention] In order to solve these problems, the applicants of the present invention provide a cooling and condensing means for condensing vapor generated by evaporation when the photographic processing waste liquid is vaporized, and further generate by condensation. We have previously proposed a method and apparatus for treating photographic processing waste liquid that treats condensed water and also treats non-condensed components and discharges it to the outside. 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 low, the ratio of the vapor that is not condensed and is discharged to the outside of the device becomes high, and even if it is treated with activated carbon, it produces a bad odor. The ratio of harmful gas released to the outside of the device also increases. Furthermore, the condensed water condensed by the cooling condensing means,
Even if it is treated with activated carbon, it may be disposed of at the time of disposal, or it may not be discharged as it is into the sewer because of its high pollution load. Further, in the minilab, the space of the store is extremely limited, and not only the bad smell generated by processing the photographic processing liquid becomes a problem, but also the installation space of the waste liquid processing device itself becomes a problem. Also, the price of equipment and running cost are important issues. Therefore, there is a demand for a compact, inexpensive and low-cost processing apparatus capable of processing photographic processing waste liquid without generating an offensive odor and harmful gas. The present invention has been made in view of the above-mentioned conventional problems, and the present invention has good cooling and condensation efficiency during evaporation processing, more effectively suppresses harmful or malodorous components, and makes the device compact and inexpensive, and It is an object of the present invention to provide an evaporative concentration treatment device for photographic processing waste liquid, which has less harmful or odorous components generated by the heated portion of the photographic processing waste liquid. [Means for Solving the Problems] In order to solve the above-mentioned problems of the present invention, an evaporation concentration processing apparatus for a photographic processing waste liquid having an evaporation pot, a heating means, a steam discharge pipe for guiding evaporated steam, and a steam cooling condensation means. The means for cooling and condensing the steam includes at least means for supplying water to the steam discharge pipe. In the present invention, the vapor discharge pipe of the cooling / condensing means may have any structure of a double pipe type, a coil type, a spiral type, a plate type, a fin tube type, and a trombone type. It is preferable that (air cooling fin) is installed. In the present invention, the water supplied onto the steam discharge pipe may be supplied onto the steam discharge pipe from, for example, a tap of the tap water through the water supply pipe, and optionally via a valve or a solenoid valve (in this case, The means for supplying water is preferably a tap water tap, a water supply pipe, a valve, an electromagnetic valve, etc.), and is a cooling water introducing pipe and a pump (for example, a tube pump,
On the steam discharge pipe via a water supply means such as an electromagnetic metering pump, a plunger metering pump, a bellows pump, a gear pump, a magnet pump, a metering magnet pump, a screw pump, a diaphragm pump, etc. Supplied. Particularly, it is preferable that the water in the water tank, which is provided in the lower portion of the cooling and condensing means, be supplied in the form of a shower on the steam discharge pipe via the pump and is again accumulated in the water tank because of the lower portion. It is configured to do. In this case, by installing a liquid level sensor in the water tank and sending a signal when the liquid level falls below a certain level, you can know that the water has run out,
It is better to supply water again. An air-cooling fan is preferably installed in the cooling / condensing means, but in this case, in particular, in the air-cooling fan, air is discharged to the outside of the evaporative concentration treatment apparatus of the present invention through the radiator plate device. It is preferable to be installed as described above because condensation can be prevented in the electrical equipment section in the evaporative concentration treatment apparatus of the present invention. In the present invention, the heating means may be a nichrome wire, or may be a heater formed by processing such as a cartridge heater, a quartz heater, a Teflon heater, a rod heater or a panel heater. As another embodiment of the heating means, one or more of the heaters described above may be replaced by a high boiling solvent such as silicon oil, magnesium carbonate,
It may be installed in magnesium oxide, diatomaceous earth, etc., and these may be further added to titanium, SUS304 or SUS316.
It may be embedded in a block such as stainless steel and carbon steel. Preferably the heat density of the heating means is substantially 17.2kcal / cm ² or less in the present invention, and particularly preferably more 8.6kcal / cm ² or less. In the present invention, the heat density of the heating means is a value obtained by dividing the total heat capacity of the heating means by the area in which the heating means is in contact with the waste liquid, and in the present invention, the heat density is approximately 17.2 kcal / cm ² or less. As a result, it is possible to suppress the generation of bad odor and harmful gas and prevent bumping. That is, the heat density is about 17.2
When it exceeds kcal / cm ² , the evaporation rate of the waste liquid due to the heating of the heating means is high and the supply of the waste liquid to the surface of the heating means cannot be completed in time, so that a vapor layer is formed on the surface of the heating means. For this reason, it is considered that the steam is superheated in the immediate vicinity of the surface of the heating means to cause a bad odor and also cause bumping. In the present invention, the heat density of the heating means is set to about 17.2 kcal / cm ² or less, and the gas is supplied through the means for supplying the gas into the waste liquid in the evaporation tank to further superheat the steam as described above. It can be efficiently prevented. Further, in the present invention, the heat density of the heating means is approximately 17.2 kcal / c.
m ² or less, and further keep the surface tension of the photographic processing waste liquid in the evaporation tank.
It has a means for supplying a compound capable of controlling 20 to 65 dyne / cm (hereinafter referred to as antifoaming agent or surfactant),
By supplying the defoaming agent into the evaporator through this means, it is possible to prevent an accident that the waste liquid is blown out from the introduction pipe for introducing the vapor into the cooling and condensing means. Furthermore, the most preferred embodiment of the present invention is such that the heat density of the heating means is approximately 17.2 kcal / cm ² or less, and the gas is supplied through the means for supplying the gas into the waste liquid in the evaporation tank,
The anti-foaming agent is supplied through the means for supplying the anti-foaming agent into the evaporation kettle, which effectively prevents the generation of malodorous gas or toxic gas and the accident that the waste liquid in the evaporation kettle is blown out by bumping. You can The heating means may be installed in the waste liquid in the evaporating pot, but in order to further enhance the effect of the present invention and to prevent the deterioration of the thermal efficiency and the corrosion caused by the photographic processing waste liquid sticking to the surface of the heating means. It is preferable that the waste liquid in the evaporation tank is heated through the wall of the evaporation tank provided outside the evaporation tank.
