JPS63235943A - Device for evaporating and concentrating photograph processing waste liquid - Google Patents

Abstract

PURPOSE:To decrease a generated harmful or malodorous component by supplying continuously or intermittently a waste liquid in accordance with a signal of a means for detecting the waste liquid quantity in an evaporating oven. CONSTITUTION:When the waste liquid quantity in an evaporating oven 1 increases, and a liquid surface level in a communicating tube 4 increases, and a level is detected, for instance, >=3secs by a liquid surface level sensor 5, an operation of a bellows pump 28 stops and simultaneously a switch of a heating means 2 is turned on, and a heating evaporation is started. By the heating evaporation, the liquid quantity of a waste liquid in the evaporating oven 1 decreases, the liquid surface level in the communicating tube 4 falls, and when the level is not detected >=3secs by the liquid surface level sensor 5, a switch of the bellows pump 28 is turned on, and an operation for supplying a waste liquid in a waste liquid supply tank 26 into the evaporating oven 1 is repeated. In such a way, the waste liquid is always brought to a heating condensation in an optimum state, and a harmful or malodorous component generated by a photograph processing waste liquid can be suppressed small.

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. Regarding evaporation concentration processing equipment,
In particular, the present invention relates to an 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 it is possible to dispose of washing water and cooling water into sewers and rivers, but it is not possible to dispose of washing water and cooling water into sewers or rivers, but it is possible to dispose of washing water and cooling water into sewers and rivers. It has become virtually impossible to dispose of fixing solutions (or bleaching solutions, fixing solutions), stabilizers, etc.]. 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 large 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 takes a large area to set up. It has disadvantages such as requiring a large space.

Furthermore, specifically, as a pollution treatment method for reducing the pollution load of photographic processing waste liquid, activated sludge method (for example, Japanese Patent Publication No. 51-12943 and Japanese Patent Publication No. 51-7952, etc.);
Evaporation method (JP-A-49-89437 and JP-A-56-339)
No. 98, etc.), electrolytic oxidation method (JP-A-48-84462,
No. 49-119458, Special Publication No. 53-43478,
JP-A-49-119457, etc.), ion exchange method (JP-A-51-37704, JP-A-53-383, JP-A-53-43271, etc.), reverse osmosis method (JP-A-50-22)
No. 463, etc.), chemical treatment method (Japanese Patent Application Laid-Open No. 49-84257)
No., JP 57-37396, JP 53-1215
No. 2, No. 49-58833, No. 53-63763,
Japanese Patent Publication No. 57-37395, etc.) are known, but these are still not sufficient.

On the other hand, due to constraints from water resources, rising water supply and drainage costs, the simplicity of automatic processor equipment, and the work environment around automatic processors, in recent years stabilization treatments have been used instead of washing with water, and Photographic processing using automatic developing machines (so-called waterless automatic developing machines) that do not require piping for water supply and drainage is becoming popular. In such processing, it is desired that cooling water for controlling the temperature of the processing liquid can also be omitted. In this type of photographic processing, which does not substantially use rinsing water or cooling water, compared to the case where there is photographic processing waste liquid from automatic processors, the pollution load is extremely large because it is not diluted with water, and on the other hand, the amount of waste liquid is small. be.

Therefore, due to the small amount of waste liquid, it is possible to omit the piping outside the machine for supplying and waste liquid, which is considered to be a disadvantage of conventional automatic processors, as it is difficult to move after installation. The disadvantages such as the small space required, the high cost of piping work during installation, and the high energy cost of hot water supply pressure have been eliminated, and the machine has been made compact and simple enough to be used as an office machine. Benefits are demonstrated.

However, on the other hand, the waste liquid has an extremely high pollution load, and it has become completely impossible to dispose of it not only in rivers but also in sewers in view of pollution regulations. Furthermore, although the amount of waste liquid from this type of photographic processing (processing that uses a large amount of running water and does not involve washing with water) is small, for example, even a relatively small-scale color processing laboratory uses 10 J2 per ton of waste liquid.
It will be about.

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.

On the other hand, in order to solve these problems, research has been conducted on heating 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. , Jitsukai Showa 6O-70flll
It is shown in No. 1 etc. According to research conducted by the inventors, 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, Utility Model No. 60-708.
'I 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 applicant et al. installed a cooling condensing means to condense the vapor generated by the evaporation when evaporating photographic processing waste liquid, and further treated the condensed water generated by the condensation. We have previously proposed a method and apparatus for treating photographic processing waste liquid that also processes non-condensed components and releases them to the outside.

However, it has been discovered that the above proposal has the following problems. In other words, the vapor generated by the evaporation process is condensed by the cooling condensing means, but if the cooling condensation efficiency is poor, the proportion of vapor that is not condensed and is released to the outside of the device increases, resulting in a bad odor even if treated with activated carbon. The rate at which harmful gases are released to the outside of the device also increases. Further, even if the condensed water condensed by the cooling condensing means is treated with activated carbon, it may not be able to be discharged directly to the sewer or the like due to the high pollution load or water loss when discarded.

Furthermore, the space available in minilabs is extremely limited, and not only is the bad odor generated by processing photographic processing solutions a particular problem, but the installation space for the waste solution treatment equipment itself becomes a problem. In addition, the price and running cost of the equipment are important issues, so there is a need for a compact, inexpensive processing equipment that can process photographic processing waste without emitting foul-smelling and harmful gases and has low running costs. There is.

(Object of the Invention) This invention has been made in view of the conventional problems mentioned above, and the first object of the present invention is to provide an evaporative concentration treatment apparatus for photographic processing waste liquid that has few harmful or malodorous components generated by the photographic processing waste liquid. The goal is to provide the following. A second object of the present invention is to provide an apparatus for evaporating and concentrating photographic processing waste liquid that can reliably supply waste liquid to be processed.

(Means for Solving the Problems) In order to solve the above-mentioned problems of the present invention, in an evaporative concentration processing apparatus for photographic processing waste liquid having an evaporating pot and a heating means, the amount of waste liquid in the evaporating pot is detected. The present invention is characterized by comprising means for continuously or intermittently supplying waste liquid into the evaporator according to a signal from the means.

As a method for supplying photographic processing waste liquid into the evaporator, a method can be considered in which the amount that can be stored in the evaporator is supplied at one time, and the waste liquid is not supplied into the evaporator during evaporation and concentration. The evaporator has a means for detecting the amount of waste liquid, and the detected signal is used to continuously or intermittently supply finished liquid into the evaporator, thereby minimizing the generation of foul-smelling and harmful gases. I found out that it can be done.

The means for detecting the amount of waste liquid in the evaporator is preferably a liquid level sensor, but by measuring the evaporation rate in advance, a timer may be used to control the supply of waste liquid to the evaporator. Since the evaporation rate changes as the evaporation progresses and varies depending on the liquid composition, it is preferable to detect the amount of waste liquid in the evaporator using a liquid level sensor.

The operation of the liquid level bell sensor and the means for supplying waste liquid into the evaporator is configured such that the liquid level sensor stops detecting the liquid level for a certain period of time and starts not detecting the liquid level for a certain period of time. It is preferable that That is,
In the evaporator, the liquid level changes constantly due to boiling, so
If such a configuration is not adopted, the 0N10FF of the means for supplying waste liquid will be repeated frequently, causing a failure.

