JPH05154488A - Treatment of processing waste liquid of nonsilver salt photosensitive material - Google Patents

Abstract

PURPOSE:To prevent formation of harmful substance having offensive odor and to enhance work environment by adding an oxidizing agent to processing waste liquid, furthermore neutralizing the processing waste liquid by acid and filtrating the solution to separate it into solid and liquid. CONSTITUTION:Exhausted wasting liquid which has been circulated and reused in an automatic developing machine 1 is introduced into a flocculation tank 3 to the prescribed height of liquid surface by a pump 2. An oxidizing agent is added to the flocculation tank 3 from an oxidizing agent tank 5 by a pump 6. Acid is added thereto from a neutralizer tank 7 by a pump 8. The solution is agitated by an agitator 17 and also the pH of processing waste liquid is regulated to a prescribed range. Further a powdery filter aid is added from a vessel 132 thereof and the other powdery filter aid is added from a vessel 13b thereof at the same time as addition of acid. Thereby contained dissoluble components and colloidal component are flocculated. These are sent to a centrifugal filter 20 by a pump 19 and separated into liquid and solid. Filtrate is sent to the automatic developing machine 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for treating a waste liquid generated in the development of a light-sensitive material containing a non-silver salt substance as a light-sensitive substance to separate it into a solid content and a liquid. The present invention relates to a method for treating a waste liquid containing a reducing agent that has an offensive odor or a substance that is harmful to hygiene during neutralization.

[0002]

2. Description of the Related Art Development of a non-silver salt light-sensitive material such as a light-sensitive lithographic printing plate is usually carried out by using an automatic developing machine while the image-wise exposed light-sensitive lithographic printing plate is conveyed to the surface of the light-sensitive layer thereof. A developing step of supplying a developing solution to elute the photosensitive layer imagewise to form a lithographic printing plate, and after the developing step, a washing step, a treatment with a rinsing solution, a desensitizing step, etc. are added if necessary. Processing is taking place.

As a method for treating the waste liquid discharged in such a developing process, the waste liquid is neutralized with a neutralizing agent, and a coagulant is added to agglomerate dissolved components and colloidal substances for filtration to obtain a solid content and a liquid. There is known a method for treating a treatment waste liquid, in which the liquid is separated into a solid content and a liquid component by further evaporating the liquid by heating (Japanese Patent Laid-Open No. 3-90239, etc.).

[0004]

However, when such a treatment waste liquid contains a reducing substance such as a sulfite salt, addition of an acid in the neutralization treatment causes an offensive odor such as sulfurous acid gas or causes a hygienic problem. There is a problem that harmful gas is generated and the indoor environment deteriorates.

Therefore, an object of the present invention is to provide a method for treating a processing waste liquid (including a fatigue liquid) of a non-silver salt light-sensitive material,
Providing a processing waste liquid treatment method that prevents the generation of odorous or hygienic substances by neutralizing the processing waste liquid containing a reducing agent, and improves the working environment around the processing waste liquid processing equipment. It is to be.

[0006]

The processing method of the present invention which achieves the above-mentioned object of the present invention is, at the same time as or after the addition of an oxidizing agent to a processing waste liquid of a non-silver salt light-sensitive material containing a reducing substance, It is characterized in that it is neutralized with an acid and the treated waste liquid is separated into a solid content and a liquid by filtration.

The present invention will be described in detail below.

The treatment waste liquid to which the method of the present invention is applied contains a reducing substance such as a sulfite salt (for example, potassium sulfite, sodium sulfite, etc.) which has an offensive odor and produces a gas harmful to hygiene by neutralization with an acid. It is the contained liquid.

Examples of the oxidizing agent added to the processing waste liquid containing such a reducing substance include hydrogen peroxide, silver oxide, oxyacids (nitrous acid, nitric acid, permanganic acid, chromic acid,
(Chloric acid, hypochlorous acid, etc.) and salts thereof, air, oxygen, ozone, and compounds that easily release oxygen. The oxidizing agent may be added in a chemical equivalent amount or more with respect to the amount of the reducing agent contained in the treatment waste liquid, and is usually in the range of 0.1 to 10% by weight.