In this case, the heat density of the heating means is a value obtained by dividing the total heat capacity of the heating means by the area in which the heating means is in contact with the waste liquid through the wall of the evaporation tank, and this value is 17.2 kcal / cm ² or less. If it is good. When the heating means is structured to be installed in the waste liquid in the evaporation pot, the heating means adheres to the surface of the photographic processing waste liquid in the process of concentrating or drying the photographic processing waste liquid to dryness, thereby improving the thermal efficiency. In order to prevent the deterioration and the corrosion from occurring remarkably, it is preferable that the surface of the heating means is subjected to a sticking preventive process such as Teflon process (for example, fluororesin coating). Examples of Teflon processing means other than the fluororesin coating include a binder type, a plating type, an oil mixed type, a heat treatment type, and a room temperature compress type. The heating means may be installed at any of the upper, middle, and lower positions of the kettle as long as it can heat the waste liquid in the evaporating kettle. Japanese Patent Application Nos. 60-259001 and 61-288328
As described in No. 3, the heating means is installed so as to heat the upper part of the photographic processing waste liquid in the evaporation pot, and the temperature is different between the photographic processing waste liquid near the heating means and the bottom of the photographic processing waste liquid. It is preferable to install the heating means so that the temperature difference is 5 ° C. or more in order to further enhance the effect of the present invention. The evaporator in the present invention may have any form, and may be a polygonal prism such as a cube, a cylinder, or a quadrangular prism, a cone, a polygonal pyramid such as a quadrangular pyramid, or a combination of some of these. Although it may be present, it is preferable that it is vertically long so that the temperature difference between the photographic processing waste liquid in the vicinity of the heating means and the bottom part becomes large, and in order to minimize the above-mentioned blowout accident due to bumping to the minimum, It is preferable to make the space above the surface of the waste liquid as wide as possible. The material of the evaporator is heat resistant glass, titanium, stainless steel,
Carbon Steel, "Composite Material Technology Collection" (1976, Industrial Technology Center, p213-219), "New Material 1984" (198
4 years, Toray Research Center, p287-315), "Composite materials" (1984, published by The University of Tokyo Press) From the viewpoint of safety and corrosion resistance, stainless steel (preferably SUS304 and SUS316, particularly preferably SUS316) and titanium are preferable. It is also preferable that the evaporation pot is subjected to a sticking prevention process such as the above-mentioned Teflon process. The processing apparatus of the present invention preferably has a means for supplying a gas into the waste liquid inside the evaporation tank, but the gas according to the present invention may be a gas such as air, nitrogen gas, carbon dioxide gas, oxygen gas, or chlorofluorocarbon gas. Any air may be used, but air is preferably used for economic reasons and safety. As the means for supplying the gas, a cylinder in which the gas is sealed may be provided with a pressure valve or a solenoid valve, and when the gas is air, a compressor, an air pump or a bellows type air pump is preferable. Used. When introducing air into the waste liquid tank with an air pump,
The air may be the air inside the processing apparatus or the air outside the processing apparatus. Further, for example, the air in the waste liquid storage tank that stores the waste liquid may be used. In the most preferred embodiment, when the processing apparatus of the present invention has a means for cooling and condensing evaporated vapor, a condensed water storage tank (reservoir) for storing condensed water condensed by means for cooling and condensing air. It is the air in the tank). In this case, the malodorous gas or poisonous gas generated from the condensed water, and the malodorous gas or poisonous gas contained in the vapor not condensed by the cooling condensing means can be sent to the evaporation tank again, so that the malodorous gas or poisonous gas is evaporated and concentrated. Leakage from the processing device can be prevented. The evaporative concentration processing apparatus of the present invention preferably has a means for supplying a compound capable of adjusting the surface tension of the photographic processing waste liquid to 20 to 60 dyne / cm in the evaporation tank. It is particularly preferable that this compound is a compound that can bring the surface tension to 25 to 60 dyne / cm. This compound is a so-called antifoaming agent or a surfactant such as organosiloxane or higher alcohol. As means for supplying this compound into the evaporation tank, there are fixed pumps such as tube pumps, electromagnetic metering pumps, plunger metering pumps, bellows pumps, gear pumps, magnet pumps, metering magnet pumps, screw pumps, diaphragm pumps and non-metering pumps. Is used, but a metering pump is particularly preferably used. The evaporative concentration processing apparatus of the present invention preferably has a means for supplying the photographic processing waste liquid into the evaporation tank. As a means for supplying the photographic processing waste liquid into the evaporator, the same quantitative pump or non-quantitative pump as the means for supplying a compound capable of adjusting the surface tension of the photographic processing waste liquid to 20 to 65 dyne / cm is used. Particularly, a metering pump is preferably used. In the evaporative concentration processing apparatus of the present invention, the means for supplying a compound capable of adjusting the surface tension of the photographic processing waste liquid to 20 to 65 dyne / cm is preferably a means for supplying the photographic processing waste liquid into the evaporation tank. In this case, the compound capable of adjusting the surface tension of the photographic processing waste liquid to 20 to 65 dyne / cm is previously contained in the photographic processing waste liquid. The photographic processing waste liquid overflowing from the automatic processor may be directly supplied as it is to the evaporation tank of the processing apparatus of the present invention. In this case, the means for supplying the photographic processing waste liquid into the evaporation tank is simply an introduction pipe for introducing the overflow into the evaporation tank, but this introduction pipe may be provided with a solenoid valve or the like. It is preferable that the photographic processing waste liquid overflowing from the automatic processor is temporarily stored in a tank (waste liquid tank) and then introduced into the evaporation tank. However, when this waste liquid tank is located above the evaporation tank, It is not always necessary to use a pump as a means for supplying the waste liquid into the evaporation tank, and this means may be an introduction pipe for simply introducing the waste liquid from the waste liquid tank into the waste liquid tank. Etc. may be installed. When the photographic processing waste liquid overflowing from the automatic processor is temporarily stored in the waste liquid tank, this waste liquid tank is a tank (first overflow tank) for storing the overflow from the automatic developing machine, and at the same time, the waste liquid to be supplied to the evaporator is It may be a tank for storing (waste liquid supply tank), or may receive the overflow once in the overflow tank and store a certain amount, and then transfer the overflow to the waste liquid supply tank.
It is preferred that the overflow tank and the supply tank are the same. In this case, the overflow may be stored in the waste liquid tank and then the waste liquid may be supplied from the tank to the evaporation tank. However, after the overflow is stored in the waste liquid tank, the waste liquid tank may be provided near the evaporative concentration apparatus of the present invention or It may be installed inside the evaporative concentration treatment apparatus and used as a waste liquid supply tank. It is preferable to install the waste liquid supply tank inside the evaporative concentration treatment apparatus of the present invention because it can reduce the space. When the waste liquid supply tank is installed inside the evaporative concentration treatment apparatus of the present invention, it is preferable to install the waste liquid supply tank on a frame that can be pulled out in order to improve workability. A liquid level sensor and a means for detecting the weight are installed in the waste liquid supply tank, and when the waste liquid in the waste liquid supply tank is exhausted, the operation of the waste liquid supply means and the operation of the heating means are stopped. Is preferred. As described above, in the waste liquid concentration processing apparatus of the present invention, it is preferable that the photographic processing waste liquid is supplied from the waste liquid supply tank into the evaporation tank through the means for supplying the photographic processing waste liquid into the evaporation tank. The supply of the photographic processing waste liquid by means of has a method of supplying the amount that can be stored in the evaporation pot at a time and not supplying the waste liquid into the evaporation pot during the evaporative concentration, and a means for detecting the amount of the waste liquid in the evaporation pot, According to the signal of this detecting means,
There is a method of continuously or intermittently supplying the waste liquid into the evaporator, but the latter method is preferable because it produces less offensive odor gas or harmful gas. The means for detecting the amount of waste liquid in the evaporation tank is preferably a liquid level sensor, but the supply of waste liquid to the evaporation tank may be controlled by a timer by measuring the evaporation rate in advance, but Since the evaporation rate changes or changes depending on the liquid composition as it advances, it is preferable to detect the amount of waste liquid in the evaporation tank with a liquid level sensor. The operation of the liquid level sensor and the means for supplying the waste liquid into the evaporator is stopped when the liquid level sensor detects the liquid level for a certain period of time, and starts to stop not detecting the liquid level for a certain period of time. Preferably. That is,
In the evaporating pot, the liquid level changes constantly due to boiling,
If this configuration is not adopted, even if the liquid level in the evaporation pot rises and falls due to the liquid level rising and falling due to boiling, waste liquid is not supplied and empty cooking is likely to occur. Repeatedly turning OFF causes a failure. Depending on the capacity of the evaporator, the fixed time differs from 1 second to 10 minutes.
