JPS61231546A - Treatment of photographic processing solution and photographic processing machine applying said treatment - Google Patents

Abstract

PURPOSE:To rapidly lower the COD of a spent photographic processing soln. by an electrolytic method as well as to effectively reutilize a used photographic processing soln. by electrolytic oxidation by using a bed electrode as an anode. CONSTITUTION:A photographic processing soln. for a silver halide photographic sensitive material contg. dissolved silver ions is electrolyzed in an electrolytic cell I provided with a bed electrode as an anode. Fluidized bed granules 5 acting as an anode have been put in the lower part of the cell I. The processing soln. flows in the cell I from the bottom as shown by an arrow 7 and flows out of the cell I from the top. The soln. contacts with the anode 6 and the granules 5. By this contact, Fe (II) in the soln. is oxidized to Fe (III). The soln. further contacts with an upper cathode 2, flows out of the cell I and returns to a storage tank 4. Thus, the processing soln. is circulated and electrolyzed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing photographic processing liquids and a photographic processing machine used to implement this processing method. In particular, it is possible to electrolytically treat the used photographic processing solution, recover silver electrolytically, suppress the decomposition of the components that dissolve silver, and perform an effective electrolytic oxidation treatment, thereby improving the photographic performance of the photographic processing solution. Regarding technology that can be reused without problems.

[Conventional technology and its problems]

A development and fixing step is provided for post-processing the silver halide photographic material to obtain an image. Color photographic materials are provided with color development, bleaching, fixing, and stabilization processing steps, or a bleach-fixing step in which bleaching and fixing are performed in one step. A water washing process is provided between each process as necessary.

In these processing steps, as the processing progresses, for example, in the developing step, the developing agent is oxidized, and in the bleaching and bleach-fixing steps +, the bleaching agent is reduced and accumulated in the processing solution. Similarly, in the fixing and bleach-fixing steps, silver halide in the photographic material is dissolved by silver halide solvents such as thiosulfate and thiocyanate, and is accumulated as silver ion-dissolved components such as silver complex ions. In addition, sensitizing dyes, oils, active molecules, etc. eluted from photographic materials are also accumulated in the same way.

They are also contained in or attached to photographic materials during continuous processing, flow out to other processes, and accumulate.

It is known that the accumulation of various impurities including silver complex ions significantly lowers the photographic processing performance and the quality of the formed images. Therefore, in order to prevent performance deterioration during continuous processing of such photographic materials, processing liquid is replenished. The overflow liquid corresponding to the refilled liquid is! Not only does it contain a large amount of III ions, but its COD value due to various inorganic and organic compounds is extremely high, and its disposal poses a major problem in terms of pollution prevention.

Furthermore, in recent years, from the perspective of pollution prevention and effective use of resources, there has been a trend toward low overflow, that is, the supply of replenisher per unit area of photographic materials to be processed as small as possible. This causes an excessive accumulation of concentration, an increase in the concentration in the overflow liquid, and an increase in COD.

Therefore, it is strongly desired to reduce the COD of the treated waste liquid while recovering silver.

Such a method of reducing COD is the method of adding an oxidizing agent (US-3615507, US-3767401,0L
S-2149314) Oxygen (air) contact method (U
S-3634086, US-3700450,0LS-
2113651), electrolytic oxidation method (Japanese Unexamined Patent Publication No. 1819-1983)
1) Among these, the electrolytic method does not require treatment chemicals compared to other methods, it is possible to control the oxidation rate with the current value, and it is possible to achieve relatively strong oxidation by regulating the voltage. It is known to be an excellent processing method because of its power and cleanliness. In addition to these advantages, it also has the advantage that it can be carried out simultaneously with electrolytic silver recovery, which will be described later.

As such a method, negative electrolytic treatment of the fixer is used.
A method is known in which silver is recovered and CO♂-reduced at the same time by applying an alternating voltage to both anodes (Japanese Patent Publication No. 53-43478).

However, when an electrolytic cell of the size used for conventional electrolytic silver recovery is used, a sufficient oxidation rate cannot be obtained, and therefore, when continuous processing is performed, sufficient carbon dioxide is not produced at the electrolytic cell outlet.
OD has not been reduced, and on the other hand, with the reduction of replenishment fluid, the tan in the tank is increasing while continuously recovering lIn ions.
From the viewpoint of pollution prevention and resource reuse, it is strongly desirable to maintain the ion concentration at a low concentration to maintain the deterioration of photographic processing performance, and to regenerate the processing solution after silver recovery and use it again as a replenisher. It will be done.

Examples of anodic oxidation combined with electrolytic silver recovery include a method in which the bleaching agent is regenerated at the anode and silver is recovered from the fixer at the cathode as described above (Japanese Patent Publication No. 50716/1983);
An anode that regenerates the bleaching solution in the bleach-fix solution (Special Publication No. 57-16345, Special Publication No. 55-9637);
Some attempts have been made to recover silver from the fixing solution and reduce COD by applying an alternating voltage to the cathode (Japanese Patent Publication No. 53-43478). However, the specific problems with electrolytic processing of photographic processing solutions are The processing solution is not a solution containing only silver complex ions and aminopolycarboxylic acid iron (11) complex salts, but also contains many other photographic processing chemicals, all of which are compounds that are easily susceptible to oxidation or reduction. It is to be. That is, if reduction of 1111 ions occurs at the cathode, a portion of the photographic processing chemicals are simultaneously subjected to anodic oxidation at the anode, producing substances that cause deterioration in processing performance as described above. This is because the electrode does not have selectivity only for regenerating oxidation of useful substances.