The constant time varies depending on the capacity of the evaporator, but it is 1 second or more.
Within minutes, preferably between 1 second and 1 minute. Furthermore, in a preferred embodiment, the liquid level sensor is installed in a communication pipe provided outside the evaporation pot. This case is preferable because the change in liquid level due to boiling is small. In this case, as mentioned above, when the liquid level sensor does not detect the liquid level for a certain period of time, the supply of waste liquid stops, and by adding a function that starts when the liquid level sensor does not detect the liquid level for a certain period of time, it is possible to prevent the failure from occurring. It is preferable that the amount of

In this invention, the means for continuously or intermittently supplying waste liquid into the evaporator (hereinafter abbreviated as means for supplying waste liquid into the evaporator) includes a tube pump, an electromagnetic metering pump, a plunger fixed amount pump, a bellows pump, Metering pumps and non-metering pumps such as gear pumps, magnet pumps, metering magnet pumps, screw pumps, diaphragm pumps, etc. are used, and metering pumps are particularly preferably used.

The photographic processing waste liquid overflowing from the automatic processor may be directly supplied as it is into the evaporation pot of the processing apparatus of the present invention. In this case, the means for supplying the photographic processing waste liquid into the evaporator simply refers to an introduction pipe for introducing the overflow into the evaporator, but this introduction pipe may be provided with a solenoid valve or the like. It is preferable that the photographic processing liquid overflowing from the automatic processor is once stored in a tank (waste liquid tank) and then introduced into the evaporator. However, if this waste liquid tank is located above the evaporator, the photographic processing liquid It is not necessarily necessary to use a bomb as a means for supplying waste liquid into the evaporation tank; this means may simply be an introduction pipe that introduces waste liquid from a waste liquid tank into the waste liquid tank, and this introduction pipe is equipped with a solenoid valve. etc. may be installed. When photographic processing waste liquid that overflows from an automatic processor is temporarily stored in a waste liquid tank, this waste liquid tank is a tank (first overflow tank) that stores the overflow from the automatic processor, and at the same time is used to store the waste liquid to be supplied to the evaporator. It may be a storage tank (waste liquid supply tank), or the overflow may be once received in an overflow tank and a certain amount stored, and then the overflow may be transferred to a waste liquid supply tank.
Preferably, the overflow tank and the supply tank are the same. In this case, since the overflow is stored in the waste liquid tank, the waste liquid may be supplied from this tank into the evaporator. It may be installed inside the concentration processing equipment and used as a waste liquid supply tank. It is preferable to install the waste liquid supply tank inside the evaporation concentration treatment apparatus of the present invention because the space can be reduced. When the waste liquid supply tank is installed inside the evaporation concentration processing apparatus of the present invention, it is preferable to install the waste liquid supply tank on a removable frame in order to improve workability.

The waste liquid supply tank shall be equipped with a liquid level sensor and a means for detecting weight, and shall be constructed so that the operation of the waste liquid supply means and heating means will stop when the waste liquid in the waste liquid supply tank runs out. is preferred.

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. Another embodiment of the heating means is one of the heaters described above,
Alternatively, a plurality of them may be placed in a high boiling point solvent such as silicone oil, magnesium carbonate, magnesium oxide, diatom, etc.
It may be embedded in a block made of stainless steel such as US304 or 5TJS316 or carphone steel.

In this invention, the heat density of the heating means is approximately 17°2 kcal.
/cm2 or less, more preferably about 8,6
It is particularly preferable that it be below kcal/cm2.

In this invention, the thermal density of the heating means is the value obtained by dividing the apparent capacity of the heating means by the area where the heating means is in contact with the waste liquid, and in this invention, the thermal density is approximately 17,2 k
By setting the temperature to below cal/cm2, it is possible to suppress the generation of bad odors and harmful gases, and to prevent bumping. In other words, when the heat density exceeds approximately 17.2 kcal/cm2, the evaporation rate of the waste liquid due to heating by the heating means is fast, and the waste liquid cannot be supplied to the surface of the heating means in time, so a layer of vapor is formed on the surface of the heating means. . For this reason, it is thought that the steam is superheated very close to the surface of the heating means, causing a bad odor and causing bumping.

In this invention, the heat density of the heating means is approximately 17°2 kca.
l/cm2 or less, and further by supplying gas through a means for supplying gas into the waste liquid in the evaporator,
Superheating of steam as described above can be prevented more efficiently.

Further, in this invention, the heat density of the heating means is approximately 17,2
kcal/cm2 or less, and further has a means for supplying a compound (hereinafter referred to as an antifoaming agent) capable of making the surface tension of the photographic processing waste liquid approximately 20 to 65 dyne/cm into the evaporating pot. By supplying an antifoaming agent into the evaporator via the evaporator, it is possible to prevent an accident in which waste liquid blows out from the introduction pipe for introducing the vapor into the cooling and condensing means.

Furthermore, in the most preferred embodiment of the present invention, the heat density of the heating means is approximately 17.2 kcal/cm2 or less, gas is supplied through the means for supplying gas into the waste liquid in the evaporator, and defoaming is carried out in the evaporator. By supplying the antifoaming agent through a means for supplying the antifoaming agent, it is possible to effectively prevent the generation of foul-smelling gases and toxic gases, as well as accidents in which the waste liquid in the evaporator is blown out due to bumping.

The heating means may be installed in the waste liquid in the evaporator, but in order to further enhance the effect of the present invention and to avoid a decrease in thermal efficiency and corrosion caused by the photographic processing waste liquid sticking to the surface of the heating means. , it is preferable to provide it outside the evaporator and heat the waste liquid in the evaporator through the wall of the evaporator.

In this case, the thermal density of the heating means is the value obtained by dividing the apparent capacity of the heating means by the area where the heating means is in contact with the waste liquid through the wall of the evaporating pot, and this value is approximately 17. 2kcal/
C[[It is sufficient if it is 12 or less.

If the heating lower stage is installed in the waste liquid in the evaporator, the heating means will be used during the process of concentrating or drying the photographic processing waste liquid, causing the photographic processing waste liquid to stick to the surface and reduce thermal efficiency. In order to prevent significant deterioration or corrosion, it is preferable that the surface of the heating means is subjected to an anti-adhesion treatment such as Teflon treatment (for example, fluororesin coating).

Examples of Teflon processing methods other than fluororesin coating include binder type, plating type, oil mixed type, heat treatment type, and room temperature compress type.

The heating means may be installed at any position at the top, middle, or bottom of the evaporation pot as long as it can heat the waste liquid in the evaporation pot.
As described in No. 1-288328, a heating means is installed to heat the upper part of the photographic processing waste liquid in the evaporator, and a temperature difference between the photographic processing waste liquid near the heating means and the bottom part of the photographic processing waste liquid is created. 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.

The evaporation pot in this invention may be in any form, including a cube, cylinder, polygonal prism including square prism, cone, polygonal pyramid including square pyramid, or a combination of some of these. However, it is preferable that the evaporator be vertically long so that the temperature difference between the photographic processing waste liquid near the heating means and the bottom is large. It is preferable to make the space above the surface of the waste liquid in all the pots as wide as possible.

In addition, the materials for the evaporation pot include heat-resistant glass, titanium,
Stainless Steel, Carbon Steel, Composite Materials Technology Collection J
(1976, published by Industrial Technology Center, p.213-2
19), “New Materials 1984J (1984, published by Toshi Research Center, p. 287-315), [Composite Materials J
(1984, published by the University of Tokyo Publishing) Any heat-resistant material may be used, such as the front crosspiece fiber described in and 5US316, particularly preferably 5O5316) and titanium.

The evaporating pot is also preferably treated with anti-sticking treatment such as the Teflon treatment described above.

It is preferable that the processing apparatus of this invention has a means for supplying gas to the waste liquid inside the pot. You can also use the one that makes the difference, but
Air is preferably used for economical and safety reasons.

The means for supplying the gas may be a cylinder filled with the gas and equipped with a pressure valve or a solenoid valve, or if the gas is air, a compressor, an air pump, or a bellows air pump is preferably used. It will be done.