It is preferably 1 second or more and 1 minute or less. Further, as a preferred embodiment, the liquid level sensor is installed in a communication pipe provided outside the evaporation tank. In this case, the change in the liquid surface due to boiling is small, which is preferable. In this case, as described above, the liquid level sensor does not detect the liquid level for a certain period of time, so that the supply of the waste liquid is stopped, and the function to start by not detecting the liquid level for a certain period of time is further added to further improve the malfunction. Is preferred, which is preferable. The evaporative concentration treatment apparatus of the present invention preferably has a means for supplying an alkaline agent into the evaporation vessel. In this case, by preventing the sulfurization of the waste liquid caused by the decrease of the pH of the waste liquid in the evaporator, the generation of offensive odor gas and toxic gas is prevented. Examples of the alkaline agent include hydroxides, carbonates, silicates, phosphates and iodates of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide. . The alkaline agent may be supplied from the stock tank of the alkaline agent aqueous solution in which the alkaline agent is dissolved in water to the evaporator through the various quantitative or non-quantitative pumps as described above, but it is preferable that the alkaline agent is previously waste liquid. It is preferable to add to the waste liquid in the supply tank and supply the waste liquid into the evaporation tank via a supply means for supplying the waste liquid. In this case, the means for supplying the alkaline agent also serves as the waste liquid supply means. It is preferable that the evaporative concentration treatment apparatus of the present invention has means for cooling and condensing the vaporized steam, because it is possible to prevent the generation of malodorous gas or harmful gas, but the condensed water obtained by this is (1) condensed. At least one secondary treatment selected from the following (A) to (J) is performed on water, that is,
(A) Activated carbon treatment, (B) UV irradiation treatment, (C) Reverse osmosis treatment, (D) Oxidizing agent treatment, (E) Electrolytic oxidation treatment,
(F) Aeration treatment, (G) Electrodialysis treatment,
(H) Redistillation treatment, (I) Ion exchange resin treatment, (J)
Adjusting the pH, and (2) using condensed water as dissolved water for the photographic processing liquid. The activated carbon used for the treatment of the activated carbon of the present invention may be any activated carbon capable of adsorbing at least one substance of benzyl alcohol, ammonium compound and sulfur compound. In the present invention, regardless of the raw material and the activation method, either powdered or granular activated carbon can be used, preferably granular activated carbon, particularly preferably palm shell activated carbon and activated carbon having a molecular combing ability. Here, activated carbon having a molecular combing function has slit-shaped pores, and the pores preferably have a size of 6 A or more and a width of 15 A or less. Japanese Patent Application Laid-Open No. 58-14831 discloses activated carbon having such a molecular combing ability.
The contents described in the publication can be referred to. In addition to the activated carbon, the following substances can be used as the adsorptive substance used for the adsorption treatment of the condensed water of the photographic processing waste liquid of the present invention. (1) Clay substance (2) Polyamide-based polymer compound (3) Polyurethane-based polymer compound (4) Phenolic resin (5) Epoxy resin (6) Polymer compound having a hydrazide group (7) Having polytetrafluoroethylene Polymer Compound (8) Monohydric or Polyhydric Alcohol Methacrylic Acid Monoester-Polyhydric Alcohol Methacrylic Acid (9) Polyester Copolymer For details of these substances (1) to (9), see Japanese Patent Application No.
Reference can be made to the description of No. 59-124639 (especially pages 62 to 66). It can be obtained by an ultraviolet irradiation device or a halogen lamp used in the ultraviolet irradiation treatment of the condensed water of the photographic processing waste liquid of the present invention, but it is not particularly limited. The output of this ultraviolet lamp or the like is known to have an output of 5 W to 1 KW, but the output is not limited to this. In the present invention, the ultraviolet lamp may generate electromagnetic waves and light having wavelengths outside the range of 190 nm to 400 nm and irradiate the condensed water obtained from the photographic processing liquid. In addition, infrared rays or the like may be used in combination. The ultraviolet lamp or the like used in the present invention may have a double tube. In the present invention, ultraviolet irradiation means irradiating the condensed water obtained from the photographic processing waste liquid with an ultraviolet ray by using an ultraviolet lamp or the like, and these ultraviolet rays are continuously applied to the condensed water. It may be carried out intermittently as needed. In the reverse osmosis treatment, various reverse osmosis membranes,
A desalination / concentration method and device using a reverse osmosis membrane can be used without limitation. As the reverse osmosis membrane, cellulose acetate, aromatic polyamide, polyvinyl alcohol and polysulfone are preferable, and cellulose acetate is particularly preferably used. Reverse osmosis apparatus, it is operated at a pressure of 40Kg / cm ² ~55kg / cm ² is separation performance, from the viewpoint of throughput. The oxidizing agent used in the oxidizing agent treatment used in the present invention includes metals, non-metal oxides, oxide-oxygen acids and salts thereof, peroxides, compounds containing organic oxygen, and the like. Nitrogen peroxide NOx, chromic anhydride CrO ₃ , selenium dioxide SeO ₂ , manganese dioxide MnO ₂ , lead dioxide PbO ₂ , osmium tetroxide OsO ₄ , silver oxide Ag ₂ O, copper oxide CuO, mercury oxide HgO etc. as oxides. Can be mentioned. Oxygen acids include hot concentrated sulfuric acid H ₂ SO ₄ and nitrite H
NO ₂ , nitric acid HNO _{3 and the} like can be mentioned. As the salt, sodium hypochlorite NaOCl, bleached powder CaOCl ₂ , potassium dichromate K ₂ CrO ₇ , potassium chromate K ₂ Cr ₂ O ₄ , potassium permanganate KMnO ₄ , potassium chlorate KCLO ₃ , perchloric acid Potassium KClO _{4 and the} like can be mentioned. Hydrogen peroxide H as peroxide
₂ O ₂ , sodium peroxide Na ₂ O ₂ , benzoyl peroxide (C ₆ H ₅
COO) ₂ etc. are typical. There are also substances capable of having two or more kinds of valences, for example, trivalent iron ion Fe ³⁺ , divalent copper ion Cu ²⁺ , lead tetraacetate Pb (CH ₃ CO ₂ ) _{4 and the} like.
