JPS63287588A - Method and device for evaporating and concentrating waste photographic processing solution - Google Patents

Abstract

PURPOSE:To control development of malodor when a waste photographic processing soln. is evaporated and concd. and to control the generation of free sulfur, etc., by evaporating and concentrating the soln. at a temp. below the b.p. at least at a part in the process, and condensing the generated vapor. CONSTITUTION:The waste photographic processing soln. is heated to evaporate at least a part of the soln., and the remainder is concd. and recovered. In this case, the soln. is evaporated and concd. at a temp. (e.g., 30-95 deg.C) below the b.p. at least at a part in the process, and the generated vapor is condensed. As a result, development of malodor in the evaporation and concentration, and the generation of free sulfur, etc., can be prevented, the evaporation rate is improved, and the evaporation at a temp. below the b.p. can be promoted. In addition, an increase in the pressure in the device can be reduced, the gas is not leaked to the outside, and the device can be safely operated.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention is directed to 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. The present invention relates to an evaporative concentration processing method and an apparatus thereof, and more particularly to an evaporation concentration processing method and an apparatus thereof for a single photographic processing solution placed in or near an automatic processor for processing.

(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 the photographic processing of 11 light-sensitive materials, the components consumed during processing are replenished, while the components that are eluted into the processing solution or concentrated by evaporation during processing, such as bromide ions in the developer and bromide ions in the fixer, are replenished. lol
A method is used to maintain the performance of the processing solution at a constant level by removing components (such as complex salts) and keeping the processing solution components constant.
A portion of the processing solution is discarded to remove thickening components during photographic processing.

In recent years, systems have been changing to systems in which the amount of replenishment fluid, including washing water, which is used as a replenishment fluid for washing, has been 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. It has disadvantages such as requiring

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, in the research and experiments conducted by the inventors, when photographic processing waste liquid is continuously evaporated at a temperature above its boiling point, evaporation progresses and the concentration rate increases, resulting in the formation of sulfur dioxide gas, hydrogen sulfide, ammonia gas, etc. Harmful or extremely foul-smelling gases 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. Due to this pressure, the harmful or malodorous gas leaks 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 present 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. We have previously proposed a method and apparatus for concentrating photographic processing waste liquid in which condensed components are also treated and discharged to the outside.

However, when photographic processing waste liquid is subjected to evaporative concentration treatment and the degree of concentration increases, it has the disadvantage that the amount of evaporation of sulfur-based malodorous gases increases significantly. Additionally, as the amount of sulfur-based malodorous gas generated increases, free sulfur also begins to be generated.
The condensate becomes in a state where it cannot be disposed of in the sewage system or the like. For this reason, various studies and experiments were conducted to suppress the generation of sulfur-based malodorous gases due to the progress of concentration, and the results were as follows: It is most effective to suppress the generation of foul-smelling hydrogen sulfide and free sulfur by condensing the resulting vapor. Furthermore, it is easy to evaporate and concentrate below the boiling point, making the equipment safer. It was also found to be optimal from the standpoint of efficient operation.

(Object of the Invention) This invention has been made in view of the above-mentioned conventional problems, and the first object of the invention is to suppress the generation of foul odors, free sulfur, etc. that occur during 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 and an apparatus therefor. A second object of the present invention is to provide a method for evaporating and concentrating photographic processing waste liquid and an apparatus therefor, which enable safe and efficient operation of the apparatus.

(Means for Solving the Problems) In order to solve the above-mentioned problems of the present invention, the first invention heats the photographic processing waste liquid, evaporates at least a part of it, and concentrates and collects the remaining part. The method for evaporating and concentrating photographic processing waste liquid is characterized in that the photographic processing waste liquid is evaporated at a temperature lower than its boiling point during at least a part of the processing process, and the resulting vapor is condensed.

In this invention, it is further preferable to evaporate and concentrate at least at the boiling point of the photographic processing waste liquid at the beginning of the process, since this improves the evaporation rate.

