JPS63310694A - Method and device for evaporating and concentrating waste photographic processing solution - Google Patents

Abstract

PURPOSE:To prevent the generation of a harmful gas such as a malodorous sulfur compd. from the condensate obtained by cooling and condensing the vapor generated in the evaporation and concentration of a waste photographic processing soln. by liberating a gas from the condensate, and returning the gas contg. the condensate to the waste photographic processing soln. side to be heated. CONSTITUTION:The waste photographic processing soln. is heated in an evaporator 1 by a heating means 2, evaporated, and concn., and the generated vapor is cooled and condensed by a condensing means 11 to obtain a condensate. The condensate is sent into a distillate tank 19 through a distillate inlet pipe 12 along with the remaining gas, and discharged from the tip 12a of an inlet pipe as a bubbling means 20 under the distillate surface. The gas ascends in the condensate in the distillate tank 19, hence bubbling is carried out, and a gas such as hydrogen sulfide dissolved in the condensate is driven out to the outside of the liq. The gas liberated from the condensate is discharged into the waste photographic processing soln. at the lower part in the evaporator 1 by the operation of an air pump 23 from the distillate tank 19 through an air inlet pipe 22, and the evaporation and concentration of the soln. are promoted.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an evaporative concentration processing method and an apparatus for evaporating waste liquid (hereinafter referred to as photographic processing waste liquid or waste liquid) generated during the processing of photographic light-sensitive materials by an automatic photographic processor. In particular, the present invention relates to a method and apparatus for evaporating and concentrating photographic processing waste liquid, which is suitable for processing by being placed in or near an automatic processor. (Background of the Invention) In general, photographic processing of silver halide photographic materials includes development, fixing, washing, etc. in the case of black and white materials, and color development, bleach-fixing (or bleaching and fixing) in the case of color photographic materials. ,
A combination of processes using a treatment liquid having one or more functions such as water washing and stabilization is carried out. In photographic processing in which a large amount of light-sensitive material is processed, the components consumed during processing are replenished, while the components that are concentrated by elution or evaporation into the processing solution (
For example, methods are used to maintain the performance of the processing solution at a constant level by removing bromide ions in the developing solution and silver complex salts in the fixing solution and keeping the processing solution components constant. A replenisher is added to the processing solution, and a portion of the processing solution is discarded to remove thickening components in photographic processing. In recent years, systems have been changing to systems in which the amount of replenishment fluid, including washing water, which is used as a replenishment fluid for washing, has been significantly reduced due to pollution and economic reasons, but photographic processing waste fluid is removed from the processing tank of automatic processors. It is led through a waste liquid pipe, diluted with waste liquid from washing water, cooling water from automatic processors, etc., and then disposed of in a sewer or the like. However, due to stricter pollution regulations in recent years, it is possible to dispose of washing water and cooling water into sewers or rivers, but other photographic processing solutions [e.g. developer, fixer, color developer, bleach-fixer] (or bleaching solution, fixing solution), stabilizing solution, etc.] has become virtually impossible to dispose of. For this reason, each photo processing company pays a collection fee to a specialized waste liquid processing company to collect the waste liquid, or installs pollution treatment equipment. However, the method of outsourcing to a waste liquid treatment company is
A considerable amount of space is required to store the waste liquid, and it is also extremely expensive.Furthermore, the initial investment (initial cost) of pollution treatment equipment is extremely large, and it requires a fairly large space to maintain it. However, there are disadvantages such as the need for Therefore, waste liquid is generally collected by a waste liquid collection company and rendered harmless through secondary and tertiary processing.However, not only is the price of waste liquid collection increasing year by year due to rising collection costs, but collection efficiency is low in minilabs, etc., so it is difficult to do so. No one can come to collect the liquid, causing problems such as waste liquid filling the store. In order to solve these problems, research has been conducted to heat the photographic processing waste liquid to evaporate the water to dryness or solidify it, with the aim of making it easier to process the photographic processing waste liquid even in minilabs. It is shown in JP-A No. 60-70841 and the like. By the way, the inventors' research has shown that when photographic processing waste liquid is evaporated, harmful or extremely malodorous gases such as sulfur dioxide gas, hydrogen sulfide, and ammonia gas are generated. It has been found that this is caused by the decomposition of ammonium thiosulfate and sulfites (ammonium salt, sodium salt, or potassium salt), which are commonly used as fixing solutions and bleach-fixing solutions in photographic processing solutions, due to high temperatures. Further, during the evaporation process, moisture and the like in the photographic processing waste liquid becomes vapor and gasifies, thereby expanding the volume and increasing the pressure in the evaporation pot. Therefore, this pressure causes the harmful or malodorous gases to leak out of the evaporation treatment apparatus to the outside of the apparatus, resulting in an extremely unfavorable working environment. Therefore, in order to solve these problems,