Other Fenton's reagent (Fe ⁺⁺ ₊ H ₂ O ₂ ), dehydrogenation catalyst (Pt
Se Zn) or the like can also be used as an oxidizing agent. The electrolytic oxidation treatment used in the present invention is a method of oxidizing a substance at an anode by electrolysis, and increases the positive charge of cations, decreases the negative charge of anions, polymerizes anions, oxygen atoms in atomic groups. To increase the number of hydrogen atoms and decrease the number of hydrogen atoms, and the advantage of such electrolytic oxidation as compared with oxidation by an oxidant is that very strong oxidation is possible and there are few by-products. Is. The aeration process used in the present invention is to promote the oxidation by blowing air into the condensed water of the photographic processing waste liquid, and it is preferable to make the air bubbles finer by using a distributor or the like, which improves the bubbling effect. It is possible to improve the efficiency of removing the organic solvent and the like. The electrodialysis treatment used in the present invention is that the cathode and the anode of the electrodialysis tank are partitioned by a diaphragm, the condensed water of the photographic processing waste liquid is put in the partitioned room, and a direct current is passed through the electrodes. The diaphragm is preferably an ion exchange membrane, and more preferably, the space between the cathode and the anode is partitioned by an anion exchange membrane and a cation exchange membrane to form a cathode chamber and a plurality of concentrating chambers (the cathode side is anion exchange membrane). Membrane, chamber with anode side partitioned by cation exchange membrane), multiple desalination chambers (cathode side with cation exchange membrane,
The anode side is composed of a room partitioned by an anion exchange membrane) and an anode room. Condensed water of the photographic processing waste liquid is preferably put into the desalting chamber, but it is also preferable to put it into the concentrating chamber. The electrolytic chamber solution to be placed in the concentrating chamber and the cathode chamber is not particularly limited, and for example, a 0.1 to 0.2 N solution of sodium sulfite, sodium sulfate, sodium chloride, potassium sulfate, sodium thiosulfate, etc. can be preferably used. At this time, it is very preferable to use a processing solution having a fixing ability (bleach-fixing or fixing solution) or a waste solution thereof as an electrolyte solution to be put in the concentrating chamber and the anode chamber, since no electrolyte is required. When used in the present invention, the distillation treatment means a distillation treatment on a concentrated liquid obtained from a photographic processing waste liquid, which is one of so-called rectification operations. It may be batch distillation (including simple distillation and batch rectification) or continuous distillation, and a continuous equilibrium distillation method for continuous rectification can also be adopted. Obtaining pure water (having a remarkably small amount of fractions other than water) by the distillation process can effectively supply water to the photographic processing liquid. It is also advantageous to use suitable separating agents in azeotropic and extractive distillation.
In the present invention, the so-called steam distillation also causes
The next treatment effect can be obtained. The operating pressure may be any of high pressure distillation, atmospheric distillation, vacuum distillation, molecular distillation and molecular distillation. The ion-exchange resin treatment used in the present invention can be carried out by contacting various ion-exchange resins with a photographic processing waste liquid. As the ion-exchange resin, a functional group is bonded to a polymer substrate which is three-dimensionally polycondensed. There are cation exchange resins and anion exchange resins, chelate resins, adsorption resins and the like. Regarding the chemical structuring agent and the usage of the ion exchange resin preferably used in the present invention, Japanese Patent Application No. 59-124639 (particularly No.
See page 57). The pH adjusting treatment used in the present invention is most generally to add a pH adjusting agent to adjust the pH of the condensed water to around neutral, and an acid or an alkali is added depending on the pH of the condensed water. Condensed water is alkaline because it usually contains ammonia, and acids such as sulfuric acid, hydrochloric acid, phosphoric acid, boric acid,
Inorganic acids such as sulfamic acid, carboxylic acids such as acetic acid, oxalic acid, citric acid, malonic acid and tartaric acid, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and acidic salts such as sodium hydrogensulfate and ammonium sulfate Is used. Further, in the present invention, it is desirable that part of the vapor that has not been condensed is discharged to the outside by the cooling / condensing means through the gas treatment column communicating with the outside air. This can prevent the toxic gas from being vaporized by the slight decomposition of the photographic processing waste liquid during the evaporation process and leaking out to the outside, or the evaporation vessel being pressurized so that the toxic gas easily leaks. Furthermore, when this processing device is stopped, the steam or gas expanding due to the heating inside the evaporation kettle contracts, resulting in a depressurized state, and the evaporation kettle is damaged by the load in a completely sealed state. Can also be. The gas treatment column makes it possible to prevent these by introducing outside air from the outside. An adsorbent such as activated carbon or zeolite or a deodorant may be used in the gas treatment column. Since these adsorbents or deodorants require gas flowability, granular ones are preferable, such as those having a particle diameter in the range of 0.3 mm to 15 mm, 0.8 mm to 6 m.
Adsorbents or deodorants having a particle size in the m range are particularly preferred. It is preferable that these deodorants or adsorbents, for example, are pre-packed in cloth, paper or the like and molded, and then placed in the gas treatment column, since the effort at the time of association is small. In the present invention, the concentrated solution after evaporation and concentration may be discharged from the evaporation tank, or, for example, a bag having heat resistance and chemical resistance may be provided in the evaporation tank, and the concentrated solution may be taken out together with the bag after the treatment.
For example, the evaporative concentration treatment apparatus of the present invention is disclosed in Japanese Patent Application No. 60-259001.
In the case of the evaporative concentration treatment device described in Japanese Patent Application No. 61-288328, a device using a rotary screw pump or a concentrated liquid such as a heat-resistant or chemical-resistant bag is supplied from the bottom of the evaporation kettle through a valve. Can be taken out. Examples of heat-resistant and chemical-resistant bags include carbon fiber, aramid fiber,
Teflon resin fiber, hemp, glass fiber, polyethylene foam, polypropylene foam and the like are preferable. In the present invention, it is preferable that the concentrated liquid of the photographic processing waste liquid is absorbed by the carrier to be solidified and then collected. As the carrier, a liquid absorbing resin or a solidifying agent can be considered. The carrier used in the present invention is preferably a carrier that can absorb a concentrated liquid of a photographic processing waste liquid and that does not drip with a liquid-absorbing carrier that has been absorbed, and a so-called liquid-absorbing resin is preferably used. As the liquid absorbing resin, for example, the following ones can be used. Seed polysaccharide, seaweed polysaccharide, resin polysaccharide, fruit polysaccharide, rhizome polysaccharide. Furthermore, zansan gum, zanflow, guaran, succinoglucan, schizophyllan, bullan, succinoglucan, schizophyllan, pullulan, gelatin, casein, albumin, shellac and the like. Starch dielectric, guar gum, locust bean gum derivative, cellulose conductor, alginic acid derivative, vinyl compound, acrylic compound. In addition, polyethylene oxide, etc. Next, preferred examples of the highly absorbent liquid resin used in the present invention will be given. (A) Grafted starch system (A-1) Starch-acrylonitrile graft polymer (A-2) Starch-acrylic acid graft polymer The above (A-1) is described in JP-A-49-43395 and US Pat. 4th, 1st
It can be produced by the method described in JP-B No. 34,863, and the above-mentioned (A-2) can be produced by the method described in JP-B-53-46199. (B) Acrylic acid type (B-1) Sodium polyacrylate type (B-2) Vinyl alcohol-allylic acid copolymer The above (B-2) can be repeatedly used by natural drying and / or forced drying. (C) A polymer having a repeating unit having a structural formula represented by the following (I) or (II), more preferably 10 to 70% by weight of (I) and / or (II), A polymer obtained by copolymerizing with an ethylene-based saturated monomer. In the above formula, R is a hydrogen atom, a methyl group or a halogen atom, Z is an oxy group or an imino group, and n is 0.