Further, a second aspect of the present invention provides an evaporative concentration processing apparatus for photographic processing waste liquid, which heats the photographic processing waste liquid to evaporate at least a part of the photographic processing waste liquid, and concentrates and recovers the residual portion. It is characterized by having means for evaporating and concentrating by controlling the temperature in part to be lower than the boiling point, and means for condensing the vapor produced thereby.

The temperature for evaporating and concentrating the photographic processing waste liquid of this invention is preferably set at 30°C to 95°C, more preferably 35°C to 90°C, and even more preferably 40°C to 80°C, at a temperature that does not boil the photographic processing waste liquid. . Further, it is preferable to change the temperature of evaporation concentration depending on the evaporation concentration of 1.5 times or more. For example, the temperature of evaporation concentration of photographic processing waste liquid is 30°C to
The case of 0°C is particularly preferable when the concentration is 2 times or more,
In the case of 40°C to 80°C, it is preferably used when the concentration is 3 times or more. When concentrating, it is preferable to evaporate at a temperature close to the boiling point at the start of the process because the evaporation process time can be shortened.

As a means for evaporating and concentrating the photographic processing waste liquid of the present invention by controlling the temperature to be lower than the boiling point, there is a heating means, and in addition to the heating means, at least one of a cooling means or a means for stopping heating, Means for detecting temperature and operating to keep the temperature constant.

Further, in order to keep the temperature constant in a steady state even if the temperature is not detected, the heater capacity may be adjusted by heat radiation or cooling, for example.

Any known method can be used as the heating means,
For example, it may be a nichrome wire, or it 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.

Here, the evaporation means 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 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., but from the viewpoint of safety and corrosion resistance, stainless steel (preferably 5trs304 or 5US316) is used. , particularly preferably 5US316) and titanium.

In addition, any known method can be used as the cooling means, such as using a cooler such as an air bubbling chiller, cooling water or waste liquid before treatment, but a method that does not reduce the concentration during treatment is used. It is preferable.

Furthermore, all kinds of heat exchange means can be adopted as means for condensing the vapor generated by the evaporative concentration of this invention, including (1) shell and tube type (multi-tube type, cannula type) (2) double back It may be of any 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.

Adopting an air-cooled heat exchanger is also advantageous, (1) Push-in ventilation type (2) Blowing ventilation type It may be either.

This condensation of vapor facilitates evaporation and concentration, which not only reduces the generation of sulfur-based gases outside the system, but also improves the evaporation rate and has the effect of promoting evaporation below the boiling point.

The means for stopping the heating means turning off the power supply for the heater.
Any known means such as opening and closing a burner valve can be used.

As the means for detecting the temperature of the evaporation concentration, any known method can be used as long as it can measure the photographic processing waste liquid during the evaporation process, such as a resistance thermometer, a thermistor, or a thermoelectric device. For example, semiconductor applied sensors, vibration applied crystal temperature sensors, and N
Examples include a QR thermometer and a thermometer that uses changes in magnetic susceptibility, but it is preferable to use one that can extract some kind of "signal" because the device can be electrically controlled.

In this invention, evaporation concentration means reducing the volume of waste liquid to less than half of the volume when it comes out of the photographic processing tank,
From the viewpoint of disposal, it is preferably one-fourth or less, more preferably one-fifth or less, and optimally one-tenth or less. Evaporation and concentration may generate precipitation or tar. A liquid that is fluid as a whole or in a liquid state is a concentrate.

(Example) Next, an example of the method and apparatus for evaporating and condensing photographic processing waste liquid according to the present invention will be described with reference to the accompanying drawings.

A Automatic developing machine The automatic developing machine to which this invention is applied is designated by the reference numeral 10 in FIG.
Color developing tank CD, bleach-fixing MIBF, water washing alternative stable Wi
It is of a type in which it is continuously guided through a sb, subjected to photographic processing, and after drying, it is rolled up. Reference numeral 11 denotes a replenishment tank, in which a sensor 21 detects the processing amount of the photographic light-sensitive material F, and a control device 20 replenishes each processing tank with a replenisher based on the information.