No. 1 discloses a method of providing an exhaust gas treatment section such as activated carbon in the exhaust pipe section of an evaporation treatment device. However, this method has the serious drawback that water vapor from a large amount of water in the photographic processing waste liquid condenses or condenses in the exhaust gas treatment section, covering the gas absorption processing agent and causing it to instantly lose its gas absorption ability. However, it has not yet been put to practical use. In order to solve these problems, the inventors installed a cooling condensing means to condense the vapor generated by evaporation when photographic processing waste liquid is evaporated, and further processed the condensate generated by condensation and removed non-condensable components. We have previously proposed a method and apparatus for concentrating photographic processing waste liquid that is also processed and discharged to the outside. However, when photographic processing waste liquid is subjected to evaporative concentration treatment and the degree of concentration increases at this time, it has the disadvantage that generation of sulfur-based malodorous gases increases significantly. Furthermore, when the amount of sulfur-based malodorous gases generated increases, free sulfur also begins to be generated, and the condensate becomes unable to be discharged into sewage or the like. For this reason, various studies and experiments have been conducted to suppress the generation of sulfur-based malodorous gas due to the progression of 11AfI, and it has been found that by generating gas from the condensed liquid, the gas containing the odor components dissolved in the condensed liquid can be removed. Let it go,
It has been discovered that by returning this gas to the evaporation means, the sulfur-based odor of the condensate can be effectively prevented. (Object of the Invention) This invention has been made in view of the above-mentioned conventional problems, and the object of the invention is to cool and condense the vapor generated by the evaporative concentration treatment of photographic processing waste liquid. An object of the present invention is to provide a method for evaporating and concentrating photographic processing waste liquid, which prevents the generation of harmful gases such as sulfur-based odors, and an apparatus therefor. (Means for Solving the Problems) In order to solve the above-mentioned problems of the present invention, the method for evaporating and concentrating photographic processing waste liquid of the first invention heats the photographic processing waste liquid and evaporates and concentrates the photographic processing waste liquid. A method for evaporating and concentrating photographic processing waste liquid in which a condensate liquid is obtained by cooling and condensing vapor, characterized in that a gas is generated from the condensate liquid, and the gas containing the condensate component is returned to the heated photographic processing waste liquid side. It is said that Further, the evaporative concentration processing apparatus for photographic processing waste liquid of the second invention has an evaporation means and a heating means for heating the photographic processing waste liquid to evaporate and concentrate the photographic processing waste liquid, and a condensing means for cooling and condensing the evaporated vapor. The processing apparatus is characterized by comprising a gas generating means for generating gas from the condensate condensed by the condensing means, and a means for returning the gas containing the condensed liquid component to the evaporating means. In this invention, it is preferable that the gas that has passed through the condensing means and the gas generated by the gas generating means be returned to the evaporating means, and more preferably, the means for returning the gas that has passed through the condensing means and the gas generated from the gas generating means to the evaporating means can be returned to the evaporating means. It is preferable that the liquid be forcibly returned to the evaporation means side. Also,
This gas returned to the evaporation means side contains a condensate component,
The flow rate is preferably 0.1 fl/min or more, more preferably IJl/min or more, and most preferably 3 J1/min to 3 m3/min. Further, the gas generation means is configured to store condensate and generate gas. This gas generating means includes, for example,
(1) Bubbling, (2) Liquid circulation using a pump, etc. (discharged into the gas by showering, etc.), (3) Liquid agitation (gas may be drawn in), (4) Liquid with a large surface area and into the air stream. Measures such as encouraging gas generation are used. The stored condensate is preferably treated with an acid or alkaline agent such as NaOH1, OH, alkali metal hydroxide such as LiOH, Na2(:Q3, ni2CO3 or other alkali metal carbonate, N Ha O )(, Ca 01M
g0. Ca, (OH)2, Mg(OH)2
．． An alkaline agent such as Na5PO, 3PO4, and more preferably an alkali metal hydroxide or an alkali metal carbonate is used. The amount of the alkali metal hydroxide and alkali metal carbonate added is preferably 0.1 to 100 g/J2, more preferably 1 to 50 g/l. Moreover, the following is also a preferable embodiment of the gas generating means. For example, adding an alkaline agent to photographic processing waste liquid makes it easier to generate alkaline gas.
The amount added is preferably 1 to 300 g/J! , more preferably 5 to 300 g/fl. Another method is to add sulfites such as sodium sulfite, potassium sulfite, and ammonium sulfite to the photographic processing waste liquid. This makes it difficult to generate sulfur-based gas, and the amount of addition is preferably 0.1 to 100 g/ il, more preferably 1
~50g/J! , is. The return means in this invention is a pa (
piping connecting between the upper part of the evaporation means (retained liquid tank) and the evaporation means;
It consists of an air pump, a blower, etc. that forcefully sends the gas in this piping to the evaporation means. The evaporation means in this invention may be in any form, including a cube, a cylinder, a polygonal prism including a square prism, a cone, a polygonal pyramid including a square pyramid, or a combination of some of these. However, it is preferable that the evaporating means be vertically long so as to increase the temperature difference between the photographic processing waste liquid near the heating means and at the bottom. It is preferable to make the space above the surface of the waste liquid as wide as possible. The material of the evaporation means may be any heat-resistant material such as heat-resistant glass, titanium, stainless steel, carbon steel, etc. However, from the viewpoint of safety and corrosion resistance, stainless steel (preferably 5US304 or 5US316) is used. , particularly preferably 5US316) and titanium. In this invention, the heating means may be a nichrome wire, or may be a processed heater such as a cartridge heater, quartz heater, Teflon heater, rod heater, or panel heater. The heating means may be installed in the waste liquid in the evaporation means, but in order to further enhance the effect of the present invention and to avoid a decrease in thermal efficiency or 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 evaporating means is heated through the wall of the evaporating means by being provided outside the evaporating means. The heating means may be installed at any position as long as it can heat the waste liquid from the evaporation means.
As described in No. 1-288328, the heating means is installed to heat the upper part of the photographic processing waste liquid in the evaporating means, and the difference in temperature between the photographic processing waste liquid near the heating means and the bottom part of the photographic processing waste liquid is maintained. Preferably, the heating means is installed so that this temperature difference is 5° C. or more, in order to further enhance the effects of the present invention. This invention has a condensing means for cooling and condensing evaporated vapor, and all kinds of heat exchange means can be adopted as the condensing means. (1) Shell and tube type (multi-tube type, jacket type) It may be of any of the following configurations: double tube type (3) coil type (4) spiral type (5) plate type (6) fin tube type (7) trombone type (8) air cooling type. Heat exchange reboiler technology can also be used: (1) vertical thermosiphon type, (2) horizontal thermosiphon type, (3) overflow tube bundle type (kettle type), (4) forced circulation type, and (5) interpolated type. etc. may be adopted. Furthermore, a condenser type heat exchange technology may be adopted, and any of the following types may be used: (1) direct condenser type, (2) built-in tower type, (3) tower top type, (4) separation type, etc. Moreover, it is also possible to use a cooler, and the type of cooler is also arbitrary. It is also advantageous to employ an air-cooled heat exchanger, which may be either (1) forced draft type, or (2) blown draft type. In a preferred embodiment, the condensing means is configured as a heat sink device in which a heat sink (air cooling fan) is installed in a steam exhaust pipe for discharging spontaneous steam, and means for supplying water onto the heat sink. It is to have the following. In this case, water is preferably supplied onto the heat sink from above the heat sink device in the form of a shower. For example, water may be supplied onto the heat sink from a tap water tap via a valve or a solenoid valve as necessary, and in this case, the means for supplying water may include a tap tap, a water supply pipe, etc. However, it is preferable that the stored water is supplied onto the heat sink through various metering pumps or non-metering pumps as described above, and in particular, it is preferable that the reservoir water is supplied onto the heat sink through the various metering pumps or non-metering pumps as described above. The water in the tank is supplied to the heat sink via a pump in a shower-like manner, and is then collected in the water tank at the bottom, so that the water is circulated. In this case, by installing a liquid level sensor in the reservoir water tank and sending out a signal when the liquid level drops below a certain level, you will be able to know that the reservoir water has run out and supply water again. It's good. The condensing means is configured as a heat sink device in which a heat sink (air cooling fan) is installed on a steam exhaust pipe that discharges evaporated steam, and if it has a means for supplying water onto this heat sink, It is preferable to have an air-cooling fan, and in particular, in this case, the air-cooling fan is installed so that air passes through the heat sink device and is discharged to the outside of the evaporation concentration processing device of the present invention. It is preferable that the evaporative concentration treatment apparatus of the present invention be present in the evaporative concentration treatment apparatus because it can prevent condensation in the electrical components. The condensate obtained by cooling and concentrating the evaporated vapor is stored in a tank for storing the condensate (distillate tank), and the condensate tank is installed inside the evaporation concentrator of the present invention. This is preferable because it can save space, and in this case, it is preferable that the accumulated liquid tank is installed on a drawable pedestal to improve workability. The evaporation concentration processing apparatus of the present invention has a condensing means for cooling and condensing the evaporated vapor, but the condensate obtained by this is used in addition to the gas generation by the gas generating means of the present invention. (A) to perform at least one secondary treatment selected from the following (A) to (J) on the
Activated carbon treatment, (B) ultraviolet irradiation treatment, (C) reverse osmosis treatment, (D) oxidizing agent treatment, (E) aeration treatment, (F
) Electrodialysis treatment, (G) re-distillation treatment, (H) ion exchange resin treatment, (I) pH adjustment, and (2) using the condensate as dissolving water in the photographic processing solution are also preferred methods. In addition to the above-mentioned activated carbon, the following substances can be used as the adsorbent substance used in the adsorption treatment of the condensate of photographic processing waste liquid according to the present invention. (1) Clay material (2) Polyamide polymer compound (3) Polyurethane polymer compound (4) Phenol resin (5) Epoxy resin (6) Polymer compound having hydrazide group (7) Containing polytetrafluoroethylene High molecular compound (8) Monohydric or polyhydric alcohol methacrylic acid 1,000 ester-polyhydric alcohol methacrylic acid (9) Polyester copolymer For details of these substances (1) to (9), please refer to Japanese Patent Application No. 124639/1986. (particularly pages 62 to 66). Furthermore, the structure of the evaporating means, heating means, and condensing means of this invention is disclosed in Japanese Patent Application No. 62-694 filed earlier by this applicant.
No. 35, No. 62-69436, and No. 62-6943
It is described in detail in issue 7. Next, typical examples of photographic processing waste liquid that can be processed according to the present invention will be described in detail. However, the following will mainly discuss photographic processing solutions when the photographic materials to be processed are color ones, but photographic processing waste fluids are the overflow produced when processing silver halide color photographic materials using these photographic processing solutions. Most of it is liquid. A color developing solution is a processing solution used in a color development process (a process of forming a color image, specifically a process of forming a color image through a coupling reaction between an oxidized form of a color developing agent and a color coupler). Therefore, in the color development processing process, it is usually necessary to include a color developing agent in the color developing solution, but color developing agents are incorporated in the color photographic material. It also includes processing with a developer or alkaline solution (activator solution). The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenyresinamine amine derivatives. Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, and 2-oxy-3-amino-1,4-dimethyl-benzene. The color developing solution may contain an alkaline agent commonly used in developing solutions, and may further contain various additives such as benzyl alcohol, alkali metal halides, or development regulators.