The oxidizing agent is added to the treatment waste liquid at the same time as or before the addition of the acid for neutralization. The position of addition of the oxidant to the processing waste liquid is determined by the rinsing tank containing the rinsing water to be recycled and reused in the automatic developing machine or the pipe for sending the rinsing water in the rinsing tank to the shower nozzle for rinsing, or the processing waste liquid treatment device. A coagulation tank is preferable, and a coagulation tank is more preferable. In order to add an oxidizer to the washing water in the pipe, a check valve is provided outside the pump in the pipe line connecting the pipe and the tank for storing the oxidizer, and the reverse flow of the washing water to the tank for storing the oxidizer is performed. Prevent.

In the present invention, the acid used as a neutralizing agent for the treatment waste liquid is preferably a liquid acid such as sulfuric acid or hydrochloric acid. The pH of the treated waste liquid after neutralization is preferably 6 or less, more preferably 2 to 5. It is preferable to use a glass electrode for pH detection.

In the present invention, a filter aid may be added to the processing waste liquid. As a filter aid, diatomaceous earth,
Cellulose-based auxiliaries and other mineral-based auxiliaries (for example, pearlite) and the like are preferable. Commercially available filter aids include Radiolite # 100 and # 70 as diatomaceous earth filter aids.
No. 0, # 800 (Showa Chemical Industry Co., Ltd.), as a cellulose-based filter aid, Fiibousel SW-10, BH-40
(Nippon diatomaceous earth Co., Ltd.), as a mineral-based filter aid other than diatomaceous earth, Celite Hyflo Supercell (Nippon diatomaceous earth Co., Ltd.), Topcoperlite # 36, # 37
(The same), carbon (activated carbon), asbestos, etc. can be used. Two or more kinds of filter aids can be used in combination, and a preferred combination is a combination of a cellulosic filter aid and activated carbon. The amount of filter aid added is 0.
The amount is preferably in the range of 1 to 3% by weight, and more preferably equal to or half the residual amount of the liquid to be treated. The filter aid is preferably added at the same time as the addition of the neutralizing agent or before the addition of the neutralizing agent.

In the present invention, a coagulant may be added to the processing waste liquid. As a preferred embodiment, there is an embodiment in which after adding the first coagulant, an acid is added to neutralize and the second coagulant is added. The first aggregating agent is preferably an inorganic aggregating agent, and examples of the inorganic aggregating agent include the following compounds.

As a low molecular weight system, aluminum sulfate, aluminum chloride, iron (II) sulfate, iron (III) sulfate, iron (III) chloride, iron chloride-iron sulfate mixture, zinc chloride, zinc sulfate, magnesium oxide, magnesium carbonate Etc .; as a polymer system, polyaluminum chloride ([Al ₂ (OH) _n Cl _6-n ] _m ),
Polyaluminum sulphate ([Al ₂ (OH) _n (SO ₄ ) _{3-n / 2} ] _m ), polyiron chloride (III) ([Fe ₂ (OH) _n Cl _6-n ] _m ), polyiron sulphate ( I
II) ([Fe (OH) _n (SO ₄ ) _{3-n / 2} ] _m etc .; as a metal electrolysis product,
Electrolytic aluminum hydroxide (Al (OH) ₃ ), electrolytic iron hydroxide (F
e (OH) ₃ ) etc. The appropriate amount of the first coagulant added is usually 0.1 to 10% by weight.