When introducing air into the waste tank using an air pump,
The air may be the air inside the processing device or the air outside the processing device. Alternatively, the air may be, for example, the air inside a waste liquid storage tank that stores waste liquid. In the most preferred embodiment, when the processing apparatus of the present invention has a means for cooling and condensing the evaporated steam, a condensed water storage is provided in which condensed water condensed by the means for cooling and condensing air is stored! It is the air inside the (reservoir tank). In this case, the malodorous gases and toxic gases generated from the condensed water and the malodorous gases and toxic gases contained in the steam that was not condensed by the cooling and condensing means can be sent back to the evaporator, so the malodorous gases and toxic gases can be evaporated and concentrated. It is possible to prevent leaks from the processing equipment.

The evaporation concentration processing apparatus of the present invention preferably has means for supplying a compound capable of adjusting the surface tension of the photographic processing waste liquid to approximately 20 to 60 dyne/cm into the evaporation pot. This compound has a surface tension of approximately 25-60 dyn
Particular preference is given to compounds that can be adjusted to e/cm. This compound is, for example, a so-called antifoaming agent or surfactant such as an organosiloxane or a higher alcohol. Means for supplying this compound into the evaporator include metering pumps and non-metering pumps such as tube pumps, electromagnetic metering pumps, plunger constant rate pumps, bellows pumps, gear pumps, magnet pumps, metering magnet pumps, screw pumps, and diaphragm pumps. is used, but a metering pump is particularly preferably used.

In the evaporation concentration processing apparatus of the present invention, the means for supplying a compound capable of adjusting the surface tension of the photographic processing waste liquid to approximately 20 to 65 dyne/cm is a means for supplying the photographic processing waste liquid into the evaporator. Preferably, in this case, a compound capable of making the surface tension of the photographic processing waste liquid approximately 20 to 65 dyne/cm is included in advance in the photographic processing waste liquid.

It is preferable that the waste liquid concentration treatment apparatus of the present invention has means for cooling and condensing the evaporated vapor. All kinds of heat exchange means can be used for cooling and condensing. (1) Shell and tube type (multi-tube type, jacket type) (2) Double back type (3) Coil type (4) Spiral type ( It may have any of the following configurations: 5) plate type, (6) fin tube type, (7) trombone type, and (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 (5) Interpolation type etc. may be adopted.

Furthermore, a condenser type heat exchange technology may be adopted, and any of (1) direct condenser type, (2) in-column type, (3) column top type, (4) separation type, etc. may be used.

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 any of the following.

In a preferred embodiment, the means for cooling and condensing is configured as a heat sink device in which a heat sink (air cooling fan) is installed in a steam exhaust pipe for discharging evaporated steam, and means for supplying water onto the heat sink. It is to have the following. In this case, water is preferably showered onto the heat sink from above the heat sink device. For example, water may be supplied to the heat sink from a tap water tap via a valve or a solenoid valve as necessary; in this case, the means for supplying water is
Water faucets, water supply pipes, etc. are shown, but water is preferably stored and supplied to the heat sink via the various metering pumps or non-metering pumps as described above, and particularly preferably a heat sink. The water in the water tank installed at the bottom of the plate device is supplied to the heat sink through the pump in a shower-like manner, and then collected in the water tank at the bottom, so that the water is circulated. It is that you are. 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.

If it is configured as a heat sink device with a heat sink (air cooling fan) installed on a steam exhaust pipe that discharges evaporated steam or means for cooling and condensing, and has a means for supplying water onto the heat sink. At the same time, it is preferable to have an air-cooling fan, and in particular, in this case, the air-cooling fan is installed so that the air passes through the heat sink device and is discharged to the outside of the evaporation concentration processing device of the present invention. It is preferable to do so because it is possible to prevent condensation in the electrical components in the evaporation concentration processing apparatus of the present invention.

The condensed water obtained by cooling and concentrating the evaporated steam is stored in a tank for storing the condensed water, and this concentrated liquid tank is installed inside the evaporation concentrator of the present invention. This is preferable because it saves space, and in this case, it is preferable that the accumulated liquid tank is installed on a drawable pedestal to improve workability.

It is preferable that the evaporation concentration treatment apparatus of the present invention has means for supplying an alkaline agent into the evaporation pot.

In this case, the generation of foul-smelling gas and toxic gas is prevented by preventing sulfurization of the waste liquid, which occurs due to a decrease in the pH of the waste liquid in the evaporator.

Examples of alkaline agents include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, carbonates, silicates, phosphates, and iorates. . The alkaline agent may be supplied to the evaporation pot from a stock tank of an aqueous alkaline solution prepared by dissolving the alkaline agent in water via various metering or non-metering pumps as described above, but preferably, the alkaline agent is supplied to the evaporator in advance. Preferably, it is added to the waste liquid in the supply tank and fed into the evaporator via a feed means that supplies the waste liquid. In this case, the means for supplying the alkaline agent also serves as the means for supplying waste liquid.

It is preferable that the evaporation concentration treatment apparatus of the present invention has a means for cooling and condensing the evaporated vapor because it can prevent the generation of foul-smelling gases and harmful gases. 1) Performing at least one secondary treatment on the condensed water from the following (A) to (J), namely (A) activated + 1 carbon treatment, (B) ultraviolet irradiation treatment, (C
) reverse osmosis treatment, (D) oxidizing agent treatment, (E) electrolytic oxidation treatment, (F) aeration treatment, (G) electrodialysis treatment, (
H) Re-distillation treatment, (1) Ion exchange resin treatment, (J) p
(2) use the condensed water as dissolving water for the photographic processing solution;

The activated carbon used in the activated carbon treatment of the present invention may be any activated carbon capable of adsorbing at least one of benzyl alcohol, ammonium compounds, and sulfur compounds.

In this invention, any raw material or activation method can be used, and either powder or granular activated carbon can be used, preferably granular activated carbon, particularly preferably coconut shell activated carbon and activated carbon with molecular combing ability. Here, the activated carbon having molecular combing ability has slit-like pores, and the pores preferably have a size of 6A or more and a width of 158 or more.

Activated carbon having such molecular combing ability is described in Japanese Patent Application Laid-Open No. 1983-
The contents described in Publication No. 14831 can be referred to.

In addition to the above-mentioned activated carbon, the following substances can be used as adsorbent substances used in the adsorption treatment of condensed water 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 monoester-polyhydric alcohol methacrylic acid (9) Polyester copolymer For details of these substances (1) to (9), please refer to the patent application filed in 1983- Reference may be made to the contents of No. 124839 (particularly pages 62 to 66).

Although it can be obtained using an ultraviolet irradiation device or a halogen lamp used in the ultraviolet irradiation treatment of condensed water of photographic processing waste liquid of the present invention, it is not particularly limited. The output of this ultraviolet lamp, etc. is known to be 5 W to 1 W, but it is not limited to this. In addition, in this invention, from an ultraviolet lamp, 190 nm to 400 nm
Electromagnetic radiation and light with wavelengths outside the nanometer range may be generated and irradiated with condensed water obtained from photographic processing solutions. Further, infrared rays or the like may be used in combination.

The ultraviolet lamp etc. used in this invention can also be made into a double tube.

In this invention, irradiating ultraviolet rays means irradiating condensed water obtained from photographic processing waste with ultraviolet rays using an ultraviolet lamp or the like, and these irradiating ultraviolet rays are continuously performed on this condensed water. Alternatively, it may be performed intermittently as necessary.

In addition, in the above-mentioned reverse osmosis treatment, various reverse osmosis membranes,
Desalination/concentration methods and equipment using reverse osmosis membranes can be used without restriction. As the reverse osmosis membrane, cellulose acetate, aromatic polyamide, polyvinyl alcohol, and polysulfone are preferable, and cellulose acetate is particularly preferably used.

Reverse osmosis equipment has a capacity of 40 Kg/cm2 to 55 kg/
It is preferable to operate at a pressure of cm2 from the viewpoint of separation performance and throughput.

The oxidizing agents used in the oxidizing agent treatment used in this invention include metals, nonmetal oxides, oxide oxygen acids and their salts, peroxides, organic oxygen-containing compounds, and the like. Oxides include nitrogen peroxide NOx, chromic anhydride CrO3, selenium dioxide 5ea2, manganese dioxide MnO,..., lead dioxide PbO2, osmium tetroxide 0804, silver oxide g2
0, copper oxide CuO, mercury oxide 11go, and the like.

Oxygen acids include hot concentrated sulfuric acid H2SO4, nitrous acid HNO2,
Examples include nitric acid HNO3. Salts include sodium hypochlorite Navel, bleaching powder Ca0CI2, potassium dichromate 1 (2CrO), potassium chromate and 2
Examples include Cr204, potassium permanganate KMnO4, potassium chlorate KCLO3, potassium perchlorate KClO4, and the like. As a peroxide, hydrogen peroxide I+ 202
, sodium peroxide Na2O2, benzoyl peroxide (C
6115COO) 2nd grade is typical. Substances that can have two or more valences, such as trivalent iron ion F
C''+, divalent copper ion CI''2+, lead tetraacetate Pb (C
Il+GO□)4 etc. can also be mentioned. Other Fenton reagent (Fe+++H2O2), dehydrogenation catalyst (PL, S
Zn), etc. can also be used as oxidizing agents.

The electrolytic oxidation treatment used in this invention is a method of oxidizing a substance at an anode by electrolysis, which increases the positive charge of cations, decreases the negative charge of anions, polymerizes anions, and oxygen atoms in atomic groups. Any method can be used to increase hydrogen atoms and reduce hydrogen atoms.The advantages of electrolytic oxidation compared to oxidation using an oxidizing agent are that it performs very strong oxidation and produces fewer by-products. It is.

The aeration process used in this invention is to promote oxidation by blowing air into the condensed water of photographic processing waste, and it is preferable to use a distributor or the like to make the air bubbles thinner, thereby reducing the bubbling effect. It is possible to improve the removal efficiency of organic solvents and the like.

The electrodialysis treatment used in this invention involves placing condensed water of photographic processing waste in a partitioned room with a diaphragm between the cathode and anode of an electrodialysis tank and passing a direct current to the electrodes.

Preferably, it is a diaphragm or an ion exchange membrane, and more preferably, the cathode and anode are partitioned by an anion exchange membrane and a cation exchange membrane, and a cathode chamber and a plurality of concentration chambers (the cathode side is an anion exchange membrane) are used. membrane, a chamber partitioned by a cation exchange membrane on the anode side), multiple desalination chambers (a chamber partitioned with a cation exchange membrane on the cathode side,
The anode side consists of a room separated by an anion exchange membrane) and an anode room. The condensed water of the photographic processing waste is preferably introduced into the desalination chamber, but it is also preferred that it is introduced into the concentration chamber. The electrolytic chamber solution to be placed in the concentration chamber and the cathode chamber is not particularly limited, and for example, 0°1 to 0.2N solutions such as sodium sulfite, sodium sulfate, sodium chloride, potassium sulfate, and sodium thiosulfate are preferably used. Can be done. At this time, it is very preferable to use a processing solution (bleach-fix or fixer) having a fixing ability or its waste solution as an electrolyte solution to be introduced into the concentration chamber and the anode chamber, since no electrolytic chamber is required.

The term "distillation treatment" used in the present invention refers to distillation treatment of a concentrated liquid obtained from photographic processing waste liquid, and is one of the so-called rectification operations. Batch distillation (including simple distillation and batch rectification) or continuous distillation may be used, and a continuous equilibrium distillation method for continuous rectification can also be adopted. Obtaining pure water (with significantly less non-human fractions) by redistillation can effectively supply water to photographic processing solutions. It is also advantageous to use suitable separation agents in azeotropic and extractive distillations.

In this invention, 2
Post-processing effects can be obtained. Note that the operating pressure may be any of high pressure distillation, normal pressure distillation, vacuum distillation, molecular distillation, and molecular-distillation.

The ion exchange resin treatment used in this invention can be carried out by bringing various ion exchange resins into contact with photographic processing waste liquid, and the ion exchange resin is a three-dimensionally polycondensed polymer base with functional groups bonded to it. These include cation exchange resins, anion exchange resins, chelate resins, adsorption resins, etc.

For examples of the chemical structure and usage of the ion exchange resin preferably used in this invention, please refer to Japanese Patent Application No. 124639/1983 (
In particular, the contents of pages 54 to 57 can be referred to.

The pH adjustment treatment used in this invention is most commonly p
The pH of the condensed water is adjusted to around neutrality by adding an H regulator, and an acid or alkali is added depending on the pH of the condensed water. Because it usually contains ammonia, condensed water is alkaline and contains acids such as sulfuric acid, hydrochloric acid, phosphoric acid,
Inorganic acids such as boric acid, sulfamino acid, acetic acid, oxalic acid,
In addition to carboxylic acids such as citric acid, malonic acid, and tartaric acid, and aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, acidic salts such as sodium hydrogen sulfate and ammonium sulfate are used.

In the present invention, it is further preferable that a portion of the vapor that is not condensed by the cooling condensing means is discharged to the outside through a gas treatment column that communicates with the outside air. This prevents poisonous residue from vaporizing and leaking to the outside due to slight decomposition of photographic processing waste during evaporation processing, or from pressurizing the evaporator and causing gas to leak easily. can.

Furthermore, when this processing equipment is stopped, the steam or gas expanded by heating inside the evaporator will contract, resulting in a reduced pressure state, and if the evaporator is completely sealed, the evaporator may be damaged due to the load. It is also possible. These can be prevented by introducing outside air from the outside through this scum treatment column. Adsorbents or deodorizers, such as activated carbon or zeolites, may be used in the gas treatment column. Since these adsorbents or deodorizers require gas flowability, they are preferably granular.
Those having a particle size in the range of 0.3 mm to 15 mm are mentioned, and adsorbents or deodorizers having a particle size in the range of 0.8 mm to 6 mm are particularly preferable.

It is preferable that these deodorizing agents or adsorbents be pre-packed and molded into cloth or paper, for example, and placed in the gas treatment column, as this will save time and effort during replacement.

In this invention, the concentrated liquid after evaporation and concentration may be discharged from the evaporating pot, or, for example, a heat-resistant and chemical-resistant bag may be provided in the evaporating pot, and the concentrated liquid may be taken out together with the bag after processing. ,
For example, the evaporation concentration processing apparatus of this invention, patent application 1986-25
In the case of the evaporation concentration treatment apparatus described in No. 9001 and Japanese Patent Application No. 1983-288328, the apparatus uses a rotary screw pump, or the concentrated liquid is passed from the bottom of the evaporation pot through a Narubu to a heat-resistant, chemical-resistant, etc. You can take it out into a bag. As the heat-resistant and chemical-resistant bag, for example, carbon fiber, aramid 1a fiber, Teflon resin IA navy blue, hemp, glass fiber, polyethylene foam, polypropylene foam, etc. are preferable.

In the present invention, it is preferable that the concentrated solution of photographic processing waste is absorbed into a carrier and solidified before being recovered.

'A liquid-absorbing resin or a solidifying agent can be considered as this carrier. The carrier used in the present invention is preferably one that can absorb the concentrated liquid of photographic processing waste, and that does not corrugate when the liquid is absorbed by the liquid-absorbing carrier, and so-called liquid-absorbing resins are preferably used.

As this liquid-absorbing resin, for example, the following can be used.

Seed f′ polysaccharide, seaweed polysaccharide, resin polysaccharide, fruit polysaccharide,
Rhizome polysaccharides.

Furthermore, sunsan gum, sunflow, gardlan, succinoglucan, sysophyllan, pullulan, succinoglucan, sysophyllan, pullulan, gelatin, casein, albumin, shellac, etc.