May also contain preservatives. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide may be appropriately contained. Further, the color developing solution may contain an antioxidant, if necessary. Furthermore, various chelating agents may be used in combination as metal ion sequestrants in the color developing solution. The bleach-fix solution is used in the bleach-fixing process (a process in which metallic silver produced during development is oxidized and replaced with silver halide, and then a water-soluble complex is formed and the uncolored areas of the color former are colored).
It is a processing solution used in the bleach-fixing solution, and the bleaching agent used in the bleach-fixing solution does not matter. In addition, various pHM buffers may be used alone or in combination in the bleach-fix solution.
It may contain more than one species in combination. Furthermore, it may contain various optical brighteners, antifoaming agents, or surfactants. It may also contain a preservative such as a bisulfite adduct, an organic chelating agent such as an aminopolycarboxylic acid, a stabilizer such as nitro alcohol or nitric acid, an organic solvent, etc. as appropriate. Furthermore, the bleach-fix solution is disclosed in Japanese Patent Application Laid-open Nos. 46-280, 45-8506, and 46
-556, Belgian Patent No. 770,910, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854, Japanese Patent Publication No. 1983-
Various bleaching accelerators such as those described in No. 71634 and No. 49-42349 may be added. In this invention, it is preferable that the treatment function is combined with the water washing alternative stabilization treatment, and the amount of treated waste liquid is small and the effect of heat exchange is large. There are also stabilizers that have the function of stabilizing color images and those that have a draining bath function that prevents contamination such as uneven washing. These stabilizers also include coloring adjustment liquids for coloring color images and antistatic liquids containing antistatic agents. When bleach-fixing components are brought into the stabilizing solution from the pre-bath, measures are taken to neutralize, desalt and inactivate them so as not to deteriorate the shelf life of the dye. The components contained in such a stabilizing solution include those having a chelate stability constant of 6 or more (especially preferably 8 or more) with iron ions.
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, etc. For the effects of this invention, diethylenetriaminepentaacetic acid, l-hydroxyethylidene- These are 1,1-diphosphonic acid and salts thereof. These compounds are generally used in concentrations of about 0.1 g to 10 g for stabilizer 11, and more preferably about 0.5 g to 5 g for stabilizer 12. Compounds added to the stabilizing solution include ammonium compounds. 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, ammonium fluoride, acidic ammonium fluoride, ammonium fluoroborate, ammonium phosphate, ammonium bicarbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate , ammonium adipate,
Ammonium lauryltricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium lactate, apple ammonium acid, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4.6- )-linitrophenol ammonium, etc. The amount of these ammonium compounds added is in the range of 0.05 to tOOg per 11 stabilizers. 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 others Patent application 1982-1
46325 (pages 26 to 30), preservatives such as water-soluble metal salts, ethylene glycol, polyethylene glycol, polyvinylpyrrolidone (PVP K-1
Examples include dispersants such as 5. Rubiscol and -17), hardeners such as formalin, and fluorescent brighteners. In particular, in the present invention, when using the water washing substitute stabilizing liquid containing the anti-spill agent, it is particularly preferably used because less tar is generated in the evaporation treatment apparatus. When the photographic material to be processed is for negative use, an aldehyde derivative may be added to the negative stabilizer in order to improve the storage stability of photographic images. The stabilizer for negatives may contain various additives as necessary, such as a water droplet unevenness preventive agent, a pH adjuster, a hardening agent, an organic solvent,
Additives may be added to improve or extend the processing effect, such as humidity control agents and other color toning agents. In this invention, the stabilization treatment performed using a water-washing substitute stabilizing solution is not a process in which a large amount of normal running water is used to wash away the previous processing solution that has adhered to or penetrated into the photographic light-sensitive material. Only 30mjE/m2 to 9000m fl 7m2 per unit area of photosensitive material. More preferably 60 Jl/la2~3000m Jl/rr
By supplementing with r2, it has an effect equivalent to or better than the above, and specifically, it is described in Japanese Patent Application Laid-Open No. 58-134836.
Refers to image stabilization processing as described in the issue. Therefore, when the washing substitute stabilizing liquid according to the present invention is used, there is no need to provide a supply/discharge pipe to the outside of the automatic developing machine for washing, unlike the conventional method. In addition, stilbene-based optical brighteners are sometimes used in color developing solutions and stabilizers for color paper. The components contained in the waste liquid of the color developing solution include the various components or additives mentioned above, and components that are eluted and accumulated from the photographic material being processed. The components contained in the waste liquid of the bleach-fix solution and stabilizer include the various components or additives mentioned above, and components that are eluted and accumulated from the photographic material being processed. The evaporation concentration processing apparatus of the present invention is effective when the waste liquid is a photographic processing waste liquid and contains a large amount of thiosulfate, sulfite, or ammonium salt, and is particularly effective when it contains a large amount of organic acid ferric complex salt and thiosulfate. It is extremely effective when In a preferred application of the present invention, photographic processing waste liquid generated during the processing of photographic light-sensitive materials by an automatic processor is passed for processing within or near the automatic processor. Here, automatic processors and photographic processing waste liquid will be explained. Automatic processor In FIG. 1, the automatic processor is designated by the reference numeral 100, and the one shown in the figure continuously passes a roll of photographic material F into a color development tank CD, a bleach-fix tank BF, and a stabilization processing tank sb. This method involves guiding the film through the process, photo-processing it, and winding it up after drying. Reference numeral 101 denotes a replenisher tank, and a sensor 102 detects the photographic processing amount of the photosensitive material F, and a control device 103 replenishes each processing tank with replenisher according to the detected information. When the replenisher is replenished for each photographic processing amount, the overflow waste liquid is discharged from the processing tank and collected in the stock tank 104. A simple way to transfer the overflowing photographic processing waste liquid to the stock tank io4 is to let it fall naturally through a guide pipe. There may also be cases where it is forcibly transferred using a pump or the like. Further, as described above, although there are differences in the components of the photographic processing waste liquid in each of the photographic processing tanks CD, BF, and sb, in the present invention, it is preferable to mix all the photographic processing waste liquids and process them all at once. (Example) FIG. 2 is a schematic diagram showing an apparatus for evaporating and concentrating photographic processing waste liquid according to the present invention. In the figure, reference numeral 1 denotes an evaporation pot as an evaporation means, which is composed of a cylindrical upper part 1a with a large diameter and a cylindrical lower part 1b with a small diameter.Heating means 2 is provided above the lower part 1b, and is provided with ball pulp 3. The evaporator 1 is provided with a liquid level sensor 4, and a support 5 disposed at the bottom of the evaporator 1 is provided with a sludge receiver 6.