The second coagulant is preferably an organic coagulant, particularly a cationic polymer coagulant. As a cationic polymer flocculant, polyethyleneimine (PEI),> NOCR
(R represents a linear alkyl group or a linear allyl group having 3 to 21 carbon atoms), which is an acylated water-soluble polyethyleneimine compound, xanthone collected from crab shells, and the like. > NOCR as partially acylated water-soluble polyethyleneimine, usually with an average molecular weight of 800-657
Polyethylenimine of 00 is acylated and the acyl group becomes 5
15% bound is used. Typical examples of the partially acylated water-soluble polyethyleneimine represented by> NOCR include those having a linear alkyl group. For example, ROC-is _{CH 3 (CH 2) 2 CO-} , CH 3 (CH 2) 6 CO-, CH 3 (CH 2)
₁₀ CO−, CH ₃ (CH ₂ ) ₁₆ CO−, CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₇ CO−
And the like. Tables 1 to 3 show specific examples of the organic flocculant, but guar gum can also be used. Tables 1 3 in the structural formula, R and R 'each represent a alkyl group, X ^- represents an anion. The amount of the second coagulant added is usually 0.1 to 5% by weight in the case of a 0.25% by weight aqueous solution.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

In the treatment method of the present invention, neutralization with an acid,
If necessary, a filter aid and / or a flocculant is added to form a coagulated product, and the treated waste liquid is separated into a solid content and a liquid by filtration. As a filtration method, known means such as centrifugal filtration, suction filtration, belt press and filter press can be used, but centrifugal filtration is preferred. For the filtration method, the descriptions in Japanese Patent Application Nos. Sho 62-193051 and Sho 63-217403 can be referred to.

Next, an apparatus for carrying out the processing method of the present invention will be described with reference to the drawings.

FIG. 1 is a view showing the schematic arrangement of an apparatus for carrying out the method of the present invention. Reference numeral 1 denotes an automatic developing machine for processing a non-silver salt photosensitive material, the internal structure of which is not shown in the drawing, while the non-silver salt photosensitive material is being conveyed, a developing solution is supplied to the photosensitive layer and is exposed by a brush roller. After the layer surface is rubbed to perform elution development for imagewise removal of the photosensitive layer, the squeeze roller is used to remove the deposits and send it to the washing section. In the rinsing section, the rinsing water in the rinsing water tank is pumped to the shower nozzle by a pump, from which it is sprayed onto the surface of the photosensitive material for rinsing, and the water used for rinsing is returned to the rinsing water tank for circulation and reuse It has become. The light-washed photosensitive material is configured to remove adhered substances on the surface with a squeeze roller and then sent to the next step (rinse treatment or desensitization treatment) to be rinsed or desensitized.

The wash-fatigue liquid, which has been circulated and reused in the automatic processor 1 and is exhausted, is sent to the coagulation tank 3 by operating the pump 2, and the liquid is sent to a predetermined liquid level by a liquid level sensor and control mechanism (not shown). And the operation of the pump 2 is stopped. In the flocculation tank 3, the oxidant contained in the oxidant tank 5 is sent by the pump 6 and added, and then the acid contained in the neutralizer tank 7 is sent by the pump 8 to be added to the washing fatigue liquid. It

The acid addition is such that the operation of the pump 8 is controlled by a control mechanism (not shown) so that the pH of the treatment waste liquid is adjusted within a predetermined range. 10 is the glass electrode of the pH meter. On the other hand, at the same time as the addition of the acid, the filter aid (powder) contained in the filter aid container 13a is moved by the rotary feeder 14a into another filter aid (powder) contained in the other filter aid container 13b. ) Is the flocculation tank 3 by the rotary feeder 14b.
A predetermined amount is added to each of the water-washed fatigue liquid. 17 is a stirrer.

In this way, the oxidative agent, the neutralizing agent, and the filter aid are added, and the water-washed fatigue liquid in which the contained dissolved components and colloidal components are aggregated is sent to the centrifugal filter 20 by the pump 19. In the centrifugal filter 20, the filtrate and the residue are centrifugally filtered by a rotating inner tank 21 and a filter cloth 22 mounted therein, and the filtrate is sent to the automatic processor 1 by a pump 24 and reused as washing water. . 23 is a motor for rotating the inner tank 21. As the material of the filter cloth, cotton, polyethylene, woven cloth, polyvinyl chloride, etc., the rotation speed of the inner tank is 500 ~ 180
0 rpm is preferred.