Or 1 and R ¹ is an alkylene group having 1 to 6 carbon atoms (including a substituted alkylene group), a cycloalkylene group having 5 to 6 carbon atoms, an arylene group, an arylenealkylene group or an arylenebis. An alkylene group, wherein the alkylene moiety has 1 to 6 carbon atoms and the arylene moiety (which may be substituted) has 6 to 10 carbon atoms, and, for example, Including arylene substituted with a hydrophilic polar group such as where R is an alkyl group having 1 to 4 carbon atoms, R ² , R ³ and R ⁴ are each a hydrogen atom or 1 to 6 An alkyl group having 4 carbon atoms, or together with N to form a heterocyclic group optionally containing a sulfur or oxygen atom, M being a hydrogen atom, a soluble cation or 6
Are ammonium groups, including quaternary ammonium cations having an alkyl group with up to 4 carbon atoms, and X is an acid anion. The halogen substituent of R can be bromine or chlorine,
The alkylene group having ¹ to 6 carbon atoms of R ¹ may be substituted with a hydroxyl group, and the arylene alkylene group of R ¹ contains a phenylene methylene group, a phenylene ethylene group, a phenylene propylene group and a phenylene butylene group. And the arylene bisalkyl group of R ¹ contains a phenylenedimethylene group. Soluble cations of M include sodium and potassium. Heterocyclic groups formed from R ² , R ² and R ⁴ and the N atom to which they are attached include pyridinium, imidazolium, oxazolium, thiazolium and morpholium. The acid anion of X includes chloride, bromide, acetate, p-toluenesulfonate, methanesulfonate, ethanesulfonate, methylsulfate, ethylsulfate and perchlorate. The monomer of the general formula (I) and / or the general formula (II)
The ethylenically unsaturated monomer to be copolymerized with the monomer is preferably one or more monomers having a crosslinkable group, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and active It consists of a methylene group-containing monomer. Polymerized copolymerizable ethylenically unsaturated monomers of this type are described, for example, in US Pat.
3,459,790, 3,488,708, 3,554,987, 3,658,878, 3,929,482 and 3,939,130. Preferred polymers for use in the above are derived from 10-70% by weight of one or more of the monomers listed below or have repeating units thereof: 2-aminoethylmethacrylate hydro Chloride, N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium chloride, N- (2-methacryloyloxyethyl) -N, N, N-trimethylammonium methosulfate, sodium 2
-Methacryloyloxyethyl-1 sulfonate, and 2- (N, N-dimethylamino) ethyl methacrylate hydrochloride. An acid addition salt conforming to the above structural formula (I) can be converted to a free amine when it is neutralized with a base. The above polymer can be prepared by polymerizing an appropriate monomer in an aqueous solution according to a conventional method. The monomer of the structural formula (I) has a structure of Earl. Etch. RYOCUM and E. Bee. Niquist (EBNyq
ist), “Functional Monomers” (Functio
nal Monomers), Marcel Dekke
r), Inc., New York (1974) and US Pat. No. 2,780,604.
It can be prepared by the method described in No. The monomer of structural formula (II) can be prepared by the method described in US Pat. Nos. 3,024,221 and 3,506,707. Optionally, the polymer is quaternized with a (a) polymer having amine groups with an alkylating agent, or
(B) It can be prepared by reacting an amine with a polymer having a group reactive with the amine, for example, an active halogen group. Such techniques are known in the art and are described in US Patent 3,488,706.
And Canadian Patent No. 601,958. The resins listed above are commercially available. Examples of commercially available products include Sumikagel N-100, Sumikagel SP-520, Sumikagel S-50, and Sumikagel NP-102.
0, Sumikagel F-03, Sumikagel F-51, Sumikagel F-75, Sumikagel R-30 (above trade name, Sumitomo Chemical Co., Ltd.), Sunwet IM-300, Sunwet I
M-1000 (Trade name, Sanyo Chemical Co., Ltd.), Aqua Keep IOSH-P (Trade name, Steel Chemical Co., Ltd.),
Randiel F (trade name, manufactured by Japan Exlan)
Etc. The liquid-absorbent resin preferably used in the present invention preferably has a shape that easily absorbs liquid, and has a powder form or a diameter of 0.01 to
A granular material having a size of about 3 mm can be advantageously used for handling. Further, the solidifying agent used as the carrier used in the present invention may be any one as long as it can solidify the concentrated liquid of the photographic processing waste liquid, and may or may not be accompanied by a chemical reaction. Examples of the solidifying agent of the present invention include CaO and Ca (O
H) ₂ , CuCO ₃ , silica gel, calcium chloride, aluminum oxide, calcium sulfate, magnesium oxide, barium oxide, granular soda lime, diphosphorus pentoxide and the like are preferably used. The evaporative concentration treatment apparatus of the present invention preferably has a rupture disk in order to prevent an accident in which the evaporation pot is pressurized due to a clogging of a vapor discharge chamber for discharging vaporized vapor and an explosion is caused. The rupture disk is configured to connect, for example, an evaporation pot and a waste liquid supply tank, and to interrupt the middle of the communication pipe with a sheet of polyethylene or the like that can be broken by pressurization. The evaporative concentration treatment apparatus of the present invention preferably has a temperature sensor in the evaporation pot. When the temperature sensor detects a certain temperature or more, for example, a temperature of 120 ° C. or more, the heating means is turned off, so that emptying can be prevented. The evaporative concentration treatment apparatus of the present invention is configured so that the door provided in the apparatus cannot be opened unless the temperature inside the evaporating vessel or the temperature inside the treatment apparatus becomes lower than a certain level (for example, 50 ° C. or lower), It is preferably arranged to emit a warning signal to open. When the waste liquid is processed by the evaporative concentration processing apparatus of the present invention, the color processing waste liquid and the color paper processing waste liquid may be separately processed for each processing line for processing various light-sensitive materials, or a mixture thereof. May be processed. Also,
Even in the same treatment line, the waste liquid in each tank may be treated individually, or a mixture of a plurality or all of the waste liquids may be treated. In the evaporative concentration treatment apparatus of the present invention, it is preferable to have a means for reducing the pressure in the evaporation tank, because the temperature in the evaporation tank can be lowered, so that a foul odor gas or a toxic gas is not generated. Further, even in the same processing line, the waste liquid in each tank may be treated separately, or a mixture of a plurality or all of the waste liquids may be treated. In the waste liquid concentration treatment apparatus of the present invention, it is preferable to have a means for decompressing the inside of the evaporating vessel because the temperature in the evaporating vessel can be lowered, so that an offensive odor gas or a toxic gas is less generated. Further, even in the same treatment line, the waste liquid in each tank may be treated individually or a mixture of a plurality or all of the waste liquids may be treated. Next, a typical example of a photographic processing waste liquid capable of performing the processing according to the present invention will be described in detail. However, the following mainly describes the photographic processing solution when the photographic material to be processed is for color, but the photographic processing waste solution is an overflow generated when processing a silver halide color photographic material using these photographic processing solutions. Most of the liquid. A color developing solution is a processing solution used in a color developing processing step (a step of forming a color color image, specifically, a step of forming a color color image by a coupling reaction between an oxidant of a color developing agent and a color coupler). Therefore, in the color development processing step, it is usually necessary to include a color developing agent in the color developing solution, but it is necessary to incorporate the color developing agent into the color photographic material to develop a color developing agent-containing color developing agent. Treatment with a developing solution or an alkaline solution (activator solution) is also included. The color-developing agent contained in the color-developing solution is an aromatic primary amine color-developing agent, and includes aminophenol-based and p-phenylenediamineamine-based derivatives. Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-
2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene are included. The color developing solution may contain an alkaline agent usually used in the developing solution, and further various additives such as benzyl alcohol, an alkali metal halide or a development regulator,
It may also contain preservatives. Further, various defoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide, dimethylsulfoxide and the like may be contained as appropriate. Further, the color developing solution may contain an antioxidant if necessary. Further, various chelating agents may be used in combination in the color developer as a sequestering agent. The bleach-fixing solution is a bleach-fixing step (a step of oxidizing metallic silver produced by development and replacing it with silver halide, then forming a water-soluble complex, and developing an uncolored portion of the color former).