The sludge receiver 6 is placed under the lower part 1b, and a polypropylene bag 7 is fixed therein by an O-ring 8. A steam exhaust pipe 9 is provided in the upper part 1a of the evaporating pot 1, and this steam exhaust pipe 9 is connected to a heat exchanger 10 and a condensing means 11.
It is connected to the reservoir liquid introduction pipe 12 through the pipe. Condensing means 11
In this case, a large number of cooling heat sinks 13 are provided on the steam exhaust pipe 9, and a liquid level sensor 14 is further provided. A cooling water introduction pipe 15 is provided at the lower part of the condensing means 11,
It is connected via a cooling water circulation pump 16 to a shower pipe 17 in which a large number of small holes are drilled. The air in the condensing means 11 is cooled by an air cooling fan 18.
Released outside the processing equipment. The accumulated liquid introduction pipe 12 is connected to the accumulated liquid tank 19, and the tip @ 12a of the accumulated liquid introduction pipe 12 is located below the accumulated liquid surface of the accumulated liquid tank 19, and the bubbling mechanism 20 as a gas generating means is connected to the accumulated liquid introduction pipe 12. It consists of Furthermore, an activated carbon cartridge 21 that stores activated carbon is provided at the upper part of the reservoir tank 19. The accumulated liquid tank 19 is also provided with an air introduction pipe 22 as a return means,
The tip 22a is connected to the evaporation pot 1 via an air pump 23.
has been introduced into the waste liquid of 24 is a waste liquid supply tank, which is provided with a waste liquid introduction pipe 25;
A bellows pump 26 is connected to the evaporator upper part 1a via a heat exchanger 1o. The waste liquid supply tank 24 is further provided with a liquid level gauge 27. The upper part 1a of the evaporator 1 is further provided with a guide pipe 28, which is connected to the waste liquid supply tank 24 via a plunger disk 29, and the upper part 1a of the evaporator 1 is also provided with a temperature sensor 30. This evaporation concentration processing apparatus is further provided with a chemical liquid addition mechanism 31 as a gas generating means, and a chemical liquid introduction pipe 33 provided in a chemical liquid tank 32 of the chemical liquid addition mechanism 31 is connected to a pump 34.
It is connected to a reservoir tank 19 via a tank 7 for supplying, for example, an alkali metal carbonate. Next, an outline of the heating and evaporation process using this apparatus will be explained. Approximately 201 overflow liquid from the automatic developing machine is stored in a waste liquid supply tank 24, and an activated carbon cartridge 20 filled with activated carbon 21, a accumulated liquid introduction pipe 12, and an air introduction pipe 22 are connected to the accumulated liquid tank 19. Lower part of evaporator pot 1! A polypropylene bag 7 is installed in the sludge receiver 6 under b, and fixed to the lower part 1b of the evaporating pot 1 with two O-rings 8. After supplying water to the condensing means 11, turn on the switch. , air pump 2
3 is activated, the air in the accumulated liquid tank 19 flows into the air introduction pipe 22.
This air is introduced into the evaporation pot 1 through the heating means 2.
It is emitted from the tip 22a located further below. Then, the air cooling fan 18 and the cooling water circulation pump 16 operate in this order, and the stored water passes through the cooling water introduction pipe 15 to the shower vibe 17 or onto the heat sink 13 of the steam exhaust pipe 9 housed in the condensing means 11. The water is supplied and collected again at the bottom of the condensing means 11, thus circulating. The bellows pump 26 is activated, and the waste liquid in the waste liquid supply tank 24 passes through the waste liquid introduction pipe 25, passes through the heat exchange means 10, and is then sent into the evaporation pot 1. When the amount of waste liquid in the evaporation pot 1 increases and the liquid level is detected by the liquid level sensor 4 for, for example, 3 seconds or more, the operation of the bellows pump 28 is stopped, and at the same time the heating means 2 is switched on, and the heating evaporation is started. will be started. Evaporation pot by heating evaporation! When the amount of waste liquid inside decreases, the liquid level drops, and the liquid level is not detected by the liquid level sensor 4 for more than 3 seconds, the bellows pump 26 is switched on again.
The operation of supplying the waste liquid in the waste liquid supply tank 24 into the evaporation pot 1 is repeated. The steam evaporated from the evaporation pot 1 passes through the steam exhaust pipe 9, exchanges heat with the waste liquid in the heat exchanger 10, and then passes through the condensing means 11, where a part of it is condensed to become condensed water. This condensed water passes through the accumulated liquid introduction pipe 12 together with the remaining gas in the steam, is sent into the accumulated liquid tank 19, and is sent to the tip 912a below the accumulated liquid surface.