Starch derivatives, guar gum, locust bean gum derivatives, cellulose conductors, alginic acid derivatives, vinyl compounds, acrylic compounds.

Others, such as polyethylene oxide.

Next, preferred examples of the superabsorbent liquid resin used in the present invention will be listed.

(A) Grafted starch system (A-1) Starch-acrylonitrile graft polymer (A-2) #Powder-acrylic acid graft polymer Above (A-
1) is disclosed in Japanese Patent Application Laid-open No. 49-43395 and U.S. Patent No. 4,1
34,863, and the above (A-2) can be produced by the method described in Japanese Patent Publication No. 53-41i199.

(B) Acrylic acid type (B-1) Sodium polyacrylate type (B-2) Vinyl alcohol-acrylic acid copolymer The above (B=2) can be used repeatedly by natural drying and/or forced drying.

(C) A polymer having a repeating unit having the structural formula shown below (I) or (II), more preferably (I)
and/or a polymer containing 10 to 70% by weight of (TI) and copolymerized with other ethylene-based saturated monomers.

(I) R (II) R ■ 1+CI+,, -G + 10ZR・-5!3 In the above formula, R is a hydrogen atom, a methyl group or a halogen atom, and Z is an oxy group or an imino group, n is 0
or 1, and R1 is an alkylene group (including substituted alkylene groups) having 1 to 6 carbon atoms f, a cycloalkylene group or arylene group having 5 to 6 carbon atoms r,
an arylene alkylene group or an arylene bisalkylene group, where the alkylene moiety has 1 to 6 carbon atoms and the arylene moiety (optionally substituted) has 6 to 10 carbon atoms. and, for example, ONR5 →1lcR', -Yo, -(,=N, -C=
arylene substituted with a hydrophilic polar group such as 0° or -c-o-, where R is an alkyl group having 1 to 4 carbon atoms, and R2, R3 and R4 are each hydrogen atom or 1-6
is an alkyl group having up to 6 carbon atoms, or together with N forms a heterocyclic group which may optionally contain sulfur or oxygen atoms, M is a hydrogen atom, a soluble cation or up to 6 carbon atoms; It is an ammonium group including a quaternary ammonium cation having an alkyl group having a carbon atom, and X is an acid anion.

The halogen substituent of R can be bromine or chlorine;
The alkylene group having 1 to 6 carbon atoms in R1 may be substituted with a hydroxyl group, and the arylene alkylene group in R1 includes a phenylenemethylene group, a phenyleneethylene group, a phenyleneboropyrene group, and a phenylenebutylene group. , and the arylenebisalkyl group of R1 contains a phenylene dimethylene group.

Soluble cations of M include sodium and potassium.

Heterocyclic groups formed from R2, R3 and R4 and the O N atoms to which they are attached include pyridinium, imidazolium, oxacillium, thiazolium and morpholium.

Acid anions of X include chloride, bromide, acetate, p-toluenesulfonate, methanesulfonate, ethanesulfonate, methylsulfate, ethylsulfate, and perchlorate.

The monomer of the general formula (I) and/or the monomer of the general formula (II)
) The ethylenically unsaturated monomer to be copolymerized with the monomer of Consists of methylene group-containing monomers. Polymerized copolymerizable ethylenically unsaturated monomers of this type are described, for example, in U.S. Pat.
No. 1, No. 3,554,987, No. 3,658,8
No. 78, No. 3,929,482 and No. 3,939
, No. 130.

Preferred polymers for use in the above are 10 to 7
Derived from or containing 0% by weight of one or more monomers listed below: 2-aminoethyl methacrylate hydrochloride, N-(2-methacryloyl (oxyethyl)-N, N, N
-1-trimethylammonium chloride, N-(2-methacryloyloxyethyl)-N, N, N
-trimethylammonium methosulfate, sodium 2-methacryloyloxyethyl-1 sulfonate, and 2-(N,N-dimethylamino)ethyl methacrylate hydrochloride.

An acid salt corresponding to the above structural formula (1) can be converted to the free amine when it is neutralized with a base.

The above polymer can be prepared by polymerizing appropriate monomers in an aqueous solution according to a conventional method.

The monomers of the structural formula (I) include R, It, Yocum and E.

B, Nyqist (IE, B, Nyqist)
ed., “°Functial Monomers (Functi
onalMonomers), Meisel Detsuka (
Marcel Dekker), Inc., N
ew York (+974) and U.S. Patent No. 2.78
It can be prepared by the method described in No. 0.604. The monomer of structural formula (II) is disclosed in U.S. Pat.
No. 024,22] and No. 3,506,707.

Optionally, the polymer is prepared by (a) quaternizing the polymer having amine groups with an alkylating agent or otherwise;
(b) Can be prepared by reacting an amine with a polymer having a group reactive with the amine, such as an active halogen group. Such techniques are known in the art and are described in U.S. Pat. No. 3,488.
, 706 and 3,709,890 and Canadian Patent No. 801.958.

The resins listed above can be manufactured manually as commercially available products.

Examples of commercially available products include Sumikagel N-100, Sumikagel 5P-520, Sumikagel 5-50, Sumikagel NP-1020, Sumikagel F-03, and Sumikagel F.
-51, Sumikagel F-75, Sumikagel R-30 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Sunwet 1M-300, Sunwet IM-1000 (trade name, manufactured by Sanyo Chemical Co., Ltd.), Aqua Keep 10S+1
-r' (trade name, manufactured by Tetsutsu Kagaku Co., Ltd.), Lanseal F (1-Rade Name, manufactured by Nippon Exlan Co., Ltd.), and the like.

The liquid-absorbing resin preferably used in the present invention preferably has a shape that easily absorbs liquid, and is powdery or has a diameter of 0.5 mm. A granular material with a diameter of about 3 mm can be advantageously used for handling.

Further, the solidifying agent used as a carrier in the present invention may be any agent as long as it can solidify a concentrated solution of photographic processing waste, and it may or may not involve a chemical reaction. As the solidifying agent of this invention, for example, CaO, Ca
(OH)2, C11CO3, silica gel, calcium chloride, aluminum oxide, calcium sulfate, magnesium oxide, barium oxide, granular soda lime, niline pentoxide, and the like are preferably used.

It is preferable that the evaporation concentration processing apparatus of the present invention has a lubrication disk in order to prevent an accident in which, for example, the vapor discharge chamber for discharging evaporated vapor becomes clogged and the evaporation pot is pressurized and causes an explosion. . The loveture disk is configured, for example, to communicate the evaporation pot and the waste liquid supply tank, and to interrupt this communication pipe in the middle with a sheet such as polyethylene that can be destroyed by pressurization. It is preferable that the evaporation concentration processing apparatus of the present invention has a temperature sensor in the evaporation pot. There is a temperature sensor.When a steady temperature is detected, for example 120℃ or higher,
By configuring the heating means to be turned off, dry cooking can be prevented.

The evaporation concentration processing device of the present invention is configured such that it cannot be opened unless the door provided in the device, the temperature inside the evaporation pot, or the temperature inside the processing device falls below a certain level (for example, 50° C. or below), Preferably, it is arranged to issue a warning signal of an attempt to open.

When waste liquid is processed by the evaporation concentration processing apparatus of the present invention, the waste liquid may be processed separately for each processing line that processes various photosensitive materials, for example, the color processing waste liquid and the color vapor processing waste liquid may be processed separately, or they may be mixed. may be processed. Also,
Even in the same treatment line, various waste liquids may be processed individually, or a mixture of a plurality of waste liquids or all waste liquids may be processed.

In the waste liquid concentration treatment apparatus of the present invention, it is preferable to have a means for reducing the pressure in the evaporator because the temperature in the evaporator can be lowered and less malodorous gas or toxic gas is generated.