B. Recovery of Photographic Processing Waste Liquid Next, representative examples of photographic processing waste liquid that can be treated according to the present invention will be described in detail. However, below we will mainly discuss the photographic processing solutions when the photographic materials to be processed are color ones, or the photographic processing waste fluids will be referred to as the overflow generated 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 for forming a color image, specifically a process for forming a color image through a coupling reaction between an oxidized product of a color developing agent and a color coupler). Therefore, in the color development 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 Hensyl 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 sequestering agents in the color developing solution.

The bleach-fixing 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 pH buffers may be added to the bleach-fix solution, either alone or in combination.
It may contain more than one species in combination.

Furthermore, it may contain various fluorescent whitening agents, 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
-558, Belgian Patent No. 770.9 ] 0, Japanese Patent Publication No. 8836/1983, Japanese Patent Publication No. 53-9854, Japanese Patent Publication No. 1987-
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., and particularly preferred for the effects of this invention are diethylenetriaminepentaacetic acid and 1-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 IJZ, more preferably about 0.5 g to 5 g for Stabilizer II1.

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 arsenate, 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, ammonium malate , ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate,
These include ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, and 2,4,6-dolinitrophenolammonium. The amount of these ammonium compounds added is 0°05~ per stabilizer IIt! It is used in the range of 00g.

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.

Particularly, in the present invention, when using a washing substitute stabilizing liquid containing an 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 the present 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 surface-stage processing solution that has adhered to or penetrated into the photographic light-sensitive material. Only 30 Ifij per unit area of photosensitive material! /m2~9000m II /rn'
, more preferably 60ml1/l112~3000m
By supplementing IL/m2, it has an effect equivalent to or better than the above, and specifically, it is described in JP-A-58-134.
Refers to image stabilization processing as described in No. 636.

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.

Hereinafter, recovery of photographic processing waste liquid will be explained.

When each treatment tank is replenished with replenisher liquid, it is discharged from the treatment tank as overflow waste liquid and is sent to the stock tank 3.
0 (numeral 31 indicates a case where there is a plurality of stock tanks). In this automatic developing machine, the amount that overflows from the upper part of the processing tank due to replenishment of the replenisher is treated as photographic processing waste solution.

Stock tank 30 for overflowing photographic processing waste liquid
A simple way to supply soot is to let it fall naturally through a guide tube, but it is also possible to arrange a heat exchanger in the middle to collect the thermal energy possessed by the photographic processing waste solution, or to use an automatic developing method. The stock tank 3 is
As indicated by reference numeral 12, a means for preheating or evaporating the water content of the photographic processing waste liquid may be provided before the photographic processing waste liquid is collected in the tank 0, or it may be forcibly transferred by a pump 23 or the like.

Moreover, as mentioned above, each photographic processing tank CD, BF,
Due to differences in Sb components in photographic processing waste liquids, all photographic processing waste liquids are not treated at once, but are stored in stock tanks for each photographic processing tank or for each waste liquid of processing tanks divided into two or more groups. This also includes the case where 30 (31) are prepared and processed separately. In particular, it is effective to separate the waste liquid from the color developer tank CD from the waste liquid from the bleach-fix tank BF and washing alternative stabilizing tank SB from the point of view of recovering silver, and it is also effective when reusing distilled water. .

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

In addition, when applying this invention, the stock tank 30
It also includes a method in which the overflowing photographic processing waste liquid is directly supplied to the processing means without using a processing tank, or the photographic processing waste liquid is directly supplied to the processing means from the processing tank.

C Processing Means The processing means 40 of the present invention includes means for evaporating and concentrating the photographic processing waste liquid by controlling the temperature to be lower than the boiling point, and the temperature of the evaporative concentration is preferably 30°C to 95°C, more preferably 40°C. The temperature is set at a temperature that does not boil the photographic processing waste liquid at ~80°C. Furthermore, it is preferable to change the temperature of evaporation concentration according to the evaporation concentration of 1.5 times or more. For example, especially when the temperature of evaporation concentration of photographic processing waste is 30°C to 95°C, the concentration is 2 times or more. Preferably when the temperature is 40°C to 80°C
In the case of , it is preferably used when the concentration is 3 times or more.

As a means for evaporating and concentrating the photographic processing waste liquid of this invention by controlling the temperature to be lower than the boiling point, there is a heating means 41. chamber 42, means 43 for discharging the processed photographic processing waste liquid (11A condensed liquid) from the processing chamber 42;
It includes.

Further, it is preferable to add gas adsorption means 50 using a filter, adsorbent, etc., and distilled water reuse means 60 including steam cooling means.

Evaporative concentration in this invention means reducing the volume of waste liquid to one-half or less of the volume when it comes out of the photographic processing tank, preferably one-fourth or less from the viewpoint of disposal, and more preferably five minutes or less. Optimally, it is one-tenth or less. When concentrated, precipitation or tar may be generated. A liquid that is fluid as a whole or in a liquid state is a concentrate.

As the heating means 41, the heat source and its transmission method are important, and although it is not limited to a specific one, electric,
It is preferable to use one or a combination of two or more heat sources, such as gas, whose heat capacity can be easily and quickly changed.

There are those that collect the photographic processing waste liquid in the processing chamber 42 and heat the whole, for example, those that drop or drop (including spraying) the photographic processing waste liquid onto a heating zone such as an overheated metal plate and evaporate it, and those that evaporate it in fixed quantities. Various configurations are possible, including one that supplies the heat source to the heat source and processes the heat source continuously.

Furthermore, the photographic processing waste liquid may be sprayed into the processing chamber 42 in the form of a mist and heated air is applied to evaporate the photographic processing waste liquid, or the heated air may be introduced into the photographic processing waste liquid. Good too. In such embodiments, it is also desirable to utilize drying air.

In addition, for spraying, it is preferable to place the photographic processing waste liquid on a heated swirling air stream, and a spray drying apparatus can be used.

The position of the heating means 41 is arbitrary, such as inside the collected photographic processing waste liquid, inside the processing chamber 42, or outside the processing chamber 42.

Note that when the heating means 41 is in direct contact with the photographic processing waste liquid, such as a quartz tube with a built-in heat source such as a nichrome wire or a heat exchanger plate,
In order to prevent concentrated photographic processing waste from adhering to the surface and reducing thermal efficiency, for example, fluororesin (e.g.
It is preferable to contact the waste liquid through a metal having a protective film such as Teflon (Teflon) or the like.

There are various methods for making the heat capacity variable in the heating means, but electrical control such as a quartz tube with a built-in heat source such as a nichrome wire or a heat exchanger plate is preferable. In the case of electrical control, it can also be performed by controlling voltage and current, but for example, by arranging a plurality of devices with the same wattage or a plurality of devices with different wattages, each ON10F
F control may be used to control the overall heat capacity. In this case, for example, if combined with a timer, it is possible to easily control the wattage to automatically switch to the maximum wattage at the beginning of the evaporation process.

Furthermore, the heat capacity can be changed freely, from stepwise to gradual curves.

The configuration of the processing chamber 42 is determined in accordance with the configuration of the heating means 41 described above, but if the processing chamber 42 is a hard one that stores photographic processing waste liquid to be processed or processed materials, it may be made of metal, ceramics, etc. It is preferable that the inner pot is formed of synthetic resin or the like, and the treated concentrated liquid is taken out of the inner pot and disposed of or treated.

The gas adsorption means 50 absorbs hydrogen sulfide, sulfur oxide, or ammonia gas (H2) contained in the evaporated photographic processing waste liquid.
This method separates and recovers harmful gases such as S 502 N113 etc. using zeolite adsorbents, activated carbon, etc.