The bleaching agent used for the bleach-fixing solution is not limited to any kind. The bleach-fix solution may contain various pH buffering agents alone or in combination of two or more kinds. Furthermore, it may contain various optical brighteners, antifoaming agents, or surfactants. Further, a preservative such as a bisulfite adduct, an organic chelating agent such as aminopolycarboxylic acid, a stabilizer such as nitroalcohol or nitric acid, an organic solvent and the like may be optionally contained. Further, bleach-fixing solutions are disclosed in JP-A-46-280, JP-A-45-8506, JP-A-46-556, and Belgian Patent No. 770,910.
No. 5, Japanese Patent Publication No. 45-8836, No. 53-9854, JP-A-54-7163
Various bleaching accelerators described in No. 4 and No. 49-42349 may be added. In the present invention, it is preferable that the treatment combined with the water-washing alternative stabilization treatment and the treatment waste liquid amount are small and the effect of heat exchange is large. As the stabilizing solution, there is a stabilizing solution having a function of stabilizing a color image and a function of a draining bath function to prevent contamination such as uneven washing with water. In addition, a color adjusting liquid for coloring a color image and an antistatic liquid containing an antistatic agent are also included in these stabilizing liquids.
When the bleach-fixing component is brought into the stabilizing solution from the pre-bath, the bleach-fixing component is neutralized, desalted and inactivated to prevent deterioration of the storage stability of the dye. As a component contained in such a stabilizing solution, a chelate stability constant with iron ion is 6 or more (particularly preferably 8 or more).
There are chelating agents that are. These chelating agents include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, polyhydroxy compounds, inorganic phosphoric acid chelating agents and the like. Particularly preferred for the effect of the present invention are diethylenetriaminepentaacetic acid and 1-hydroxyethylidene- 1,1-diphosphonic acid and salts thereof. These compounds are generally used in concentrations of about 0.1 g to 10 g for Stabilizer 1, more preferably about 0.5 g to 5 g for Stabilizer 1. The compound added to the stabilizing solution is an ammonium compound. These are supplied by ammonium salts of various inorganic compounds. Specifically, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, fluorinated ammonium, etc. Ammonium, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, lauryl tricarboxylic acid Ammonium acid, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, hydrogen malate Ammonium, ammonium hydrogen oxalate, ammonium hydrogen phthalate,
Ammonium hydrogen tartrate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidinedithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, thioglycolic acid Examples include ammonium and 2,4,6-trinitrophenol ammonium. The amount of these ammonium compounds added is in the range of 0.05 to 100 g per stabilizer. Compounds added to the stabilizing solution include pH adjusters, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-
Octyl-4-isothiazolin-3-one, 1-2-benzisothiazolin-3-one and other anti-bacterial agents described in Japanese Patent Application No. 59-146325 (pages 26 to 30), water-soluble metal salts, etc. Agent, ethylene glycol, polyethylene glycol, polyvinylpyrrolidone (PVP K-15, rubiscol K-1
7 etc.) and the like, hardeners such as formalin, optical brighteners and the like. In particular, the present invention is particularly preferably used because the tar-generation in the evaporation treatment device is small when the water-washing alternative stabilizing solution containing the anti-biological agent is used. When the light-sensitive material to be processed is for a negative, an aldehyde derivative may be added to the negative stabilizing solution in order to improve storability of photographic images. In the negative stabilizing solution, various additives are added as necessary, for example, a water droplet unevenness preventing material, a pH adjusting agent, a film hardening agent, an organic solvent, a humidity adjusting agent, and other color adjusting agents for improving and expanding the processing effect. Additives may be added. In the present invention, the stabilizing treatment using the alternative stabilizer for washing with water is not the usual treatment for washing away the processing liquid of the previous stage which has adhered to or penetrated into the photographic light-sensitive material by using a large amount of running water, but for the photographic treatment in the stabilizing liquid. Small per unit area of photosensitive material
30m / m ^{2 to} 9000m / m ² , more preferably 60m / m ^{2 to} 3000m / m ² having the same or more actions as above by supplementing, specifically, JP-A-58-134636. Image stabilization processing as described in. Therefore, when the stabilizing solution as a substitute for rinsing according to the present invention is used, there is no need for a facility for supplying and discharging a pipe to the outside of the automatic developing machine for rinsing as in the conventional case. Further, a stilbene-based fluorescent whitening agent may be used in a color developing solution for color paper or a stabilizing solution. The components contained in the waste liquid of the color developing solution are the above-mentioned various components or additives and the components that are eluted and accumulated from the photographic material to be processed. The components contained in the waste liquid of the bleach-fixing solution and the stabilizing solution are the above-mentioned various components or additives and components that are eluted and accumulated from the photographic material to be processed. In the evaporative concentration processing apparatus of the present invention, the waste liquid is a photographic processing waste liquid and is effective when it contains a large amount of thiosulfate, sulfite, and ammonium salt, and particularly contains ferric organic acid complex salt and thiosulfate. It is extremely effective when doing. As a preferred application example of the present invention, it is suitable for processing a photographic processing waste liquid generated during the development processing of a photographic light-sensitive material by an automatic developing machine in or near the automatic developing machine. 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 more specifically showing the evaporative concentration treatment apparatus of the photographic processing waste liquid of the present invention, and FIG. 3 is a configuration diagram showing its specific arrangement. In the figure, reference numeral 1 is an evaporator, which is composed of a cylindrical upper portion 1a having a large diameter and a cylindrical lower portion 1b having a small diameter.
The heating means 2 is provided above the lower portion 1b, and the ball valve 3 is provided below. A communication pipe 4 that communicates with the upper portion 1a extends from slightly above the ball valve 3, and a liquid level sensor 5 is provided on the way. Lower part 1b of the evaporator 1
A sludge receiver 6 is provided below the bag, and a polypropylene bag 7 is fixed to the inside by an O-ring 8. A vapor discharge pipe 9 is provided in the upper portion 1a of the evaporator 1 and the vapor discharge pipe 9 includes a heat exchanger 10 and cooling / condensing means 11.
And is connected to the liquid sump introduction pipe 12. Cooling and condensing means 11
In, the steam discharge pipe 9 is provided with a large number of cooling radiator plates 13 (a part of which is omitted), and a liquid level sensor 14 is further provided. A cooling water introducing pipe 15 is provided below the cooling / 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 cooling condensing means 11 is cooled by the air cooling fan 18.
It is released outside the processing equipment. The sump introduction pipe 12 is a sump tank
Although it is connected inside 19, an activated carbon cartridge 20 is installed inside this tank and inside it is an activated carbon packed in a paper bag.
21 are stored. In addition, outside the reservoir tank 19,
An activated carbon cartridge 22 is provided, and an activated carbon 23 packed in a paper bag is stored inside. The reservoir tank 19 is also provided with an air introduction pipe 24, which is installed in the waste liquid of the evaporation tank 1 via an air pump 25. 26 is a waste liquid supply tank, a waste liquid introduction pipe 27 is provided, a bellows pump 28,
It is connected to the upper portion 1a of the evaporation pot via the heat exchanger 10. The waste liquid supply tank 26 is further provided with a liquid level sensor 29. As shown in FIG. 3, the waste liquid supply tank 26 and the reservoir tank 19 are installed on a pedestal base 30 with a handle. A guide pipe 31 is further provided on the upper portion 1a of the evaporation tank 1 and is connected to a waste liquid supply tank 26 via a plunger disk 32. A temperature sensor 33 is also provided on the upper portion 1a of the evaporation tank 1. Next, an outline of the process of heating and evaporating using this apparatus will be described. The waste liquid supply tank 26, which stores about 20 overflow liquids from the automatic developing machine, is carried to the evaporative concentration processing apparatus and is installed on the pedestal 30 that is pulled out, and the waste liquid introduction pipe 27 and the liquid level sensor 29 are connected. . Further, on the pedestal 30, a reservoir tank 19 provided beforehand with activated carbon cartridges 20 and 22 filled with activated carbons 21 and 23 packed in paper bags, respectively, is installed, and the reservoir liquid introducing pipe 12 and the air introducing pipe 24 are connected. After that, it is stored in the evaporative concentration treatment device. Next, in the sludge receiver 6 below the lower portion 1b of the evaporation tank 1,
Install polypropylene back 7 and 2 O-rings 8
Then, it is fixed to the lower portion 1b of the evaporation pot 1. Next, when water is supplied into the cooling / condensing means 11 and the switch is turned on, the air pump 25 is operated, and the air in the reservoir tank 19 is introduced into the evaporator 1 via the air introduction pipe 24. Evaporative discharge pipe 9
Is at a position further below the heating means 2 provided outside the evaporation pot 1. Next, the air cooling fan 18 and the cooling water circulation pump 16 are operated in this order, and the accumulated water collects the cooling water introduction pipe 15
It is supplied through the shower pipe 17 or the heat radiating plate 13 of the vapor discharge pipe 9 housed in the cooling / condensing means 11 and circulates in such a manner that it is accumulated in the lower part of the cooling / condensing means 11 again. Next, the bellows pump 28 is activated and the waste liquid supply tank 26
The waste liquid therein passes through the waste liquid introducing pipe 27, the heat exchanger 10, and then is sent into the evaporator 1. When the amount of waste liquid in the evaporator 1 increases, the liquid level in the communicating pipe 4 increases, and the liquid level sensor 5 detects the liquid level for, for example, 3 seconds or more,
The operation of the bellows pump 28 is stopped, and at the same time, the heating means 2 is turned on to start heating and evaporation. When the amount of waste liquid in the evaporator 1 decreases due to heating and evaporation, the liquid level in the communication pipe 4 decreases, and the liquid level sensor 5 no longer detects the liquid level for 3 seconds or more, the bellows pump is again used.
The operation of turning on the switch 28 and supplying the waste liquid in the waste liquid supply tank 26 into the evaporator 1 is repeated. The vaporized vapor passes through the vapor discharge pipe 9, exchanges heat with the waste liquid in the heat exchanger 10, and then is condensed through the cooling condensing means 11, and the condensed water passes through the distillate introduction pipe 12 and the distillate tank 19. After entering the inside and passing through the activated carbon 21 in the activated carbon cartridge 20, a reservoir tank
Stored within 19. When the liquid level sensor 29 detects that there is no waste liquid in the waste liquid supply tank 26, the bellows pump 28
The operation of the is stopped, the switch of the heating means 2 is turned off,
After 2 hours, the cooling water circulation pump 16 and the air-cooling fan 18 are stopped, the lamp is turned on, the buzzer sounds to notify the completion of the evaporative concentration process, and the air pump 25 is stopped. Here, the ball valve 3 is opened, the sludge in the evaporator 1 is dropped into the polypropylene bag 7, and then the O-ring 8 is removed and taken out. During the evaporative concentration process, when the liquid level sensor 14 detects that there is no water in the cooling / condensing means 11, the lamp is turned on and the buzzer sounds.
Notify that there is no more water. During the evaporative concentration process, the liquid level in the evaporation kettle 1 is abnormally lowered for some reason, and the temperature in the evaporation kettle 1 is lowered by emptying.
When the temperature sensor 33 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 is turned off, the evaporative concentration process is interrupted by the series of operations described above. FIG. 4 is a sectional view of the heating means 2 shown in FIGS. 2 and 3. That is, the SU is placed around the wall 34 of the titanium evaporation pot 1.
A heater block 36 made of S304 is provided, and four cartridge heaters 35 are embedded in this heater block 36. Further, a heat insulating agent 37 is provided on the peripheral surface of the heater block 36. 5 to 7 are views showing other examples of the vapor cooling and condensing means of the present invention. In FIG. 5, the cooling and condensing means are two sets of the upper cooling and condensing means 11a and the lower cooling and condensing means 11b, and water is accumulated in the lower part of the lower cooling and condensing means 11b. This water is sent by a cooling water circulation pump 16 through a cooling water introducing pipe 15 to a shower pipe 17 provided above the cooling and condensing means 11a, and on a steam discharge pipe 9 provided with a cooling radiator plate 13. After being supplied, it is sent to the shower pipe 17 above the cooling and condensing means 11b below. Similarly, after being supplied on the steam discharge pipe 9, it returns to the water tank due to the lower part. In FIG. 6, in the embodiment in which the air cooling fan 18 is provided in the upper part, air is introduced from both sides 11c and 11d of the cooling and condensing means 11 and is discharged to the outside of the evaporative concentration treatment apparatus via the air cooling fan 18. It FIG. 7 shows an embodiment in which the external duct 38 of the air-cooling fan 18 is provided, in which case the means for supplying water does not function. As described above, it may be configured such that water is not supplied when the duct can be installed and water can be supplied when the duct cannot be installed.

【Example】

After painting on a commercially available color photographic paper, continuous processing was performed using the following processing steps and processing solutions. Standard processing step (1) Color development 38 ° 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 solution] Benzyl alcohol 15ml 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-methanesulfonamide Ethyl) aniline salt 4.5g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0g Hydroxylamine sulfate 3.0g 1-Hydroxyethylindene-1,1-diphosphonic acid 0.4g Hydroxyethyliminodine Acetic acid 5.0 g Magnesium chloride hexahydrate 0.7 g 1,2-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2 g Water was added to 1 and pH was adjusted to 10.20 with potassium hydroxide and sulfuric acid.
And [Color development replenisher] Benzyl alcohol 20 ml Ethylene glycol 20 ml Potassium sulfite 3.0 g Potassium carbonate 24.0 g Hydroxyamine sulfate 4.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline Sulfate 6.0g 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-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 1.0g 2-Methyl-4-isothiazolin-3-one 0.20g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) 1.0 g Ammonia water (25% ammonium hydroxide in water) 2.0 g Water to 1 and 50% sulfuric acid to pH 7.0. An automatic processor was filled with the above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution, and the above-mentioned color developing replenishing solution and bleach-fixing replenishing solution A were processed at intervals of 3 minutes while processing the commercially available color photographic paper sample. , B and a stable replenisher were replenished through a bellows pump to perform a running test. The replenishing amount is 190 ml per 1 m ² of color paper as the replenishing amount to the color developing tank, 50 ml of each of the bleach-fixing replenishing liquids A and B as the replenishing amount to the bleach-fixing tank, and the washing replacement stable replenisher as the replenishing amount to the stabilizing tank Was replenished with 250 ml. In addition, the stabilizing tank of the automatic processor is a stabilizing tank which is the first tank to the third tank in the direction of the sample flow, replenishment is performed from the final tank, and the overflow liquid from the final tank is allowed to flow into the previous tank. In addition, a multi-tank countercurrent system in which this overflow liquid is allowed to flow into the previous tank is also adopted. Continuous treatment was carried out until the total replenishment amount of the stabilizing solution as a substitute for washing was 3 times the capacity of the stable tank. However, 400 g of potassium carbonate was previously dissolved in the photographic processing waste liquid, and 500 g of sodium hydrogensulfate was put into the reservoir tank. Further, the heat density of the heating means was set to 4 kcal / cm ^2, and 4 g of the antifoaming agent FS Antifoam 025 (manufactured by Dow Corning) was previously added to the photographic processing waste liquid. Then, an evaporative concentration treatment was carried out in the same manner with an evaporative concentration treatment apparatus having a cooling and condensing means having no means for supplying water. In the above two experiments, at the end of the experiment, the amount of the accumulated liquid in the accumulated liquid tank was measured, and the odor generated from the evaporative concentration treatment apparatus was observed in the course of the experiment. The results are shown in Table 1. The symbols used in Table 1 to indicate the odor evaluation means the following evaluations. D: Bad odor A: No bad odor As is apparent from Table 1, in Experiment NO1 using the evaporative concentration treatment apparatus of the present invention, the condensation rate is high and there is no odor, but a comparative evaporative concentration treatment apparatus is used. In the experiment NO2 used,
It can be seen that the condensation rate is low and the odor is bad. The heating means (cartridge heater) used in Experimental Example 1 was changed to the heat densities shown in Table 2 below, and the experiment was conducted in the same manner as in the present Example. During the experiment, the odor and the corrosion of the evaporation concentrator were observed and summarized in Table 2 below. The odor evaluation in the table is as follows. A: No odor at all. B: There is a slight odor. C: It has a bad odor. D: It smells bad. The evaluation of corrosion in the table is as follows. ◯: No corrosion is observed in the pot. Δ: There is slight corrosion. X: Corrosion is clearly observed. From Table 3 above, it can be seen that when the heat density is 17.2 Kcal / cm ² or less, there is no bad odor or corrosion of the kettle. [Effects of the Invention] As described above, according to the present invention, since the cooling / condensing means is composed of at least means for supplying water to the steam discharge pipe, it is possible to effectively cool and condense the evaporated photographic processing waste liquid. The harmful or malodorous components generated by the evaporative condensation treatment can be suppressed to a small amount, and the photographic processing waste liquid can be treated without generating an offensive odor and harmful gas.
It is possible to obtain a processing device that is compact, inexpensive, and low in running cost. Further, the water supplied to the steam discharge pipe is stored water, and the structure for supplying the water is simple. In addition, by combining the means for supplying water to at least the steam discharge pipe with the cooling / condensing means and setting the heat density of the heating means to about 17.2 kcal / cm ² or less, the peculiar odor and harmfulness in the processing of the photographic processing waste liquid are combined. It is possible to more effectively suppress the generation of various gases and prevent bumping. Especially, the heat density of the heating means
By setting the rate to 17.2 kcal / cm ² or less and further supplying gas through the means for supplying gas into the waste liquid in the evaporation tank, a vapor layer is formed on the surface of the heating means, and steam is superposed in the immediate vicinity of the surface of the heating means. It can be efficiently prevented from being heated and causing an offensive odor and also causing bumping. Further, the heat density of the heating means is about 17.2 kcal / cm ² or less, and by having a means for supplying a compound capable of adjusting the surface tension of the photographic processing waste liquid to 20 to 65 dyne / cm in the evaporation tank,
By supplying the defoaming agent into the evaporator, it is possible to prevent the accident that the waste liquid blows out from the introduction pipe for introducing the vapor into the cooling and condensing means.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an automatic developing machine, FIG. 2 is a schematic configuration diagram showing an embodiment of the present invention, FIG. 3 is a configuration diagram showing its specific arrangement, FIG. 4 is FIG. 2 and FIG. FIG. 3 is a cross-sectional view of the heating means shown in FIG. 3, and FIGS. 5 to 7 are schematic configuration diagrams of main parts showing another embodiment. In the drawings, reference numeral 1 is an evaporator, 2 is heating means, 5 is a liquid level sensor, 11 is cooling / condensing means, 19 is a reservoir tank, and 26 is a waste liquid supply tank.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayuki Kurematsu No. 1 Sakura-cho, Hino-shi, Tokyo Photo of Konishi Roku Photo Industry Co., Ltd. (72) Inventor Naoki Takabayashi No. 1 Sakura-cho, Hino-shi, Tokyo Photo Photo 6 (56) References JP-A-52-30774 (JP, A) JP-A-63-236585 (JP, A)

Claims (4)

[Claims] 1. An apparatus for evaporating and condensing a photographic processing waste liquid, comprising: an evaporation pot, a heating means, a steam discharge pipe for guiding evaporated steam, and a steam cooling condenser means, wherein the steam cooling condenser means supplies water to at least the steam discharge pipe. And a heat density of the heating means of about 17.2 kcal / cm ² or less. 2. The apparatus for evaporative concentration of photographic processing waste liquid according to claim 1, wherein the water supplied to the steam discharge pipe is pooled water. 3. An apparatus for evaporative concentration of photographic processing waste liquid according to claim 1, further comprising means for supplying gas into the waste liquid in the evaporation tank. 4. The surface tension of the photographic processing waste liquid is set to 20 to 20 in the evaporation tank.
The apparatus for evaporative concentration of photographic processing waste liquid according to claim 1, characterized in that it has means for supplying a compound capable of producing 65 dyne / cm.