The treatment waste liquid to which the treatment method of the present invention is applied is a treatment waste liquid containing a reducing agent such as sulfite which reacts with an acid to produce an offensive odor and a sanitary harmful substance such as sulfurous acid gas. Such a processing waste liquid includes, for example, a negative or positive photosensitive lithographic printing plate using a diazo resin, an o-quinone diazide compound, a photopolymer or the like as a photosensitive substance, and a waste liquid of the developing solution or washing after development. There is a waste liquid of washing water in the process, for example, a light-sensitive material and a developer thereof as described in JP-A-63-205658.

[0026]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example Positive photosensitive lithographic printing plate SMP-as a non-silver salt photosensitive material
N (manufactured by Konica Corporation) 1003 mm × 800 mm size was processed by an automatic processor. In the processing by this automatic developing machine, development was carried out with a developing solution SD-32 (manufactured by Konica Corporation), followed by washing with water. For washing, 18 l of water was put in a washing water tank, this water was supplied to the plate surface from a shower nozzle to wash the water, and the water used for washing was returned to the above washing water tank and reused by circulation. The reducing agent contained in the rinsing water (rinsing fatigue solution) that was circulated and reused was K ₂ SO ₃ . Under the above conditions, the photosensitive lithographic printing plate was treated for 8 hours, and every 2 hours, 5 liters of the rinsing fatigue solution in the rinsing tank was sent to the flocculating tank 3 (the liquid volume was 5 liters) of the apparatus shown in FIG. When this liquid transfer is completed, the stirrer 17 is rotated to add 5% by weight of hydrogen peroxide (H ₂ O ₂ ) as an oxidant.
After the addition, a 9% aqueous solution of H ₂ SO ₄ was added as a neutralizing agent until the pH reached 3, and at the same time, 0.1% by weight of a cellulosic filter (Nippon Diatomaceous Co., Ltd.) was added from the filter aid container 13a and a filter aid. 0.1% by weight of activated carbon (both with respect to the amount of liquid in the coagulation tank) was added from the container 13b, and the mixture was stirred for 10 minutes after the addition was completed. Then, the washed fatigue liquid treated above is sent to the centrifugal filter 20 while being stirred, rotated at 1400 rpm to separate the residue and the filtrate, and the filtrate (regenerated washing water) is transferred to the washing water tank of the automatic processor. It was returned and reused. When the filter cloth 22 is subjected to such a treatment using a cotton cloth, no strange odor (SO ₂ odor) is generated in the treatment of the washing fatigue liquid, and the washing water tank and the washing water of the automatic processor are circulated. No generation of scale was found in the pipe.

Comparative Example The same experiment as in the above example was carried out except that no oxidizing agent was added. As a result, an offensive odor (SO
₍₂ odor) occurred.

[0029]

According to the present invention, when a processing waste solution of a non-silver salt light-sensitive material is treated with an acid, the processing waste solution containing a reducing substance such as a sulfite salt has an offensive odor and is hygienic. The generation of harmful substances is prevented, thereby improving the environment of the processing waste liquid around the processing equipment.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an apparatus for carrying out the method of the present invention.

[Explanation of symbols]

 1 Automatic processor 3 Coagulation tank 5 Oxidizer tank 7 Neutralizer tank 13a, 13b Filter aid container 20 Centrifugal filter

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiro Shimura 1 Konica Stock Company, Sakura Town, Hino City, Tokyo In-house (72) Shinya Watanabe 1 Konica Stock Company, Sakura Town, Hino City, Tokyo In-house

Claims (1)

[Claims] 1. A processing waste liquid of a non-silver salt light-sensitive material containing a reducing substance is added at the same time as or after the addition of an oxidizing agent, and then neutralized with an acid, and the processing waste liquid is separated into a solid content and a liquid by filtration. A method for treating a processing waste liquid of a non-silver salt light-sensitive material, comprising: