JPH05301087A - Treatment of waste liquid - Google Patents

Abstract

PURPOSE:To reduce the process time to change a water-base waste liquid into harmless and to enable a high-level treatment by using such a container the inner wall of which is made of titanium to heat and pressurize in the container with oxygen, the waste liquid containing org. matter which can form water-soluble complex with metal ions. CONSTITUTION:When a soln. containing >=0.1mmol/l org. matter which can form water-soluble complex with metal ions is heated and pressurized with oxygen to >=375 deg.C and >=230atm partial pressure of waster for one minute, COD and TOC of the liquid decreases. In this process, by using a container the inner wall of which is coated with titanium, heavy metals which are not included in the waste liquid before processing are not detected in the processed water. This result is espectially effective for a waste liquid cotaining >=5mmol/l halogen ion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waste liquid containing an organic substance which forms a water-soluble complex with a metal ion, particularly a waste liquid containing halogen ions of 5 mmol / liter or more, such as a developing solution and a fixing solution. The oxidizable substance in the photographic waste liquid from FUJI was purified with water and oxygen in the supercritical state, and its high C
The present invention relates to a treatment method for easily removing a component having an OD value (chemical oxygen demand).

[0002]

2. Description of the Related Art When discarding liquid waste (waste liquid) or discharging it into a river or sewage, a certain standard is set for various environmental pollution factors such as harmful metals, pH, oxygen consumption, and harmful organic compounds such as trichlorethylene. Must be satisfied and confirmed to be safe. For the treatment of such liquid industrial waste, incineration or activated sludge treatment,
Chemical oxidation method using chlorine, hypochlorite, ozone, etc.
In particular, a method using hydrogen peroxide and a metal or a metal compound,
Adsorption removal method using activated carbon, inorganic adsorbent, or organic polymer material, evaporation method to heat and evaporate waste liquid, reverse osmosis method and dialysis method to separate waste liquid into reusable concentrated liquid and disposable dilute liquid, There is a method of using waste liquid at high temperature and high pressure and using water and oxygen in a supercritical state.

[0003]

These various methods are described in C
Some are effective in reducing OD, some are effective in removing harmful metals, some are suitable for concentrated liquids but not dilute liquids, and vice versa. However, when there are a plurality of environmental pollutants in the waste liquid and it is complicated (this is a general form), it is difficult to detoxify the waste liquid to a sufficiently satisfactory level by any of the methods.

An example of such waste liquid is a silver halide photographic light-sensitive material processing waste liquid. This waste liquid includes a development waste liquid, a fixing waste liquid, a bleaching waste liquid, a bleach-fixing waste liquid, or a waste liquid from another liquid bath discharged in a photographic processing step, and is an organic or inorganic COD contributing component, a heavy metal compound such as silver or iron. , High concentrations of salts, especially many ethylenediaminetetraacetic acid, contains organic substances that form water-soluble complexes with metal ions, bromide ions and iodide ions. Environmental pollutants include COD, BOD, and heavy metals. In some cases, there are pH and phenols. Therefore, the detoxification process must be an effective means from each aspect, which is difficult and problematic.

Therefore, the evaporation method is one of the solutions that can be processed by one means at once. That is, if the waste liquid is evaporated to form a concentrated waste liquid that is easy to process or a solid sludge residue, there is no one that is discharged in a liquid state to the environment, so that the problems of various water pollution factors described above are solved. However, in that case, a large amount of vapor is generated and enters into volatile substances and the like, which causes air pollution due to bad odors and harmful substances as new problems. Therefore, a countermeasure of recondensing the evaporated gas and recovering it as a liquid can be considered, but the COD of this condensate becomes a new environmental pollution factor.

Further, a method of treating the evaporative condensate of the waste liquid with activated carbon is known. However, in the case of many photographic processing waste liquids, the life of the activated carbon column is short, the replacement frequency is high, and the replacement work is troublesome. Was a problem.

On the other hand, a waste liquid treatment method using supercritical water for such waste liquid (for example, Japanese Patent Publication No. 56-501205,
When Japanese Patent Application Laid-Open No. 57-4225) is applied, organic and inorganic oxidizable substances are not detected at all in the treated water, but a large amount of heavy metal (chromium etc.) ions which are not detected before the treatment are detected. was there.

An object of the present invention is to provide a new method for effectively solving the above problems.

That is, the first object of the present invention is to establish an effective detoxifying means without environmental pollution over both the water quality and the air of the waste liquid as described above.

A second object of the present invention is to provide an inexpensive, simple and reliable detoxifying means suitable for a concentrated waste liquid containing many kinds of components.

A third object of the present invention is to clarify treated water without increasing heavy metal ions due to waste liquid treatment.

A fourth object of the present invention is to provide a method for shortening the detoxification processing time of the waste liquid and performing the processing to a high degree as described above.

In particular, it is an object of the present invention to provide a processing method for the photographic processing waste liquid, in which the above-mentioned objects can be achieved particularly effectively.

[0014]

As a result of various investigations, the present inventors have found that the object of the present invention can be effectively achieved by using the following means. The present invention solves the above-mentioned problems by treating the above waste liquid with supercritical water in a titanium container.

That is, according to the present invention, an aqueous waste liquid containing 0.1 mmol / l or more of an organic substance capable of forming a water-soluble complex with a metal ion is used together with oxygen in a titanium container or a container whose inner wall is coated with titanium. This is a waste liquid treatment method characterized by heating and pressurizing so that the temperature is 375 ° C. or higher and the partial pressure of water is 230 atm or higher.

The present invention will be described in more detail. Aqueous waste liquid containing 0.1mmol / liter or more of an organic substance that forms a water-soluble complex with metal ions is used together with oxygen at a temperature of 37
5 ℃ or more, water partial pressure 230atm or more, preferably 400
COD of waste liquid when heated and pressurized to ℃ or more and 500 ℃ or less, and 350 atm or more and keeping the state for 1 minute or more
Value and TOC value can be reduced. At this time, by using a container made of titanium or having a titanium inner wall coated, heavy metals not contained in the treated water before the treatment are not detected. The process performed here may be either a continuous flow method or a batch method. This effect is obtained by adding halogen ions (eg, chlorine ions, bromine ions, iodine ions) to 5 mmol / liter, especially 10
It is especially effective for waste liquids containing more than molol / liter. Aminopolycarboxylic acid (formula 1), aminopolyphosphoric acid (formula 2) and salts thereof can be mentioned as the organic substance forming a water-soluble complex with the metal ion to which the present invention is applied.

Equation 1

[Chemical 1]

Equation 2

[Chemical 2]

Alkyl groups for R ₁ and R ₃ and R ₂ , R ₄
The aryl group and alkyl group may be substituted, and the substituent includes a carboxyl group, a phosphono group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and the like, and these are the same groups. It may be further replaced.

Specific examples thereof include ethylenediaminetetraacetic acid (hereinafter referred to as EDTA), ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, ethylenediaminetetraacetic acid tetra (trimethylammonium) salt, ethylenediaminetetraacetic acid tetrapotassium salt, Ethylenediaminetetraacetic acid tetrasodium salt, ethylenediaminetetraacetic acid trisodium salt, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid pentasodium salt, ethylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ', N'-triacetic acid trisodium salt, ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid triammonium salt, 1,2
-Diaminopropane tetraacetic acid, 1,2-diaminopropane tetraacetic acid disodium salt, 1,3-diaminopropane tetraacetic acid, 1,3-diaminopropane tetraacetic acid diammonium salt, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt, cyclohexanediamine Tetraacetic acid, cyclohexanediaminetetraacetic acid disodium salt, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N, N , N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N, N, N ', N - and the like can be mentioned tetramethylene phosphonic acid, of course not limited to these exemplified compounds. These are contained in the waste liquid at a concentration of 0.1 mmol / liter or more. The method of the present invention can be effectively carried out even at 1.0 mmol / liter or more.