The condensing means 60 processes the distilled water evaporated by the waste liquid treatment means 40 using activated carbon, a reverse osmosis membrane, ultraviolet irradiation, an oxidizing agent, etc. to obtain distilled water, which is used as a photographic processing solution in the automatic processor 10. be done. The photographic processing waste liquid of this invention is
In addition to the heating means 41, the means for controlling the temperature to be lower than the boiling point includes at least one of cooling means or means for stopping heating, and means for detecting the temperature, so as to keep the temperature constant. Refers to means of operation, etc.

The concentration detecting means 70 includes, for example, a measuring device that measures the transmittance (attenuation rate) and refractive index of light by placing a light emitter, a reflector, a light receiver, etc. at a certain height in the processing chamber. It will be done. It can also be detected by a change in electrical resistance that accompanies a change in concentration.

D. Control The method and apparatus for evaporating and concentrating photographic processing waste liquid of the present invention are generally applicable.

(1) Supply of photographic processing waste liquid from the stock tank 30 to the processing means 40 The photographic processing waste liquid is supplied from the stock tank 30 to the processing means 40 in fixed quantities (the amount that can be stored at one time in the waste liquid processing means 40). There are two methods: a method of supplying the fluid at once, and a method of supplying a fixed amount or a variable amount continuously. The sensor 22 detects the amount of photographic processing waste liquid in the stock tank 30 and/or the sensor 24 detects the amount of photographic processing waste liquid in the processing means 40 from the stock tank 30 to the processing means 4.
Controls the supply of photographic processing waste to 0.

In the case of a method that continuously supplies fixed amount or variable amount,
The amount is adjusted by detecting the temperature of the supplied photographic processing waste liquid and the temperature of the heating means 41 or the processing chamber 42 of the processing means 40. In addition, the amount of photographic processing waste liquid supplied is always constant,
The amount of photographic processing waste liquid in the processing stage f 40 may be detected by the sensor 24, and the heating means 41, for example, a heater, may be used or the heating time may be increased or decreased depending on the detected amount.

(2) Operation of the processing means 40 The processing means 40 is operated under the condition that the temperature for evaporating and concentrating the photographic processing waste liquid is lower than the boiling point. Furthermore, it is preferable to change the temperature of evaporation concentration depending on the evaporation concentration of twice or more. For example, when the temperature of evaporation concentration of photographic processing waste liquid is 30°C to 95°C, especially when the concentration is twice or more. In the case of 40°C to 80°C, it is preferably used when the concentration is 3 times or more.

Further, up to 1.5 times concentration is preferable from the viewpoint of improving the evaporation rate, or by evaporating and concentrating at the boiling point of the photographic processing waste liquid.

Under these conditions, the treatment of photographic processing waste is determined by the difference between the amount of photographic processing waste supplied and the amount of processed photographic processing waste, or the amount of residual photographic processing waste or the amount of processed and concentrated photographic processing waste. It is carried out according to the amount of treated waste liquid.

In addition, in the case where the photographic processing waste liquid is supplied in a fixed amount at a time to the processing means 40, if the temperature of the supplied photographic processing waste liquid and the temperature of the heating means 41 or the processing chamber 42 are detected, the processing is started. The operation of the processing means 40 can be controlled by time.

In the above, the processing progress of the photographic processing waste liquid in the processing means is controlled by the processing time, as well as by the viscosity of the photographic processing waste liquid and the processing chamber 4.
It is controlled by detecting the lower limit level of the photographic processing waste liquid in 2, the temperature, pressure, weight, conductivity, etc. mentioned above, and when the photographic processing waste liquid is concentrated to a certain concentration, the operation of the processing means 40 is stopped or low energy operation is performed. It is preferable to switch to .

[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℃ Approximately 2 minutes Processing solution composition [Color development tank liquid Coethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride
0.2g potassium carbonate
24.0g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.5g optical brightener (4,
4°-diaminostilbendisulfonic acid derivative)
1.0g hydroxylamine sulfate 4
3.0g 1-hydroxyethylindene-1,1-niphosphonic acid 0.4g hydroxyethyliminodiacetic acid 5.0g magnesium chloride hexahydrate 0.7g 1.2-dihydroxybenzene-
3,5-disulfonic acid disodium salt 0.2g Add water to adjust to 12, pH 10 with potassium hydroxide and sulfuric acid,
20.