Further, even if the same treatment line is used, various waste liquids may be treated individually, or a mixture of plural or all waste liquids may be treated.

Next, typical examples of photographic processing waste liquid that can be processed 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 by a coupling reaction between an oxidized 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 derivatives of aminophenol and p-phenyrecinamine amine.

” Examples of aminophenol-based developers include 0-
Aminophenol, P-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-
Contains benzene.

The color developing solution may contain an alkaline agent commonly used in developing solutions, and may also contain various additives such as pencil alcohol, alkali metal halides, or development regulators.
May also contain preservatives. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylpolamide 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 by development is oxidized and replaced with silver halide, 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 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., 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 per liter of stabilizer, more preferably about 0.5 g to 5 g per liter of stabilizer.

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, ammonium malate , ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4.6-dolinitro Such as phenolammonium. The amount of these ammonium compounds added is 1 for the stabilizer! It is used in a range of 0.05 to 100 g per serving.

Compounds added to the stabilizing solution include pH adjusters, 5-
chloro-2-methyl-4-isothiazolin-3-one,
2-year-old cutyl-4-inthiazolin-3-one, 1-2
- Henzin thiasoline = 3-one and other special intercondylar 59-1
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 processing solution from the previous stage that has adhered to or penetrated into the photographic light-sensitive material. By replenishing only 30 mn/m2 to 9,000 m It 7 m2 per unit area of the photosensitive material, more preferably 6 omfL/m2 to 3,000 m It 7 m2, it has an effect equivalent to or better than the above, and specifically, JP-A No. 511 -134636 Refers to image stabilization processing as described in Bow.

Therefore, when using the water washing alternative stabilizer according to the present invention, it is necessary to supply it to the outside of the automatic developing machine for water washing as in the conventional
Does not require r pipe equipment.

In addition, stilbene-based optical brighteners are sometimes used in color developing solutions and stabilizers for color vapors.

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

A preferred application of the present invention is to treat photographic processing waste liquid generated during the development of photographic light-sensitive materials using an automatic processor in 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 each photographic processing tank is replenished with the replenisher, it is discharged from the processing tank as an overflow waste liquid and collected in the stock tank 104. A simple way to prevent the overflowing photographic processing waste from being transferred to the stock tank 104 is to allow it to fall naturally through a guide pipe. There may also be cases where it is forcibly transferred using a pump or the like.

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.

(Actual 7ih example) Figure 2 shows the evaporation 11Alir6 of photographic processing waste liquid of this invention.
FIG. 3 is a schematic configuration diagram showing the processing device in more detail, and FIG. 3 is a configuration diagram showing its specific arrangement.

In the figure, reference numeral 1 denotes an evaporation pot, which is composed of a cylindrical upper part 1a with a large diameter and a cylindrical lower part 1b with a small diameter. A valve 3 is provided. ball valve 3
A communication pipe 4 that communicates with the upper part 1a comes out from the top part 2, and a liquid level sensor 5 is provided in the middle. A sludge receiver 6 is provided under the lower part 1b of the evaporator 1, and a polypropylene bag 7 is fixed therein by an O-ring 8.

The upper part 1a of the evaporating pot 1 is provided with a steam υ [mountain 9, and this steam exhaust pipe 9 is connected to a distilled liquid inlet pipe 12 through a heat exchanger 10 and a cooling condensing means 11). . In the cooling condensing means 11, a large number of cooling heat sinks 1 are installed in the steam exhaust pipe 9.
3 (described with some parts omitted), and a liquid level sensor 14 is also provided. A cooling water introduction pipe 15 is provided at the bottom of the cooling condensing means 11, and is connected via a cooling water circulation pump 16 to a shower pipe 17 having a large number of small holes.

The air in the cooling condensing means 11 is discharged to the outside of the processing device by an air cooling fan 18. The accumulated liquid inlet pipe 12 is connected to the accumulated liquid tank 19, and an activated carbon cartridge 20 is provided inside this tank, and activated carbon 21 packed in a paper bag is stored inside the tank. Furthermore, an activated carbon cartridge 22 is provided outside the reservoir tank 19, and activated carbon 23 packed in a paper bag is stored inside. The accumulated liquid tank 19 is also provided with an air introduction pipe 24, which is installed in the waste liquid of the evaporation pot 1 via an air pump 25. Reference numeral 26 denotes a waste liquid supply tank, which is provided with a waste liquid introduction pipe 27 and is connected to the evaporator upper part 1a via a bellows pump 28 and a heat exchanger 10. Waste liquid supply tank 26
Further, a liquid level gauge 29 is provided. The waste liquid supply tank 26 and the accumulated liquid tank 19 are installed on a removable pedestal 30'' with a handle, as shown in FIG.

A guide pipe 31 is further provided in a part 1a of the evaporating pot 1,
Waste liquid supply tank 26 via plunger disk 32
A temperature sensor 33 is also provided in the second part 1a of the evaporating pot 1.

Next, an outline of the heating and evaporation process using this apparatus will be explained.

The waste liquid supply tank 26, which stores about 201 overflow liquid from the automatic developing machine, is transported to the evaporation concentration processing device.
It is installed on the pulled-out pedestal 30, and the waste liquid introduction pipe 27 and liquid level meter 29 are connected to it. Furthermore, on the pedestal 30, a tank 19 is installed, which is equipped with activated carbon cartridges 20 and 22 filled with activated carbon 21 and 23 each packed in a paper bag. After connecting the tube 24, it is placed in the evaporation concentration processing apparatus.

Next, a polypropylene bag 7 is installed in the sludge receiver 6 under the lower part 1b of the evaporator 1 and fixed to the lower part 1b of the evaporator 1 with two O-rings 8. Next, after supplying water into the cooling and condensing means 11, when the switch is turned on, the air pump 25 is activated, and the air in the accumulated liquid tank 19 is introduced into the evaporation pot 1 through the air introduction pipe 24. However, the tip of the air exhaust pipe 9 is located further below the heating means 2 provided outside the evaporator 1. Next, 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 pipe 17.
The steam is supplied onto the heat radiating plate 13 of the steam exhaust pipe 9 housed in the cooling and condensing means 11, and is circulated again, collecting at the lower part of the cooling and condensing means 11.

Then, the bellows pump 28 is activated, and the waste liquid in the waste liquid supply tank 26 passes through the waste liquid introduction pipe 27, and the heat exchange means 1
After passing through zero, it is sent into the evaporator 1. When the amount of waste liquid in the evaporation pot 1 increases, the liquid level in the communication pipe 4 increases, and the liquid level is detected by the liquid level sensor 5 for, for example, 3 seconds or more, the operation of the hero's pump 28 is stopped. At the same time, the heating means 2 is turned on and heating evaporation is started.

When the amount of waste liquid in the evaporator 1 decreases due to heating and evaporation, and the liquid level in the communication pipe 4 drops, and the liquid level is no longer detected by the liquid level sensor 5 for more than 3 seconds, the bellows pump 28 is turned off again. The switch is turned on and the waste liquid supply tank 26
The operation of supplying the waste liquid in the evaporator tank 1 into the evaporator tank 1 is repeated. The evaporated steam passes through the steam exhaust pipe 9 and exchanges heat with the waste liquid in the heat exchanger 10, and then passes through the cooling condensing means 11 and is condensed. After passing through the activated carbon 21 in the activated carbon cartridge 20, it is stored in the reservoir tank 19.

When the liquid level sensor 29 detects that the waste liquid in the waste liquid supply tank 26 has run out, the operation of the bellows pump 28 is stopped and the switch of the heating means 2 is turned OFF.
After two hours, the cooling water circulation pump 16 and the air cooling fan 18 stop, the lamp lights up, the buzzer goes off to notify that the evaporation and concentration process is completed, and the air pump 25 stops. Here, ball pal 3
The bag is opened and the sludge in the evaporating pot 1 is dropped into a 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 cooling 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.