It is well known that the reaction on an electrode is determined by the potential corresponding to the set current density or the set potential and the redox potential of the reactive species. For example, iron aminopolycarboxylate (II
I) Using complex salt as a bleaching agent and using sodium thiosulfate as a fixing agent,
When electrolytic silver is recovered in a normal electrolytic bath from a bleach-fix solution containing sodium sulfite as a preservative, silver precipitation and reduction of iron(III) aminopolycarboxylate occur competitively at the cathode, but reduction occurs at the anode. In addition to the oxidation of iron(II) aminopolycarboxylic acid, a large amount of sulfate ions are generated by oxidation of thiosulfate and sulfite. In addition, tar, which is an oxide of the color developing agent which is the inflow, accumulates. Contamination of a large amount of sulfate ions into the bleach-fix solution slows down the desilvering rate and causes deterioration of processing performance. Furthermore, since sufficient reoxidation of the aminopolycarboxylic acid cannot be carried out, the redox potential of the bleaching solution becomes extremely base, which in turn reduces the silver bleaching (desilvering) rate.

This caused a serious problem of discoloration.

In order to prevent such problems as much as possible, efforts have been made to lower the current density by using carbon fibers or the like for the anode, and these have been used in practice. Despite these efforts and many others mentioned above, in each case, in order to eliminate processing problems, extremely long electrolysis times are required at low current densities, or unnecessarily long electrolysis times are required to increase the anode area. Although it has been put into practical use only for the purpose of recovering silver from processing solutions, reusing it causes problems such as the need for a large electrolytic bath, and causes serious damage to photographic materials. It has been said to be dragon-like for this reason.

In addition, in the conventional method, when molded carbon (graphite) or carbon fiber is used for the anode, if it is electrolytically treated and reused many times, even if highly corrosion-resistant stainless steel is used for the cathode, it will not work. The drawback is that it gradually corrodes, which has prevented the effective reuse of the liquid.

Furthermore, during the actual electrolytic treatment, a strange odor is generated, and harmful gases such as sulfur dioxide gas and cyan gas are detected in the bleach-fixing solution, which is not at all desirable from the viewpoint of environmental conservation.

On the other hand, in recent years, color processing has become more dispersed due to the decentralization of processing of photographic materials.
Processing machines are becoming smaller, and in processing methods using these small machines, the trend is to eliminate the water washing step and replenish the processing solution at a lower concentration, coupled with the simplification and speeding up of processes such as bleach-fixing. Stronger than before, silver complex ions, etc.
There are concerns about the effects of accumulation of dissolved components. Therefore, by taking advantage of the advantages of the electrolytic method as described above, it is desirable to efficiently reoxidize the aminopolycarboxylic acid iron (IF) complex salt in the case of a bleach-fix solution for the purpose of suppressing unnecessary oxidation at the anode while recovering electrolytic silver. There is a strong demand for an electrolytic processing method that can be used without adversely affecting photographic processing performance or corrosion of processing equipment when recycled.

Furthermore, the emergence of a method and device that can perform compact and high-capacity electrolytic treatment and recovery when connected to a processing machine is awaited.

[Purpose of the invention]

The first object of the present invention is to effectively electrolytically oxidize and reuse the used photographic processing solution, and the second object is to dissolve the COD of photographic processing waste by electrolytic method. It is an object of the present invention to provide a non-polluting processing technique capable of recovering silver from a photographic processing solution containing components by an electrolytic method and at the same time reducing COD of processing waste liquid and reducing environmental pollution.

The third purpose is to recover silver from photographic processing solutions that contain dissolved silver ions by electrolytic methods, and to eliminate unnecessary anodic oxidation that has a negative impact on photographic processing performance and electrolytic equipment when recycling processing solutions. For example, it suppresses the decomposition of hypo and sulfites that dissolve silver, enabling effective reuse, and prevents the generation of precipitation, slatch, tar, etc. due to unnecessary anodic oxidation. It is an object of the present invention to provide an electrolytic processing technique that does not cause defects in photographic performance, such as defects caused by spot-like foreign matter and fog such as stain, on processed photographic materials even when processing liquid is reused.

A fourth object is to provide an electrolytic treatment technique that efficiently reoxidizes the reduced aminopolycarboxylic acid iron complex salt during electrolytic silver recovery from a bleach-fix solution.

A fifth object is to provide an electrolytic treatment technique that can efficiently process a large amount of treatment liquid in a short time and regenerate the treatment liquid.

A sixth object is to provide a technology that can be built into an automatic processor and continuously processed in-line.

The seventh purpose is to provide a technology that can reduce the generation of odor and harmful gas during electrolysis.

[Structure and effects of the invention]

As a result of numerous experiments to achieve the above object, the present inventors have found that it is effective to use a bed electrode as an anode in a technique for electrolytically processing a photographic processing solution containing at least a silver ion-dissolved component. I found it.

As this bed electrode, a fluidized bed electrode or a fixed bed electrode made of conductive particles can be adopted. It has been found that this achieves the above object.

Furthermore, the present inventors have discovered that all of the above objects of the invention can be achieved by using a fluidized bed or fixed bed electrode mainly composed of conductive particles as a bend electrode for the anode of a normal electrolytic cell. .

Surprisingly, it has been found that the lower the surface tension of the photographic processing solution, the more the effects of the present invention are exhibited.

In addition, as a method of electrolysis using a fluidized bed, Japanese Patent Application Laid-Open No. 53-6
There is one described in the specification of No. 5218. However, in this method, non-conductive particles (particles unrelated to electrolysis) are added between the cathode and anode to create a fluidized bed, increasing the diffusion effect on the electrode surface.
This is a technology to achieve an effect equal to or higher than that of high-speed rotation using a rotating cathode plate, but the drawbacks such as generation of tar, precipitation, and floating matter have not been improved, and technically the present invention is beyond the scope of the present invention. are completely different. Although it is possible to recover silver down to low concentrations, the present invention has an effect not seen in the conventional technology, that is, it reduces COD at the electrolytic cell outlet as much as possible even during continuous processing. The effect is that it can be done. Even more surprisingly, during the electrolytic treatment, almost no odor was noticed, no sludge or tar was observed to be produced, and no harmful gases such as sulfur dioxide gas or cyan gas were detected. Not only after electrolytic treatment,
Even when recycled, no defects such as yellow stain were observed in color photographs, and the condition was extremely good.

Such an effect is completely unexpected from the effects of conventionally known fluidized bed electrodes, but unlike normal electrodes, bed electrodes such as fluidized bed electrodes and fixed bed electrodes Electron transfer is an isolated system in which conductive particles receive and take electrons from an electrode (electrode), then move away from the current collector and transfer charges, and this electron transfer is mainly due to the peculiarity that it is pulse-like. It is inferred.

The term "bed electrode" here refers to an electrode that combines a conductive particle portion and a current collector (plate, rope, etc.).

A typical example is to have conductive particles in a cage-like container with a current collecting net placed on the bottom, to flow an electrolytic solution from above or below, and to use the conductive particles in a flowing state as an electrode. Ru. A feature of this electrode is that the conductive particles are used in a cold fluid state as a fluidized or fixed bed.

For convenience, there are two types of electrodes: fluidized bed electrodes, which use conductive particles in a fluidized state by flowing a liquid from below, and electrodes which use fixed conductive particles, and electrodes which use conductive particles in a fixed state by flowing liquid upwards, and those which use conductive particles in a fixed state by flowing liquid upwards. Those used in this state are called fixed bed electrodes, however, other types such as those that are made to flow from a machine do not take the form exemplified here.

The material of the conductive particles used in the bed electrode is not particularly limited as long as it is a conductive material that does not cause anodic dissolution.
It is appropriately selected depending on the oxidizable substances contained in various photographic processing solutions. Examples of such materials include non-corrosive metals such as platinum and semiconductors. Considering cost and impact on the human body, molded carbon (graphite) and ruthenium oxide (or alloy) are preferable.

The effects of the present invention are effectively achieved in particular by using shaped carbon (graphite).

The manufacturing method of the conductive particles is not particularly limited, but the conductive material may be added as is in the form of particles, or glass, polymethyl methacrylate, polystyrene, phenol formaldehyde, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate formed into particles may be used. It is also possible to use a conductive material coated on a non-conductive material by various methods such as electroless plating (metal ion substitution method), vapor deposition, and sputtering. These particles may be hollow.

The effects of the present invention depend on the flow rate of the treatment liquid passing through the electrolytic cell, especially the space velocity of the treatment liquid passing through the fluidized bed cathode, which depends on the length of the fluidized bed electrode in the treatment liquid passage direction and the width of the bottom surface. , and the amount (bulk), particle size, granularity of the particles - cannot be determined generally, but preferably the effects of the invention are effectively obtained at a flow rate of 1 mm/sec to 5 m/sec. In particular, at a flow rate of jam/sec to 1 m/sec, the effect is that the strange odor emitted by the treatment liquid is surprisingly almost unnoticeable.
The lowest COD value can be measured in the range of seC to l m /Sec.

The particle size of the conductive particles is determined based on the balance with the flow rate and is not particularly limited, but if the particles are too small, the mesh current collectors that support the particles will become fine, causing floating matter in the processing solution. There is a possibility of clogging due to In addition, if the particles are thick, a large flow rate is required to maintain them in a fluid state, and the flow is disturbed, which may cause the deposited silver to peel off.

However, if the particles have a small specific gravity, larger particles may be used, and measures can be taken to prevent clogging and silver peeling. Kowarisei 1; version, 11·, preferably about 0.1 to 7
It is said to be about the size of a crane. If it is less than 0.1 m, the mesh of the net-like current collector supporting the particles becomes fine as described above, and clogging by suspended matter in the processing liquid may easily occur. If it exceeds 7 fl, a large flow rate may be required to maintain it in a fluid state.

When using ruthenium oxide or the like having a relatively large specific gravity, the particle size is particularly between 0.1fi and 3.0fi. Ofl is preferable, and effects such as less generation of stain during sludge generation and recycling are obtained.

Further, in the case of particles having a relatively small specific gravity such as carbon (graphite), the particle size is preferably 0.5 to 4.0 fl, and the same effect as the above-mentioned ruthenium oxide can be obtained.

Furthermore, it has been found that carbon particles have the effect of not generating tar even in a developing solution or a processing solution containing a developing agent.

A conductor called a current collector that is electrically connected to the positive terminal of the power supply is attached to the conductive particle frame (anode bed electrode frame), but the shape and size of the container depend on the amount of particles and particle size. It is determined by the flow rate and is not particularly limited.It is preferable to use a net-like current collector arranged on the bottom surface in the flow direction.In particular, in the case of a bleach-fix solution, one in which the current collector is extended from the bottom surface in the flow direction is preferable. ) compared to others,
conductive particles can achieve at least the same effect,
In particular, this method has the advantage that the bleaching agent that is reduced is reoxidized very efficiently at the same time as the silver is recovered at the cathode, which is advantageous for downsizing the electrolytic cell. Specifically, it is preferable that the fluidized bed electrode be divided into several to several dozen chambers in the flow direction, the partition walls made of a reticular conductive material, and electrically connected to the lower surface current collector, but the present invention is not limited thereto. do not have.

As materials used for the current collector, almost all materials used for conductive particles can be used. Ruthenium oxide and platinum are preferably used, but the material is not limited thereto.

In the present invention, the potential distribution within the bed electrode is preferably 300a+V or less, preferably 200s+V or less,
Particularly preferably, it is particularly effective when the voltage is 100+++V or less. Ij, although not limited to, the potential distribution in any part of the bed electrode chamber is at least 200 m.
It is preferable that the voltage is within V, more preferably within 10 V.

A conductive obstacle electrically connected to the current collector is arbitrarily arranged inside the bed electrode, and the potential distribution inside the bed electrode is
It is also preferable to make the axis V or less.

At this time, the measurement of the potential distribution within the bed electrode is as follows:
F Roe Left, Dee Hooch, A, Callanand ``Jay Apple Electrochem J (F,
Coeuret, D., Hutin SA.

Gaunand SJ, Apple, E Iectr
ochem 6.417 (1976). However, instead of the copper ring at the tip of the probe, fluidized bed conductive particles are used.

Furthermore, the present inventors found that the surface tension of the treatment liquid in the electrolysis was 65 d.
It has been found that silver can be recovered very efficiently by the present invention when yr+e or less, preferably 55 dyne or less.

The electrolyte may be stirred in the electrolytic bed using a stirrer such as a propeller near the fluidized bed electrode. In particular, stirring at the front of the fluidized bed electrode in the direction of liquid flow not only improves the current effect but also reduces sulfurization. The unexpected effect is less silver formation and less sludge formation.

Similarly, the fluidized bed cathode may be irradiated with ultrasound to increase the recovery rate. The wavelength is not particularly limited, but if the frequency is too low, it will cause discomfort, and if the frequency is too high, the practical effect will be reduced, so it is preferable to set optimal conditions.
Further, in the case of a fixed bed electrode, the conductive particles may be forcibly stirred with a propeller or the like.

When the fluidized bed particles contain 50% or less of non-conductive particles, the generation of slatch and tar can be suppressed, and it is preferable, and more preferably, the content is 10% or less, and the generation of off-flavor can be almost suppressed.

A baffle plate can also be installed between the cathode and anode.

This makes it possible to effectively lengthen the distance between the cathode and anode in a small amount of space, which is advantageous for continuous silver recovery and reuse of the bleach-fix solution, and makes it possible to use a combine electrolytic cell built into an automatic processor. Become.

Such an electrolytic cell may be directly connected to a treatment tank to electrolytically treat the overflow liquid, or the treated liquid may be regenerated through continuous electrolytic treatment and refluxed.

In the case of reusing the bleach-fixing solution, the electrolytic cell is preferably followed by a filter layer and/or an ion exchange resin layer to remove suspended matter and recover unnecessary ions.

When silver is recovered from the bleach-fix solution and then reused, the reduced f! In order to oxidize something like DTAPe (I[), a reoxidation means such as aeration may be further provided. In the present invention, for example, iron (II) can be converted into iron (III) by anodic oxidation, but aeration It is also possible to take a mode in which the oxidation is further ensured by, for example, the following.

In the case of a bleach-fix solution, a reducing agent may be added before recovering the electrolytic silver to reduce the oxidizing agent such as HDTAFe (III) in advance to a reduced form such as EI)TAFe (If). This is preferable also from the point of view of efficiency.

The potential distribution within the bed electrode is preferably as small as possible in order to suppress side reactions and cause uniform silver electrodeposition, and is at least 200 mV or less, preferably 100 mV or less, particularly preferably 50 mV or less in any part of the bed electrode. -v or less is better, and the smaller the potential distribution within the bed electrode, the more the effects of the present invention will be maximized.

For this purpose, the bed electrode preferably consists of a bed electrode chamber partitioned by a number of conductive partition walls connected to a conductive electrode substrate, and also a bed electrode chamber separated by a number of conductive barrier walls connected to a number of electrode substrates. Preferably placed at any location within the bed electrode, these methods allow minimizing the potential distribution within the electrode.

The cathode potential may be regulated at constant potential.

Further, constant current regulation may be used, and constant potential regulation is preferable (to prevent tar and slouch).

In the case of constant potential regulation, a reference electrode is required.

This reference electrode may be installed at any position within the electrolytic cell, but is preferably installed between the anode and cathode. Any electrode can be used as the reference electrode, such as a saturated caramel electrode, a silver sulfide electrode, etc. Electrodes such as platinum electrodes, stainless steel electrodes, and carbon electrodes that do not dissolve in bleach-fixing solutions or fixing solutions can also be used.

[Embodiments of the invention]

Examples of the present invention will be described below along with comparative examples.

However, the following examples are used to explain the present invention and are not intended to limit the present invention.

Comparative example: First, a comparative example will be explained using the following example.

Bleach-fix water 38
0ml ethylenediaminetetraacetic acid 10
g Ethylenediaminetetraacetic acid iron(II[) complex salt 60g
Sodium sulfite 10g,
Ammonium hydroxide (28% aqueous solution) 4g Ammonium thiosulfate (60% aqueous solution) 120g 1st color developer Add 500o+ j! Color developer 1 water 2 Anhydrous sodium sulfite 3 Kodak CD3" 4 Benzyl alcohol 5 Sodium hydroxide 9 6 Borax (IOH!O) 7 Potassium bromide 8 Add water to total pH -11.5±0.1 Adjust PTT to 7.2 with ammonium hydroxide and acetic acid. This bleach-fix solution was used to fatigue a commercially available color negative by processing it until the silver content reached 4 g/J. Using 4Il of this solution, it was carried out in an electrolytic cell using a rotating electrode method for comparison as shown below. The results will be explained.

FIG. 2 shows the configuration of a rotating electrode method as a comparative example. In FIG. 2, a indicates a power source, and a constant current power source is generally used.

b is the cathode, which is a cylinder made of stainless steel plate. C is an anode, and a carbon rod or carbon plate is used. d is a motor, and the rotation of the motor is transmitted to the stainless steel plate cathode by a belt. e is a waste liquid inlet, and f is a drain port.

Cells are operated as follows.

Inject the fixer to be desilvered and the bleach-fixer through the inlet e.
Stop the injection when the volume is sufficient for electrolysis. Alternatively, some devices detect the liquid level with a sensor or the like and automatically perform the injection operation. When the amount of liquid is sufficient for electrolysis, the cathode is rotated and a current is applied.

Conditions such as current application time are determined empirically for each device. Although silver content analysis may be carried out if necessary, there is currently no established technology to automatically determine the end point of silver recovery.After electrolysis, the desilvered fixer and bleach-fixer are discharged be done. Since silver adhering to the cathode dissolves again in the bleach-fix solution when the current is turned off, it is necessary to drain it immediately after the current is turned off.

In the conventional apparatus shown in FIG. 2, 5 g/j of silver! When electrolyzed with a bleach-fix solution, the current drops to 500 mA in 6 hours and then to 280 mA after 8 hours.

During this time, 0.9 g of silver is deposited on the cathode.

During this time, the pH of the solution in the anode chamber changes from 7.2 to 7.04.

If a substantially lower potential is applied, for example 300 mV, only 0.3 g of silver will be deposited during the same time.

The pH of the liquid increases from 7.2 to 7.62.

General description of the structure of the embodiment: Next, the present invention will be described in detail according to FIG. 1 and FIGS. 3 to 5. In each figure, the symbol I indicates an electrolytic cell.

The electrolytic cell (1) of each example has a cylindrical shape.

Fig. 1 shows a first embodiment of the present invention. In Fig. 1, ■ indicates a power supply device, and ■ indicates a cathode placed at the top of the electrolytic cell ■. The cathode ■ is a stainless steel cylindrical electrode here. be. ■
is a fluidized bed particle and carbon particles are used, which act as an anode. ■ is an anode, which is a carbon plate. In this example, the fluidized bed particles ■, which act as an anode, are the electrolytic cell ■.
is placed at the bottom of the ■ is a motor and is used to rotate the cathode. ■ is a storage tank. ■ indicates the direction of flow.

In the embodiment shown in FIG. 1, the processing liquid flows into the electrolytic cell I from below and flows out from above, as indicated by the arrow ■. Therefore,
First, it comes into contact with the anode (■) and the fluidized bed particles (■), where it undergoes actions such as oxidizing Fe(II) in the liquid and returns it to Pe(III), and then comes into contact with the upper cathode, and the electrolytic cell ■
Exit and return to storage tank ■.

In this way, the treatment liquid is circulated and electrolytically treated.

FIG. 3 shows a second embodiment of the invention. This is a dual-use bleach-fix recycle/disposal system that includes an example of the processor of the present invention attached to an automatic processor. In FIG. 3, ■ is a power supply device. (2) is the cathode, which is a stainless steel cylindrical electrode placed in the center of the electrolytic cell (2) almost concentrically with the electrolytic cell (2). 3 is an anode arranged in a cylindrical shape on the inner periphery of the electrolytic cell I, and is made of carbon. ■ is a fluidized bed particle arranged in a concentric cylindrical shape in contact with this anode ■.
In the example shown in FIG. 3, a copper wire is passed inside the cylinder constituting the electrolytic cell (1) for the purpose of reducing resistance, and connected at the bottom.

■ indicates a batch type air oxidation tank, and ■ indicates a bleach-fixing bath.

In the embodiment shown in FIG. 3, the processing liquid flows into the electrolytic cell from the lower part of the periphery and flows out from the upper part.

If the cock [phase] in Figure 3 is opened and the cock O is closed, then
It can be used as a regeneration system, and by closing the cock [phase] and opening the cock O, it can be used as a waste system.

FIG. 4 shows a third embodiment of the invention, which is a bleach-fix regeneration system including an example of the processing apparatus of the invention attached to an automatic processor. In FIG. 4, ■ is a power supply device. @ is a stainless steel disc electrode that serves as a cathode. ＠ is a conductive mesh that prevents fluidized bed particles ① from leaking out, and here a stainless steel mesh is used. (2) is a propeller, which has the role of vigorously stirring the electrolyte, especially in the vicinity of the cathode.

This propeller ■ is driven by a motor ■.

As a result of stirring near the cathode, the electrolysis rate increases.

The efficiency of silver recovery will also improve. It can be said that the same effect as using the rotating electrode in the above embodiment can be obtained. In the embodiment shown in FIG. 4, the liquid first contacts the cathode @ as indicated by the arrow (2), and then contacts the fluidized bed particles (2) which act as an anode.

At the cathode @, iron (III) is reduced to iron (U), so the liquid immediately after the cathode 0, which has the most iron (TI), is subjected to an anodic action, and iron (If) is converted to iron 1). The oxidation effect of is highly efficient.

FIG. 5 shows a fourth embodiment of the present invention, which is a fixer disposal system including an example of the processing device of the present invention attached to an automatic processor. It is combined with an anode consisting of fluidized bed particles.

■ is a conventional rotating cathode driven by motor ■. [Phase] is a conductive rope that does not leak particles (such as stainless steel mesh)
, 0 is the bath. [Phase] is the waste tank.

In the device of the present invention (Fig. 1, Fig. 3 to Fig. 5), the amount of Ag is 5
When electrolyzed with a tired bleach-fix containing g/It, the current dropped to 4.2 A in 6 hours, then 3 A after 8 hours.
．． It falls to 2A.

During this time, 4.9 g of eye power 1 was deposited on the cathode.

During this time, the pH of the solution changes from 7.2 to 7.04.

If a substantially lower potential is applied, for example -300a+V, only 0.3 g of silver will be deposited during the same time. The pn of the anolyte remains virtually unchanged and the pH of the solution is 7.
．． 2 to 7.62.

Experimental Example: Next, an experimental example of the present invention using the apparatus shown in FIGS. 1 and 3 to 5 will be described. The seed mouth fixer used was the same as that described in the comparative example.

(Experiment 1) The electrolytic device of the present invention was created so that the distance of the particles from the conductive net or rod was 3 cm, and an experiment was conducted. The flow rate of the apparatus of FIGS. 1 and 3 to 5 is g//
It was set as sin.

The device shown in Figure 2 used for comparison has a diameter of 10 cm and a length of 20 cm.
Experiments were conducted using a CII rotating cylindrical electrode at a rotational speed of 300 revolutions.

In both cases, platinum was used as the reference electrode, and an IOA potentiostat was used as the power source.

The recovery time is the time required for the amount of silver to reach 0.1 g/l, and the amount of silver was analyzed and prepared every 30 minutes by a conventional method.

The end point was determined from the decreasing curve of lI amount. The collection time is 2
Those within that time were analyzed every 10 minutes, and the end point was determined in the same manner.

No silver sulfide was produced up to the end point in any of the electrolyzers.

Table 1 shows the results of an electrolytic test using the above bleach-fix solution.
Shown in 1.

(Experiment 2) The results of silver recovery using the following fixer are shown in Table 1-2.

(Fixer) Ammonium thiosulfate 140 g Sodium sulfite 50 g Aqueous ammonia (28% aqueous solution) 4 g The above components were dissolved in drained water 11, and the pH was adjusted to 7 with aqueous ammonia.

The liquid was distributed only once, the flow rate was 417 hours, and the processing time was 1 hour.
It's time. In the comparative example, the electrolysis time was set to 1 hour, and the electrolysis was performed in a batch manner.

In this experiment, COD was reduced using chlorine. Chlorine was supplied from a chlorine cylinder through a capillary, and the experiment was conducted with the valve opening constant. Chlorine usage time is C
This is the time it takes for OD to reach 100 pp-. At this time, the experiment was carried out using the fixing bath indicated by ■ in FIG.

No silver sulfide was generated up to the end point in either device.

(Experiment 3) Table 1 shows the results of electrolysis using the device shown in Figure 3 using a constant current power supply.
-3. A glass bulb with a diameter of 2 mm was used as the non-conductive material. The bleach-fix solution mentioned above was used as the solution.

Table 1-3 Electrolytic test results (Experiment 4) A color negative was processed and fatigued with the fixer used in Experiment 2 to give a silver concentration of 5 g/l, and this fixer 41 was regenerated in the electrolytic cell of the present invention.

The flow rate of each device was defined as g Il /sin. Further, the potential of the cathode was set to 10.5 V in the same manner as in Experiment 1.

The results are shown in Table 1-4. At this time, a fixing solution was placed in the storage tank (2) of the embodiment shown in FIG. In addition, the bath (2) of the example shown in FIGS. 3 and 4 was used as a fixing bath.

The end point was determined in the same manner as in Experiment 1.

Table 1-4 Electrolytic test results Each experimental example has been explained above.

In the case of the electrolytic method of the present invention, no sludge or tar was observed even when the electrolytic solution was filtered, and no residue was left on the filter paper. Furthermore, when the purity of the electrodeposited silver was measured, it was found that the purity of the particles in all parts was 99.9% on average. On the other hand, in the comparative electrolytic silver recovery method, tar was densely electrodeposited on the upper peripheral edge of the rotating electrode and the upper edge of the graphite anode. When the filtrate was further filtered through filter paper, a large amount of blackish brown precipitate remained on the filter paper. Furthermore, the purity of the deposited silver was extremely low at 96.9%.

With the device of the invention, the air oxidation time is significantly reduced in the case of regeneration. Also Na1So by air oxidation.

is further decomposed, so the total amount of decomposition of the bleach-fixing solution components is significantly reduced. Moreover, it can be seen that even in the case of disposal, there is a great effect on reducing COD.

Other embodiments: The bleach-fix solution described in the comparative example was oxidized with an air pump using an air sparger with a mesh size of 10μ to oxidize the ferrous acetate complex salt and return it to a ferric complex salt. .

Furthermore, ethylenediaminetetraacetic acid ferric salt and ammonium thiosulfate were quantitatively analyzed, and the difference from the initial concentration was newly added and regenerated.

Two types of this bleach-fix solution (a solution prepared by a comparative silver recovery method and a solution subjected to silver recovery treatment according to the method of the present invention) were used for the following treatment.

(Stabilizing solution) Formalin 2.0 ml Add water to make 11.

For the treatment, the maximum and minimum concentrations of the samples are shown in Table 2 below.

A sample was prepared as follows. The following coupler was used in an amount of 0.1 mol per mol of silver halide, mixed with tricresyl phosphate in an amount of 1 times the weight of the coupler as a high-boiling organic solvent, and ethyl acetate was added to the mixture. It was heated to 60°C to completely dissolve. This solution was mixed with 50mj of a 10% aqueous solution of Alkanol B (registered trademark, manufactured by DuPont: alkylnaphthalene sulfonate). The mixture was mixed with 700 nl of a 10% gelatin aqueous solution and dispersed using a colloid mill to obtain an emulsion. Thereafter, this dispersion was added to 2 kg of green-sensitive silver iodobromide emulsion (silver iodide 6 mol %), and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water; methanol- A sample was prepared by coating and drying on a transparent polyester base coated with 1:1). (Average grain size: 1.2 .mu. Coated silver amount: 17 .mu./da+2) Coupler used The sample thus obtained was used as Sample 1, and after wedge exposure was carried out in accordance with a conventional method, the following treatments were carried out.

[Processing process] (35℃) Processing time 1 Color development
2 minutes 2 bleach fixing
6 minutes 3 Water washing 3 minutes 15 seconds 4 Stabilization 1 minute 30 seconds 5 The following processing solutions were used except for drying, bleaching and fixing.

[Color development]

Potassium carbonate 30g Sodium sulfite 4g Potassium bromide
1g Hydroxyamine 1/2 sulfate 2g Color developing agent (D-4) 0.012mol 11■
[Stop] Glacial acetic acid (90% solution) 10ml β-dimethylaminoethylthiourea 2HC12g Sodium sulfite 5g Add water to 1j
! Toshipo4. As can be seen from the results in Table 2, the bleach-fix solution treated with electrolytic silver recovery according to the method of the present invention does not change the stain to the state of the new solution even if the photographic material is processed after recycling. It can be seen that it is in good condition.

On the other hand, the maximum concentration also decreased in the comparative treatment, whereas in the silver recovery method of the present invention, a value equal to that of the new solution was obtained.

[Brief explanation of drawings]

FIG. 1 is a block diagram showing an embodiment of the present invention, and FIG. 2 is a block diagram showing a comparative example. FIGS. 3 to 5 are configuration diagrams showing another embodiment of the present invention. ■...Power supply device, ■,@...Cathode, ■...Fluidized bed particles ■...Anode. Patent Applicant: Konishiroku Photo Industry Co., Ltd. Agent, Patent Attorney Toru Takatsuki Figure 2 Bleach and Separation Diagram 3 Figure 4 514 Procedural Amendment (Method) April 1, 1985 April 1985 Patent side 3 submitted on the 6th, relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1
27) Roku Konishi Photo Industry Co., Ltd. Representative Director I
Megumi Te 4, Agent 〒100 As per voluntary action (no change in content) Procedural amendment May 20, 1985 Commissioner of the Patent Office Manabu Shiga 1985 Patent side No. 73009 No. 3, Person making amendment case Relationship Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 7, Contents of the amendment As per the attachment (1) In the specification (referring to the revised specification submitted on April 15, 1985; the same shall apply hereinafter): "Scope of Claims" is amended as follows. 1. A method for processing a photographic processing solution, which comprises electrolytically treating a photographic processing solution for a silver halide photographic light-sensitive material containing at least a silver ion-dissolved component using a bed electrode as an anode of an electrolytic cell. 3. The method of processing a photographic processing solution according to claim 1, wherein the bed electrode is a fixed bed electrode. 3. The method of claim 1, wherein the bed electrode is a fluidized bed electrode. 4. The photographic processing solution according to any one of claims 1 to 3, wherein the bed electrode contains non-conductive particles. 5. The bed electrode contains non-conductive particles by 50% by bulk volume.
A method for processing a photographic processing liquid according to any one of claims 1 to 4, characterized in that it contains the following: 6. The method for processing a photographic processing solution according to any one of claims 1 to 5, wherein the bed electrode has a U-shaped temporary or net-like current collecting electrode. 7. The method for processing a photographic processing solution according to any one of claims 1 to 6, wherein the bed electrode is composed of two or more parts of a partition-like and/or network-like conductive material. . 6. A photographic processing machine for processing silver halide photographic materials, characterized in that it has an electrolytic means using a bed electrode as an anode. 9. The photographic processing machine according to claim 8, wherein the bed electrode is a fixed bed electrode. 10. The photographic processing machine according to claim 8, wherein the bed electrode is a fluidized bed electrode. 11. Photographic processing according to any one of claims 7 to 9, characterized in that the surface tension of the photographic processing solution electrolyzed by the electrolytic means of the photographic processing machine is 65 dyn/am. Machine. 12. Claim 8, characterized in that the bed electrode has a bulkhead or net-like current collector electrode.
The photographic processing machine according to any one of items 1 to 11. 13. The photographic processing machine according to any one of claims 8 to 12, wherein the bed electrode is composed of two or more parts of a partition-like and/or mesh-like conductive material. 14. The photographic processing machine according to any one of claims 8 to 13, wherein the bed electrode contains non-conductive particles. 15. The bed electrode contains non-conductive particles with a bulk volume of 50
The photographic processing machine according to any one of claims 8 to 13, wherein the photographic processing machine contains % or less. (2) Same, page 14, line 5 from the bottom, page 15, line 1, line 16
In the third line from the bottom of the page and the second line from the bottom of the same page, the words "conductive particles" are corrected to "conductive bed particles." (3) In the same text, in the 16th line 4 lines from the bottom, "spread on the bottom" is corrected to "spread on the bottom or around it." (4) Same, on page 18, line 4, amend "even if added" to "even if processed." (5) "Polyethylene terephthalate" on page 18, line 8 is corrected to "polyethylene terephthalate". (6) Insert the following between lines 12 and 13 on page 18. "The detailed explanation of the present invention will be given below with a focus on a fluidized bed, but a fixed bed can also be used to obtain similar effects using similar methods, and can be considered to be equivalent to a fluidized bed. When the specific gravity of the particles is lighter than that of the photographic processing solution, as in the case where the particle specific gravity is lighter than that of the photographic processing solution, the flow direction is exactly the opposite in the convenient definitions of fluidized bed and fixed bed.'' (7) Same, line 3 from the bottom of No. 18 - bottom 2 lines from “1
w/sec~5 cm/5ecJ to rO, 1wm/s
Corrected to ec~100 cut/5ecJ. (8) Same, page 18, last line r 10/sec ~1
m/5ecJ to rO, 1mm/sec~50w/5ec
Correct it with J. (9) Same, page 19, line 3, amend "measurable" to "obtainable." (10) Same, in the 5th line from the bottom of No. 20, "net on the bottom in the direction of flow" is changed to "net or plate on the bottom or side in the direction of flow"
and correct it. (11) Same, page 22, lines 14-15, “J.
"Ampoule Electrochem" is corrected to "Journal of Applied Electrochemistry." (12) "Electrolyte bed" on page 23, line 4 of the same document is corrected to "electrolysis in progress." (13) "Recovery rate" on page 23, line 11 is corrected to "oxidation rate". (14) Same as above, on page 24, line 5, "combyte" is corrected to "compact." (15) Same as above, in the 6th line from the bottom of No. 24, change “reoxidation means” to “
``auxiliary means for reoxidation''. (16) In the last line of page 24, "electrolytic silver recovery" is corrected to "supply to electrolytic cell." (17) In the same document, page 25, line 3, "potential efficiency may be reduced" is corrected to "current efficiency may be reduced". (18) Same, page 25, lines 4-5, “To suppress side reactions and produce uniform silver electrodeposition” was changed to “To obtain sufficient oxidizing power and to control the reaction.” "Also," he corrected. (19) Same, page 25, line 7, “At least 200 s+
V or less" is amended to "at least 300IIIv or less, preferably 200 mV or less, and further." (20) Similarly, in the 25th line 3 lines from the bottom, "About the cathode potential" is corrected to "About the anode potential." (21) Similarly, in the second line from the bottom of No. 25 - the last line, "Good. Preferably constant potential regulation (from the viewpoint of preventing tar and slatch)." is a constant potential regulation.'' (22) Same, page 26, line 5, "caramel" is corrected to "calomel." (23) Same, p. 26, line 8, “can also be used” is changed to “
I am corrected by saying, ``I can use it.'' (24) “Rotating electrode method” in the same text, two lines from the bottom of No. 27
is corrected to "rotating electrode method for desilvering". (25) ``Desilver'' on page 28, line 8 of the same document is amended to ``oxidize and desilver''. (26) Same, page 29, 2nd line from the bottom - the last line, "■ is an anode" is corrected to "■ is an anode current collector." (27) "Anode" in the bottom three lines of page 30 is corrected to "anode current collector". (28) Same, page 31, lines 2 and 3, "A copper wire is passed through and connected at the bottom for the purpose of reducing resistance." is changed to "A copper wire is passed through and connected at the bottom for the purpose of reducing the resistance of the current collector." It is connected to the collector at multiple arbitrary locations.'' (29) Same, page 32, line 13, “fluidized bed particles”
Corrected as ``fixed bed particles''. (30) Same, on page 32, in the 4th line from the bottom, "bath" is corrected to read "photographic material processing bath." (31) Same, on page 33, 6 lines from the bottom, "particles" is corrected to "up to the edge of the particle layer."that's all