[Color developer replenisher] Ethylene glycol 20mM potassium sulfite 3.0g potassium carbonate
24.0g hydroxyamine sulfate 4.0g 3-methyl-4-amino-N-
Ethyl-N-(β-methanesulfonamide ethyl)aniline sulfate 7.5g Optical brightener (4,4
°-diaminostilhene disulfonic acid derivative)
2.5 g 1- and droxyethylindene-1,1-niphosphonic acid 0.5 g hydroxyethyliminodiacetic acid 5. Og Magnesium Chloride
Hexahydrate 0.8g1.2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3
Add g water to bring the pH to 11, and adjust the pH to 1 with potassium hydroxide and sulfuric acid.
Let it be 0.70.

[Bleach-fixing tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100. ml ammonium sulfite (40% solution) 27.5 mA Add water to bring the total volume to 12 and adjust the pH to 12 with potassium carbonate or glacial acetic acid.
Adjust to 7.1.

[Bleach-fixing replenisher A] Ferric ammonium ethylenediaminetetraacetate dihydrate 260.0g Potassium carbonate 42.0g Add water to make a total volume of 1
Set to 1.

The pH of this solution was adjusted to 6.7 using acetic acid or aqueous ammonia.
Let soil be 0 and 1.

[Bleach-fix replenisher B] Ammonium thiosulfate 250.0m12 (70
% solution) Ammonium sulfite 25.0ml/L (40
% solution) Ethylenediaminetetraacetic acid 17.0g Glacial acetic acid
Add 85.0ml 1 water to make 1 total
Let it be 1jZ.

This solution has a pH of 5.3 using acetic acid or aqueous ammonia.
It is ±0.1.

[Water wash alternative stable tank liquid 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 water 1
1 and adjust the pH to 7.0 with 50% sulfuric acid.

Fill an automatic processor with the above color developer tank solution, bleach-fix tank solution and stabilization tank solution, and add the above color developer replenisher and bleach-fix replenisher A every 3 minutes while processing the commercially available color photographic paper sample. A running test was conducted while replenishing B and stable replenisher through the bellows pump. The replenishment amount is 190 mIL per 1 m of color paper to the color development tank, 50 mL each for bleach-fixing replenishment iA and B as replenishment l to the bleach-fixing tank,
Add 250 ml of water washing alternative stabilizing replenisher to the stabilizing tank.
m12 was replenished. In addition, the stabilization tanks of the automatic developing machine are arranged in the direction of the flow of the sample from JJ1 tank to No. 3 stabilization tank.
A multi-vessel countercurrent system was adopted in which replenishment was performed from the final tank, and overflow liquid from the final tank was allowed to flow into the rice bowls before and after it, and this overflow fluid also flowed into the rice bowls before and after it.

Continuous processing was carried out until the total replenishment amount of the water washing substitute stabilizing solution was three times the capacity of the stabilizing tank.

Next, the following experiment was conducted regarding evaporation control by detecting the progress of photographic processing waste liquid treatment.

Example 1 Photographic processing waste liquid to be processed initially supplied into the processing chamber 4
When the heat capacity of the heater was set to 500 W and evaporation treatment was performed, the following results were obtained.

*The generation of sulfur caused the surface solution to turn yellow, and a precipitate was also formed.

** No blockage occurred even after evaporation to near dryness.

Also, if you shortcut the piping of the 4th condensation stage 60, f
Steam leaked from the stock tank that stored the effluent, and a foul odor and sulfur were generated before the concentration ratio as shown in the table above was reached. In addition, the working environment was worse than when the evaporation started due to the strong ammonia odor.

Example 2 Photographic processing waste liquid 4J2 was evaporated with a 500W heater until 3Il of concentrated surface liquid was produced without temperature control.
When the temperature was controlled at 80°C when the iL was released, the odor, sulfur generation, and tube blockage were similar to those in Example 1, but the evaporation time to reach 10 times concentration was shortened to 12 hours. .