The condensed water is stored in the reservoir tank 19. At this time, bubbling occurs as the gas released from below the surface of the reservoir rises within the reservoir, and this bubbling causes gases such as hydrogen sulfide melted in the reservoir to be expelled from the fluid. Further, from the chemical liquid tank 32, a bellows pump 34 supplies an amount of alkali metal carbonate as a chemical liquid according to the amount of the accumulated liquid in the accumulated liquid tank 19, and the alkaline gas from the accumulated liquid due to bubbling is supplied. promote the occurrence of Note that this reservoir tank 19 communicates with the atmosphere via an activated carbon cartridge 21 filled with activated carbon, thereby preventing odor from being released into the atmosphere. In this way, the gas generated from the accumulated liquid is transferred to the accumulated liquid tank 19 through the air introduction pipe 22 by the operation of the air pump 23.
From there, it is discharged into the photographic processing waste liquid located at the lower part of the evaporation pot 1, where evaporation v:i condensation has been promoted. From the condensate obtained by heating and evaporating the photographic processing waste liquid and cooling and condensing the resulting vapor,
Gas is generated by bubbling or chemical addition, and the gas that is not cooled and condensed out of this vapor and the gas generated from the condensate are returned to the photographic processing waste liquid that is being heated. The generation of hydrogen sulfide, etc., which is a malodorous component, is suppressed. When the liquid level sensor 27 detects that there is no waste liquid in the waste liquid supply tank 24, the operation of the bellows pump 26 is stopped, the heating means 2 is turned off, and after 2 hours the liquid is cooled down. The water circulation pump 16 and the air cooling fan 18 stop, the lamp lights up, and
A buzzer sounds to notify that the evaporation concentration process has been completed, and the air pump 23 stops. Here, the ball pal 3 is opened and the sludge in the evaporating pot 1 is dropped into the polypropylene bag 7, and then the O-ring 8 is removed and taken out. In addition, during the evaporation concentration process, when the liquid level sensor 14 detects that the water in the condensing means 11 has run out, the lamp lights up and the buzzer goes off, indicating that the stored water has run out. Let me know. Additionally, during the evaporation and concentration process, the temperature sensor 30 detects that the liquid level in the evaporator 1 has abnormally decreased for some reason, and the temperature in the evaporator 1 has risen to 120°C due to air stirring. Then, the lamp lights up, a warning buzzer sounds, and the heating means 2 is turned off. From then on, the evaporation concentration process is interrupted by the series of operations described above. FIG. 3 shows another embodiment. In this embodiment, a heating means 2 and a temperature sensor 30 are provided in the evaporating pot 1, and a propeller 35 is forcibly rotated by a motor 36 to stir the waste liquid, thereby promoting evaporation. A scattering prevention plate 37 is provided in the evaporation pot 1 to prevent the waste liquid from scattering into the reservoir liquid introduction pipe 12 due to stirring. The sludge receiver 6 can be removed by a gasket 38 provided under the ball valve 3, and the sludge receiver 6 is connected to the waste liquid supply tank 2 via a cock 39.
4, and forms an escape route for air when dropping the sludge in the evaporator 1. In addition, since cooling fins 40 are provided on the accumulated liquid introduction pipe 12 so that it is directly cooled by the outside air, the condensing means 11 has no moving parts and the mechanism is simplified. The reservoir tank 19 is provided with a drug addition port 40 and a reservoir circulation mechanism 41 as a gas generating means. A drug solution is added as appropriate from the drug addition port 40, and the pump 4 is fed from the tip 42a of the reservoir fluid circulation vibrator 42 of the reservoir fluid circulation mechanism 41.
3, the accumulated liquid is radiated into the air in the accumulated liquid tank 19, the accumulated liquid is circulated, and gases such as hydrogen sulfide melted in the accumulated liquid are expelled from the liquid. The accumulated liquid stored in the accumulated liquid tank 19 is discharged to the outside via the three-way cock 44. [Experimental Example] After printing a commercially available color photographic paper, continuous processing was performed using the following processing steps and processing solution. Standard processing steps (1) Color development 40℃ 3 minutes (2) Bleach fixing 38℃ 1 minute 30 seconds (3) Stabilization treatment
25℃~35℃ 3 minutes (4) Drying 75℃~1
00°C Approximately 2 minutes Processing liquid composition [Color development tank liquid] Ethylene glycol 15mL Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride
0.2g potassium carbonate
24.0g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.5g optical brightener (4,
4'-diaminostilhene disulfonic acid derivative)
1.0g hydroxylamine sulfate
3.0g 1-Hydroxyethylindene-1,1-diphosphonic ao, 4g hydroxyethyliminodiacetic acid 5.0g Magnesium chloride.
Hexahydrate 0.7g1.2-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2
Add g water to bring the pH to 11, and adjust the pH to 1 with potassium hydroxide and sulfuric acid.
Let it be 0.20. [Color developer replenisher] Ethylene glycol 20ml! Potassium sulfite 3.0g Potassium carbonate 24.0g and Droxyamine sulfate 4.0g 3-Methyl-4-amino-N
-ethyl-N-(β-methanesulfonamide ethyl)aniline sulfate 7.5g optical brightener (4,4
'-diaminostilbendisulfonic acid derivative)
2.5g 1-hydroxyethylindene-1.1-
Niphosphonic acid 0.5gHydroxyethyliminodiacetic acid 5.0gMagnesium chloride hexahydrate 0.8g1.2-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.
Add 3 g of water to make 12, and adjust to pH 10.70 with potassium hydroxide and lfEM. [Bleach-fix tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate so, 0g ethylenediaminetetraacetic acid 3.0g ammonium thiosulfate (70% solution) 100. mu Ammonium sulfite (40% solution) 27.5 ml 1 Add water to bring the total volume to 12, and dilute with potassium carbonate or glacial acetic acid.
Adjust to H7.1. [Bleach-fixing replenisher A] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260.0g Potassium carbonate 42.0g Add water to make a total amount of 1j2. The pH of this solution was adjusted to 6.7 using acetic acid or aqueous ammonia.
Set to ±0.1. [Bleach-fix replenisher B] Ammonium thiosulfate 250.0 ml (70
% solution) Ammonium sulfite 25.0ml! (40
% solution) Ethylenediaminetetraacetic acid 17.0g ice vinegar WR
85, Omj! Add water to make a total volume of 11. This solution has a pH of 5.3 using acetic acid or aqueous ammonia.
It is ±0.1. [Water wash alternative stable tank fluid and replenisher] Ethylene glycol 1.0g 2-methyl-4-isothiazolin-3-one
0.20g 1-hydroxyethylidene-1
,1-niphosphonic acid (60% aqueous solution 1.0g ammonia water (ammonium hydroxide 25% aqueous solution) 2.0g 1 with water
2 and adjust the pH to 7.0 with 50% sulfuric acid. Fill an automatic processor with the above-mentioned color developing tank liquid, bleach-fixing tank liquid and stabilizing tank liquid, and add the above-mentioned color developing replenisher and bleach-fixing replenisher A every 3 minutes while processing the color photographic vapor sample of the reprint. A running test was conducted while replenishing B and stable replenisher through the bellows pump. The amount of replenishment is 190 mJl to the color developing tank per color paper, and 50 mJ2 each of bleach-fixing replenisher A and B to the bleach-fixing tank.
, 25% of the water washing alternative stabilizing replenisher was added to the stabilizing tank.
0 mIt supplemented. In addition, the stabilization tank of the automatic developing machine is a stabilizing tank with the first to third tanks in the direction of the flow of the sample.
A multi-vessel countercurrent system was used in which replenishment was performed from the final tank, and the overflow liquid from the final tank was allowed to flow into the previous tank, and this overflow liquid was also allowed to flow into the previous tank. Continuous processing was performed until the total amount of replenishment of the water washing alternative stabilizing solution became three times the capacity of the stabilizing tank. However, 400g of potassium carbonate is added to the photographic processing waste liquid in advance.
and 4g of antifoaming agent FS Antiform 025 (manufactured by Dow Corning) were added to reduce the surface tension of the photographic processing waste to 19.
dyne/cm to 26 dyne/cm.

[Experiment 1] Using the color vapor waste liquid described above, the following three types of experiments were conducted using the photographic processing waste liquid evaporation concentrator shown in FIG. 1 to measure the degree of concentration when hydrogen sulfide was generated. (Comparison 1) Air pump 301/min, accumulated liquid introduction pipe 1
2 and the air introduction pipe 24 are connected together to the reservoir tank 19 as shown in FIG. Therefore, no gas generating means is provided. (Invention 2) Air pump 304! /m1n (Invention 3) Air pump 3042/min, 50$1iq20gel of 2CO3 as an alkaline agent in the reservoir tank 19
was added. As is clear from this table, when bubbling is used as a gas generating means, the concentration level when hydrogen sulfide is generated increases. Adding an alkaline agent to the condensed water in the distillate tank further increases the concentration, and the concentration when hydrogen sulfide is generated becomes 1/15, which is approximately equal to the final concentration. This shows that by performing bubbling and adding an alkali agent as gas generating means and returning the generated gas to the evaporator 1, the generation of hydrogen sulfide from condensed water can be almost completely suppressed even in the final concentration stage. The tip 12a of the accumulated liquid inlet pipe 12 was placed outside the liquid to eliminate bubbling, and the gas generating means had only a wide opening area. The air pump was operated at 30 IL/min, and 10 g/iL of NaOH was added to the reservoir tank 19.

[Experiment 2] Next, using the color vapor waste liquid shown in Fig. 2, add 20% liq.
30 g/fi was added, and the degree of concentration at the time of hydrogen sulfide generation with respect to the air flow rate of the near blower 25 was measured, and the evaporation efficiency was determined from the amount of evaporation and the amount of electricity. As is clear from this table, the air flow rate is 3.0 (42
/win) In the above, the concentration level when hydrogen sulfide is generated is all 1.
/15 or less, which exceeds the concentration level of the final concentration stage. It can be seen that the evaporation efficiency is maximum when the air flow rate is 10.0 (u/win), and the concentration at this time is also 1/15 or less, which is the effectively optimum air flow rate. (Effects of the Invention) As described above, the present invention provides a method for evaporating and concentrating a photographic processing waste liquid and an apparatus thereof. This gas is heated and returned to the photographic processing waste liquid side where it is evaporated and condensed, so even if the waste liquid becomes highly concentrated, the generation of malodorous components from the condensed water is suppressed. Ru. In particular, the generation of hydrogen sulfide and sulfur is greatly reduced in photographic processing waste liquids mainly composed of thiosulfates, making it ideal for processing photographic processing waste liquids.