Further, during the evaporation and concentration process, if the temperature sensor 33 detects that the liquid level in the evaporating pot 1 has dropped abnormally for some reason and the temperature in the evaporating pot 1 has risen to 120°C due to dry heating, the lamp lights up, a warning buzzer sounds, and the heating means is turned off. From then on, the evaporation concentration process is interrupted by the series of operations described above.

FIG. 4 is a sectional view of the heating means 2 shown in FIGS. 2 and 3. That is, a heater block 36 made of 5US304 is provided around the wall 34 of the evaporation pot 1 made of titanium, and four cartridge heaters 35 are embedded in this heater block 36. Further, a heat insulating agent 37 is provided on the circumferential surface of the heater block 36 .

5 to 8 are diagrams showing various specific examples of the liquid level sensor of the present invention.

In FIG. 5, a communication pipe 4 extends upward from the lower part 1b of the evaporation pot below the heating means 2 at an angle of about 45 degrees to the wall of the evaporation pot 1, and a liquid level sensor 5 is installed in the middle of the communication pipe 4. It is provided.

In FIG. 6, the liquid level sensor 5 directly
one terminal is grounded to the wall of the upper part 1a of the evaporator 1.

In FIG. 7, the lower part of the liquid level sensor 5 is a float 38, and the upper part of the liquid level sensor 5 is provided with a magnet 39, and when the liquid level rises, the installation part of the magnet 39 rises. The switch turns OFF.

In FIG. 8, similarly, the lower part 1b of the liquid level sensor 5 is 1-j'-38, and when the liquid level rises by 1,
The upper part of the liquid level sensor 5 blocks the infrared rays emitted from the infrared emitting tube 40, and the switch is turned off.

[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 38℃ 3 minutes (2) Bleach fixing 38℃ 1 minute 30 seconds (3) Stabilization treatment
25℃~35℃ 3 minutes (4) Drying 75℃~10
0°C for about 2 minutes Processing liquid composition [Color developing tank liquid] Benzyl alcohol 15mft Ethylene glycol 15+nJ2 Potassium sulfite 2.0g Potassium bromide
163g sodium chloride
0.2g potassium carbonate
24.0g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 4.5g Optical brightener (4,4
'-diaminostilbendisulfonic acid derivative)
1.0g hydroxylamine sulfate
3.0g 1-hydroxyedilindene-1,1-niphosphonic acid 0.4g hydroxyethyliminodiacetic acid 5.0g magnesium chloride hexahydrate 0.7g 1.2-dihydroxybenzene-
3,5-disulfonic acid disodium salt 0.2g water was added to make IIL, and the pH was adjusted to 10 with potassium hydroxide and sulfuric acid.
, 20.

[Color developer replenisher] Benzyl alcohol 20mj2 ethylene glycol 20mM potassium sulfite 3.0g potassium carbonate
24.0g hydroxyamine sulfate
4.0 g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamide edyl) aniline sulfate 6.0 g Optical brightener (4,4°
-diaminostilbendisulfonic acid derivative)
2.5g 1-hydroxyedilindene-1,1-niphosphonic acid 0.5g hydroxyethyliminodiacetic acid 5, Og magnesium chloride 6
Water salt 0.8g1.2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g
Add water to bring it to 1, then add potassium hydroxide and sulfuric acid to pH 10.
,70.

[Bleach-fix tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100. Add 27.5mu of ammonium sulfite (40% solution) to bring the total volume to 1°C, and dilute with potassium carbonate or glacial acetic acid.
Adjust to H7.1.

[Bleach-fix replenisher A] Ferric ammonium ethylenediaminetetraacetate dihydrate 260.0g Potassium carbonate 42.0g Add water to make a total
Let it be f1lIl.

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 cothiosulfate 500.0m, e (70
% solution) Ammonium sulfite 250.0mf! .

(40% solution) Ethylenecyaminetetraacetic acid 17.0g Glacial acetic acid
85.0m, add water to make total volume 1.

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

[Water washing alternative stable tank liquid and replenisher] Ethylene glycol 1.0g 2-methyl-4-inthiazolin-3-one
0.20g 1-hydroxyethylidene-1,
1-niphosphonic acid (60% aqueous solution 1.0g ammonia water (ammonium hydroxide 25% aqueous solution) 2.0g in water
! and adjust the pH to 7.0 with 50% sulfuric acid.

Fill an automatic processor with the color developer tank solution, bleach-fix tank solution, and stabilization tank solution, and add the color developer replenisher and bleach-fix replenisher at intervals of 3 minutes while processing the commercially available color photographic vapor sample. A running test was conducted while replenishing solutions A, B and stable replenisher through the bellows pump. The amount of replenishment is 190 mJ1 per color paper trn2 to the color developing tank, and 50 mJ1 each of bleach-fixing replenisher A and B to the bleach-fixing tank.
m! , 250 rnJ2 of a water washing alternative stabilizing replenisher was replenished to the stabilizing tank. In addition, the stabilizing tank of the automatic developing machine has the first to third tanks in the direction of the flow of the sample, and replenishment is performed from the final stack, and the overflow liquid from the final stack is allowed to flow into the previous stage. Furthermore, a multi-tank countercurrent system was adopted in which this overflow liquid also flows into the rice mill at the previous stage.

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.

400g of potassium carbonate was added to the photographic processing waste liquid in advance.
and 50% sodium hydrogen sulfate in the distillate tank.
0g was added. In addition, the heat density path of the heating means 4 kca
1/cm2, 400 g of potassium carbonate was dissolved in the photographic processing waste liquid, and 500 g of sodium hydrogen sulfate was put into the reservoir tank. In addition, the antifoaming agent FS Antiform 025 (manufactured by Dow Corning) is contained in the photographic processing waste liquid.
4g of was added in advance to the photographic processing waste solution. After the waste liquid was treated at 20°C and cooled, the pole valve at the bottom of the evaporator was opened and the sludge inside the evaporator was taken out, and it was found to be 1.2.

Next, an evaporation concentration processing apparatus other than this invention was prepared, and the photographic processing waste liquid was processed in the same manner. This evaporation concentration processing equipment is
Although the basic structure is the same as that of the waste liquid concentration treatment apparatus of the present invention as shown in FIGS. The bellows pump is not configured to turn ON and OFF, and when 20ffi of waste liquid is supplied into the evaporator, the liquid level is detected by the liquid level sensor 5 and the bellows pump stops operating. However, it does not operate due to a subsequent drop in the liquid level that accompanies the progress of evaporation. In addition, in the evaporation concentration treatment apparatus other than the present invention, the time required for 20 liters of waste liquid to be concentrated to 1.2 liters is measured in advance, and a timer is set to stop the evaporation concentration treatment when this time has elapsed. be.

The odor generated from the evaporation and concentration treatment equipment was observed when the above two types of treatments were performed, and the results are shown in Table 1.

Table 1 The symbols indicating odor evaluation used in Table 1 mean the following evaluations.

D. Bad odor A: No bad odor at all As is clear from Table 1, there was no odor at all in Experiment No. 2 using the evaporation concentration treatment device of this invention, but in Experiment No. 2 using the above-mentioned concentration treatment device for comparison. The odor (especially the mercapto odor) is terrible.

Next, when the liquid level sensor 5 was installed inside the evaporation pot in the experimental apparatus of the present invention, the hatching of the liquid level became somewhat large (Experiment No. 03).

Therefore, when the liquid level sensor 5 was installed externally and the bellows pump was changed to turn off and on immediately depending on whether or not the liquid level was detected, the same liquid level hunting occurred. Taku experiment N04)
.