Claims (1)

[Scope of Claims] 1. Processing of a photographic processing solution comprising electrolytically processing a photographic processing solution of a silver halide photographic light-sensitive material containing at least a silver ion-dissolved component using a bed electrode as an anode of an electrolytic cell. Method. 2. The method for processing a photographic processing solution according to claim 1, wherein the bed electrode is a fixed bed electrode. 3. The method for processing a photographic processing solution according to claim 1, wherein the bed electrode is a fluidized bed electrode. 4. The method for processing a photographic processing liquid according to any one of claims 1 to 3, wherein the bed electrode contains non-conductive particles. 5. The bed electrode contains non-conductive particles by 50% by bulk volume.
A method for processing a photographic processing liquid according to any one of claims 1 to 4, characterized in that it contains the following: 6. The method for processing a photographic processing liquid according to any one of claims 1 to 5, wherein the bed electrode has a current collector electrode. 7. The method for processing a photographic processing solution according to any one of claims 1 to 6, wherein the bed electrode is composed of two or more parts of a partition-like and/or network-like conductive material. . 8. A photographic processing machine for processing silver halide photographic materials, characterized in that it has an electrolytic means using a bed electrode as an anode. 9. The photographic processing machine according to claim 8, wherein the bed electrode is a fixed bed electrode. 10. The photographic processing machine according to claim 8, wherein the bed electrode is a fluidized bed electrode. 11. Photographic processing according to any one of claims 7 to 9, characterized in that the surface tension of the photographic processing liquid electrolyzed by the electrolytic means of the photographic processing machine is 65 dyn/cm. Machine. 12. The photographic processing machine according to any one of claims 8 to 11, wherein the bed electrode has a current collector electrode. 13. The photographic processing machine according to any one of claims 8 to 12, wherein the bed electrode is composed of two or more parts of a partition-like and/or mesh-like conductive material. 14. The photographic processing machine according to any one of claims 8 to 13, wherein the bed electrode contains non-conductive particles. 15. The bed electrode contains non-conductive particles with a bulk volume of 50
The photographic processing machine according to any one of claims 8 to 13, wherein the photographic processing machine contains % or less.