[Brief explanation of drawings]

Fig. 1 is a schematic diagram of an automatic developing machine, Fig. 2 is a schematic diagram showing one embodiment of the invention, Fig. 3 is a schematic diagram showing another embodiment, and Fig. 4 is a schematic diagram showing an embodiment of the invention.

【experiment! ] is a diagram in which the accumulated liquid introduction pipe 12 and the air introduction pipe 24 are combined into one and connected to the accumulated liquid tank 19. In the drawings, reference numeral 1 is an evaporation pot, 2 is a heating means, 5 is a liquid level sensor, 11 is a condensing means, 19 is a reservoir tank, 20 is a bubbling mechanism, 22 is an air introduction pipe, 24 is a waste liquid supply tank, and 31 is a The chemical solution addition mechanisms 31 and 41 are reservoir liquid circulation mechanisms. Figure 1 Procedural Amendment September 7, 1988 / '\ 'S Director General of the Patent Office Yoshi 1) Written by Mr. Takeshi 1 Indication of the case 1988 Patent Application No. 144771 2 Name of the invention Evaporation of photographic processing waste liquid Concentration processing method and device 3 Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Address 2-23-1-6 Yoyogi, Shibuya-ku, Tokyo Target of amendment
In the Detailed Description of the Invention section of the specification, in the drawings (1), on page 5, line 10 of the specification, "can be done" is corrected to "can be done." (2) In the same book, page 12, lines 3 to 5, r Cartridge heaters are processed and molded into ``cartridge heaters, quartz heaters, Teflon heaters, bar heaters, panel heaters'' corrected. (3) In the same book, page 18, line 8, "do" is corrected to "do". (4) In the same book, page 19, line 6, "aminophenol meter" is corrected to "aminophenol type." (5) In the same book, page 21, lines 17 to 18, "preferably" is corrected to "preferably." (6) In the second line of page 25 of the same book, "stabilizing bath" is corrected to "stabilizing liquid." (7) In the same book, page 26, lines 19 and 20, "to be done" is corrected to "to be done". (8) "Liquid level meter 27" on page 29, line 7 of the same book as "
"Liquid level sensor 27". (9) "Pump 34" on page 29, line 16 of the same book is corrected to "bellows pump 34." (10) r201J in the first line of page 30 of the same book is “20fL
Correct it to J. (11) ``Activated carbon cartridge 20 filled with activated carbon 21'' on page 30, line 3 of the same book is corrected to ``Activated carbon cartridge 21 filled with activated carbon.'' (12) In the same book, page 30, line 17, "heat sink 13" is corrected to "cooling heat sink 13." (13) “Bellows Pump 28” on page 31, line 5 of the same book
is corrected to "bellows pump 26". (14) "Pablung" in the first and second lines of page 32 of the same book is corrected to "babbling." (15) In the same book, page 32, lines 4 and 5, "by the bellows pump 34" is corrected to "by the bellows pump 34." (16) "r ball pal 3" on page 33, line 13 of the same book as "
Ball valve 3" is corrected. (17) “Drug addition port 40” on page 35, line 5 of the same book is changed to “
Drug addition port 45" is corrected. (18) Correct "went" in line 17, page 35 of the same N, to "did". (19) “Magnisium” in page 37, line 17 of the same book is f.
Magnesium,” he corrected. (20) In the same book, page m39, Ml, line 4, r (60% aqueous solution) is corrected to “(60% aqueous solution).” (21) In the same book, page 40, line 4, “gone” is corrected to “did”. (22) “Deed” in the same book, page 40, lines 11 and 12.
Correct it to ``do''. (23) In the same book, page 40, line 17, ``I went'' is corrected to ``I did.'' (24) "Air introduction tube 24" in line 17 of page 44 of the same book is corrected to "air introduction tube 22." (25) From page 44, line 20 to page 45, line 1 of the same book, “
5 is a liquid level sensor" is corrected to ``4 is a liquid level sensor." (26) Figures 2 and 3 of the drawings are corrected as shown in the attached sheet. that's all

Claims (6)

[Claims] (1) In a method for evaporating and concentrating a photographic processing waste liquid, the resulting vapor is cooled and condensed to obtain a condensate, in which a gas is generated from the condensate, and the components of the condensate are A method for evaporating and concentrating a photographic processing waste liquid, in which a gas containing the above is returned to the heated photographic processing waste liquid side. (2) In an evaporation and concentration processing apparatus for photographic processing waste liquid, which has an evaporating means and a heating means for heating and evaporating and concentrating the photographic processing waste liquid, and a condensing means for cooling and condensing the evaporated vapor, the condensed water is condensed by the condensing means. An apparatus for evaporating and concentrating photographic processing waste liquid, comprising a gas generating means for generating gas from a liquid, and a means for returning the gas containing the condensed liquid component to the evaporating means. (3) The apparatus for evaporating and concentrating photographic processing waste liquid according to claim 2, further comprising means for returning the gas that has passed through the condensing means and the gas generated by the gas generating means to the evaporating means. (4) The gas generating means is configured to store condensed liquid and generate gas.
An evaporative concentration treatment device for photographic processing waste liquid as described in 2. (5) The photographic processing waste liquid according to claim 2 or 3, wherein the means for returning to the evaporating means side is configured to forcibly return the gas generated from the gas generating means to the evaporating means side. evaporation concentration processing equipment. (6) The gas generating means is configured to store condensed liquid and add an acid agent or an alkaline agent to the stored condensed liquid. and the evaporative concentration treatment apparatus for photographic processing waste liquid according to any one of Item 5.