Furthermore, in Experiment No. 4, when the liquid level sensor 5 was installed inside the evaporation pot (Experiment No. 05), hunting in the liquid level was further enlarged. In addition, during the process of these experiments No. 3 to No. 4, we observed the odor coming from the evaporation concentration processing equipment.
The results are shown in Table 2.

Table 2 The symbols indicating odor evaluation used in Table 2 mean the following evaluations.

C: There is a slight bad odor B: There is a slight bad odor, but it cannot be noticed unless you smell it carefully.As is clear from Table 2, all of them are from the above-mentioned test surface level sensor, 11 is the cooling condensing means, and 19 is from the NOI reservoir. The result was bad.

(Effects of the Invention) As described above, the present invention includes a means for continuously or intermittently supplying waste liquid into the evaporator according to a signal from the means for detecting the amount of waste liquid in the evaporator. It is possible to reliably supply the waste liquid to be treated depending on the remaining amount. Moreover, since the waste liquid to be processed can always be heated and condensed at a set amount, the waste liquid is always heated and condensed in the optimal condition, and harmful or malodorous components generated by photographic processing waste liquid can be kept to a minimum. .

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an automatic developing machine, FIG. 2 is a schematic configuration diagram showing an embodiment of the invention, FIG. 3 is a configuration diagram showing its specific arrangement, and FIG. 4 is a diagram of FIGS. A sectional view of the heating means shown in FIG. 3, and FIGS. 5 to 8 are diagrams showing various specific examples of the liquid level sensor of the present invention. In the drawing, numeral 1 is an evaporation pot, 2 is a heating means, and 5 is a liquid patent.
Applicant: Konishiroku Photo Industry Co., Ltd. Figure 1 Figure 5 Figure 7 Figure 8 Figure Proceedings Amendment Statement June 24, 1988 Director General of the Patent Office Yoshi 1) Takeshi Moon 1 Indication of the Case 1988 Patent Application No. No. 069437 No. 2 Name of the invention Evaporative concentration treatment device for photographic processing waste liquid 3 Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1)
27) Konica Co., Ltd. 4 Agent 151 Address 2-23-1 Yoyogi, Shibuya-ku, Tokyo (1) Correct "process" in line 17 of page 2 of the specification to "process." (2) In the same book, page 5, line 5, "automatic processing machine" is corrected to "automatic processing machine." (3) "Processing device" on page 9, line 6 of the same book is corrected to "processing device." (4) In the same book, page 9, lines 7 and 8, "is" is corrected to "is." (5) In the same book, page 10, lines 11 and 12, the phrase ``finishing is done'' is corrected to ``based on waste liquid.'' (6) "Liquid level bell sensor" in the second line of page 11 of the same book is corrected to "liquid level level sensor." (7) "What is operation" in the third line of page 11 of the same book is changed to "operation is"
I am corrected. (8) In the same book, page 11, line 7, "composition" is corrected to "composition". (9) In the 8th line of page 11 of the same book, there is a phrase "If not," [If not, the liquid level will rise and fall due to boiling, so even if the liquid level in the evaporator rises and falls, no waste liquid will be supplied, causing dry cooking. It's easy," he corrected. (10) In the same book, page v-12, line 18, "preferably" is corrected to "preferably". (11) In the same book, page 13, line 15, “because I stored it” was replaced with “
After storing it,” he corrected. (12) In the same book, page 13, lines 18 to 19, "installed inside" is corrected to "installed inside." (13) In the same book, page 14, lines 12 to 14, ``cartridge heater, . corrected. (14) "Heater" on page 14, line 16 of the same book is corrected to "heater." (15) Ibid., page 15, lines 4, 5, 10, 1
Correct r Kcal/cm2 J in the 3rd and 20th lines to r Kcal/cm2J. (16) rKcal on page 16, lines 5 and 13 of the same ministry
/cm2 J is corrected as ``nical/cmJ. (17) rKcal/ in the same book, page 17, lines 8 to 9.
Correct c+n2j to r Kcal/c rn'. (18) In the same book, page 32, line 19, "to use" is corrected to "to use." (19) “Narbu” in the same book, page 36, line 6, is “pulp”
I am corrected. (20) In the same book, page 36, line 7, "chemical resistance" is corrected to "chemical resistance." (21) In the same book, page 40, lines 12 and 13, ``Te no yoiku,'' is corrected to ``Imo yoiku,''. (22) Same book, page 42, line 16' (1) J to r(I)
” he corrected. (23) In the same book, page 45, line 10, "communicating tube" is corrected to "communicating tube". (24) “Do” in line 20 of page 46 of the same book is “do”
I am corrected. (25) In the same book, page 47, lines 7, 8, 10, and 11, "process" is corrected to "process." (26) In the same book, page 47, line 18, "aminophenol meter" is corrected to "aminophenol type." (27) In the same book, page 48, line 18, "process" is corrected to "process." (28) "Process" in the first line of page 49 of the same book is corrected to "process." (29) "Preferably" in lines 9 and 10 of page 50 of the same book is corrected to "preferably." (30) In the same book, page 55, lines 11 and 12, ``to be done'' is corrected to ``to be done''. (31) From page 57, line 20 to page 58, line 1 of the same book, “
"Liquid level meter 29" is corrected to "Liquid level sensor 29". (32) In the same book, page 58, line 11, “approximately 201” was replaced with “approximately 201”
0°C,” he corrected. (33) “Liquid level meter 29” in the same book, page 58, line 14
is corrected to "liquid level sensor 29". (34) "Air exhaust pipe 9" in line 8 of page 59 of the same book is corrected to "steam exhaust pipe 9." (35) "Heat exchange means 10" on page 59, line 18 of the same book is corrected to "heat exchanger 10." (36) In the same book, page 61, lines 3 and 4, ``Ball Hull 3'' is corrected to ``R Pole Valve 3''. (37) In the same book, page 63, line 7, "process" is corrected to "process." (38) In the same book, page 63, line 7, ``gone'' is corrected to ``gyona futa.'' (39) "Magnesium" on page 65, line 9 of the same book is corrected to "magnesium." (40) r500 on page 66, line 12 of the same book. Correct "Omk" to "r250.0mft". (41) In the same book, page 66, line 14, "r250.0m℃" is corrected to "r25.0m1l". (42) In the same book, page 67, line 6, "(60% aqueous solution") is replaced with "
(60% aqueous solution)”. (43) In the same book, page 67, line 15, ``I went'' is corrected to ``I did.'' (44) In the same book, page 68, lines 2 and 3, “deed” is changed to “
I am corrected. (45) In the same book, page 68, line 8, ``I went'' is corrected to ``I did.'' (46) In the same book, page 70, line 16, “set up” is changed to “
"It was set up," he corrected. (47) "Hatching" in lines 16 and 17 of page 70 of the same book is corrected to "hunting." (48) Figure 2 of the drawings will be corrected as shown in the attached sheet. that's all

Claims (4)

[Claims] (1) In an apparatus for evaporating and concentrating photographic processing waste having an evaporating pot and heating means, means for continuously or intermittently supplying waste liquid into the evaporating pot according to a signal from a means for detecting the amount of waste liquid in the evaporating pot. An apparatus for evaporating and concentrating photographic processing waste liquid, comprising: (2) Claim 1, wherein the means for detecting the amount of waste liquid in the evaporating pot is a liquid level sensor.
An evaporative concentration treatment device for photographic processing waste liquid as described in 2. (3) The operation of the means for supplying the waste liquid into the evaporator is stopped when the liquid level sensor detects the liquid level for a certain period of time, and starts when the liquid level sensor does not detect the liquid level for a certain period of time. An apparatus for evaporating and concentrating photographic processing waste liquid according to claim 2. (4) Evaporation of photographic processing waste liquid according to claim 2 or 3, wherein the liquid level sensor is installed in a communication pipe provided outside the evaporation pot. Concentration processing equipment.