Similar results were obtained by measuring the amount of liquid coming out using a liquid level sensor and automatically changing the set temperature using a relay.

Example 3 When 31L of the surface solution of Example 2 came out, the temperature was controlled at 90°C,
Furthermore, when 3.5542 fB of liquid came out, the temperature was controlled at 80°C, and the evaporation time was further shortened to 10 hours.

Example 4 2 Il of a photographic processing waste solution to be processed was put into a processing chamber, and the processing chamber was further replenished with a photographic processing solution to be processed so as to keep the liquid level constant.

At this time, Example 2 is placed in the storage tank for the photographic processing solution to be processed.
Refill a floating pre-level sensor similar to ff18J1.
．． 181.2OR is installed so that it can be detected, there is no temperature control until 8IL replenishment, and after 62L replenishment, it is controlled at 90°C.
After replenishing 162, the temperature was set to be controlled at 80° C. and the operation was performed. At this time, the generation of malodorous sulfur did not occur even if 18JZ was replenished.

Example 5 The results of treating the overflow solution of the bleach-fix solution with a 4It, 500W heater are shown.

*, ** are the same as Example 1 Example 6 Bleach-fixing overflow, ・Fixed with a 42.500W heater at night! ! L Surface liquid without temperature control up to 1.3ft 3.
Temperature control 90℃ distillate up to 2 fl After 3.21, temperature control was set to 80℃, the time to 10 times concentration was 12
I was able to save time.

Example 7 In Examples 1 and 5, air was blown as a cooling means and the temperature during the evaporation treatment was 95°C and 90°C.
Results similar to actual/ih examples 1 and 7 were obtained, but the evaporation rate was increased by about 1.5-2 times.

Example 8 Photographic processing waste liquid was condensed using a 41.500W heater.
With or without ff! It was connected directly to a liquid tank for processing.

(Effects of the Invention) According to the method and apparatus for evaporating photographic processing waste liquid of the present invention, it is possible to achieve the above-mentioned objects, and in particular, it is possible to actively adjust the evaporation concentration temperature of photographic processing waste liquid. By keeping the temperature within a range that does not boil, it is expected that the condensation of the vapor that occurs during concentration will prevent as much as possible the bad odor that occurs during evaporative concentration, as well as improve the evaporation rate of evaporative concentration and promote evaporation below the boiling point. Ru.

In addition, the increase in pressure inside the device can be reduced, gas will not leak to the outside, and safe operation will be possible.
Furthermore, there is no need to provide a means to prevent foul-smelling gas from leaking to the outside.

[Brief explanation of drawings]

The figure 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 10 is an automatic developing machine, 12 is a preheating or evaporation means, 20 is a control device, 40 is a processing device, 41 is a heating means, 42 is a processing chamber, 43 is a discharge means, 50 is a gas adsorption means, and 60 is a The condensing means 70 is a means for detecting concentration. Patent Applicant: Roku Konishi Photo Industry Co., Ltd. Representative Patent Attorney Toshio Owaka Procedural Amendment 1 Case Description 1985 Patent Application No. 121743 2 Title of Invention Method and Apparatus for Evaporative Concentration Treatment of Photographic Processing Waste Liquid 3 Address of the person making the amendment 2-23-1-6 Yoyogi, Shibuya-ku, Tokyo Subject of the amendment Column for detailed explanation of the invention in the specification and column 7 for a brief explanation of the drawings Contents of the amendment As shown in the attached sheet (1) Description Correct “process” in line 9 of page 3 to “process”. (2) In the same book, page 5, line 8, ``can do'' is corrected to ``can do''. (3) "Cartridge heater,...heater" in lines 7 to 9 of page 10 of the same book is changed to "processed and molded like a cartridge heater, quartz heater, Teflon heater, rod heater, or panel heater." corrected. (4) "Heater" in the 4th line of page 14 of the same book is "heater"
I am corrected. (5) "Figure 1" in line 10 of page 15 of the same book is corrected to "Figure 1." (6) In the same book, page 15, line 20, "do" is corrected to "do". (7) Same book, page 16, lines 7, 8, 10 and 1
Correct "r process" in line 1 to "process". (8) In the same book, page 17, line 18, "process" is corrected to "process." (9) Correct "process" in the first line of page 18 to read "r process." (10) "Preferably" in lines 9 and 10 of page 19 of the same book is corrected to "preferably." (11) In the first line of page 24 of the same book, "supply soot" is corrected to "supply." (12) In the same book, page 26, line 12, "filter" is corrected to "filter." (13) In the same book, page 26, lines 13 to 14, "reuse means 60" is corrected to "condensation means 60." (14) In the same book, page 29, line 5, "curve monomo de" is corrected to "curve mono mo de". (15) On page 29, line 9, correct "already done" to "already done". (16) "Waste liquid treatment means 40" on page 29, line 19 of the same book
is corrected to "processing means 40." (1)) "2 o'clock processing" in the first line of page 30 of the same book is corrected to "secondary processing." (18) “Concentration detection means 70J” in page 30, line 9 of the same book.
(19) In the same book, page 30, line 20, "waste liquid treatment means 40" is changed to "treatment means 4".
Correct it to 0J. (20) "Heater" on page 31, line 14 of the same book is corrected to "heater." (21) "Temperature is important" on page 31, line 19 of the same book.
is corrected to ``it is said to be temperature.'' (22) In the same book, page 33, line 9, "process" is corrected to "process." (23) In the same book, page 33, line 9, ``I went'' is corrected to ``I did.'' (24) "Magnesium" on page 35, line 9 of the same book is corrected to "magnesium." (25) In the same book, page 37, line 6, replace “(60% aqueous solution” with “
(60% aqueous solution)”. (26) In the same book, page 37, line 16, ``I went'' is corrected to ``I did.'' (27) "Heater" on page 38, line 13 of the same book is corrected to "heater." (28) "Heater" on page 39, line 12 of the same book is corrected to "heater." (29) In the same book, page 41, lines 1 and 11, "heater" is corrected to "heater." (30) In the same book, page 43, lines 9 and 10, "40 is a processing device" is corrected to "40 is a processing means."that's all

Claims (7)

[Claims] (1) In an evaporative concentration treatment method for photographic processing waste liquid, which heats the photographic processing waste liquid, evaporates at least a part of it, concentrates and recovers the residual amount, the photographic processing waste liquid is heated to a boiling point during at least a part of the processing process. A method for evaporating and concentrating photographic processing waste liquid by evaporating and concentrating at a lower temperature and condensing the resulting vapor. (2) The method for evaporating and concentrating photographic processing waste liquid according to claim 1, wherein the evaporative concentration is performed at the boiling point at least at the start of the evaporative concentration. (3) In an evaporative concentration processing apparatus for photographic processing waste liquid, which heats the photographic processing waste liquid to evaporate at least a portion thereof, and concentrates and recovers the residual portion, the photographic processing waste liquid is heated at least in part during the processing process. An apparatus for evaporating and concentrating photographic processing waste liquid, comprising a means for evaporating and concentrating by controlling the temperature to be lower than the boiling point, and a means for condensing the vapor generated thereby. (4) The apparatus for evaporating and concentrating photoprocessing waste liquid according to claim 3, further comprising means for performing the evaporative concentration twice or more. (5) The apparatus for evaporating and concentrating photographic processing waste liquid according to claim 3, further comprising means for detecting the degree of evaporation concentration, whereby the evaporation concentration is doubled or more. (6) The apparatus for evaporating and concentrating photographic processing waste liquid according to claim 5, wherein the temperature of evaporation and concentration is changed in accordance with the evaporation and concentration that is twice or more. (7) The apparatus for evaporating and concentrating photographic processing waste liquid according to claim 3, further comprising means for evaporating and concentrating the photographic processing waste liquid at its boiling point at least at the start of the evaporative concentration process.