In the treatment of the present invention, an autoclave can be used, but the container for the reaction is made of titanium or the inner wall of which is coated with titanium. The plasma spraying method is preferably used to coat the inner wall of the container with titanium. Further, it is preferable that the pressure resistance of the container is enhanced by increasing the wall pressure.

In the method of the present invention, the waste liquid is heated and pressurized together with oxygen. Oxygen, waste per liter 5 Nm ³ or more, preferably 10 Nm ³ or more, more preferably 20 Nm ³ or more.

The photographic processing waste liquid for which the method of the present invention is particularly effective will be described below. The photographic processing waste liquid is mainly composed of photographic processing liquid components. In addition, in the photographic processing waste liquid, oxidant of the developing agent, sulfate, and
It contains components such as halides and other reaction products, trace amounts of gelatin dissolved from the light-sensitive material, and surfactants. Photographic processing solutions include color processing solutions, black-and-white processing solutions, reducing solutions for plate making operations, and development processing tank cleaning solutions.Photo-processing solutions include black-and-white developing solutions, color developing solutions, fixing solutions, bleaching solutions, and bleach-fixing solutions. , An image stabilizing solution, etc. The composition of the developer will be described below.

Many color developing solutions for color papers contain alkylene glycols and benzyl alcohols together with color developing agents, sulfites, hydroxylamine salts, carbonates, water softeners and the like. On the other hand, the color negative color developer, the color positive color developer, and some color paper color developers do not contain these alcohols. The method of the present invention does not contain any of these alcohols, or even if it contains them, it maintains high current efficiency or exerts an oxidizing ability up to a low COD level with respect to a waste solution of 1% by weight or less. It is even more advantageous.

The color developer usually contains an aromatic primary amine color developing agent. It is mainly a p-phenylenediamine derivative, a typical example of which is N, N-diethyl-
p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino] aniline and N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline. Also, these p-
The phenylenediamine derivatives are dono salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The content of the aromatic primary developing agent is in the range of about 0.5 g to about 10 g per liter of color developing solution.

The color developer contains various hydroxylamines as preservatives. Hydroxylamines may be substituted or unsubstituted. In the case of a substituted form, hydroxylamines in which the nitrogen atom is substituted by a lower alkyl group, especially by two alkyl groups (for example, having 1 to 3 carbon atoms) Substituted hydroxylamines. The content of hydroxylamines is 0 to 5 g per liter of color developing solution.

The black-and-white developing waste solution contains dihydroxybenzenes, 1-phenyl-3-, as a developing agent used in the developing solution.
Pyrazolidones, dihydroxybenzenes, p-aminophenols, and ascorbic acids are included.

As the dihydroxybenzene developing agent in the present invention, hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dipromhydroquinone, 2 , 5-dimethylhydroquinone, etc.

As the p-aminophenol-based developing agent in the present invention, N-methyl-p-aminophenol,
p-aminophenol, N- (β-hydroxyethyl)
-P aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p
-Benzylaminophenol and the like.

As the 3-pyrazolidone-based developing agent in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-
Pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone and the like.

The black-and-white developing agent is usually 0.001 to 1.2.
Used in an amount of mol / liter.

Examples of the sulfite preservative used in the developing solution include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and potassium metabisulfite.

The alkaline agent used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

When a buffer such as JP-A-62-186259 (borate), JP-A-60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate or carbonate is included. There is also.

The developer may contain a hardener.

As the hardener, a dialdehyde hardener or a bisulfite adduct thereof is preferably used. Specific examples thereof include glutaraldehyde, and a bisulfite adduct thereof.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, Organic solvent such as ethanol and methanol: 1-phenyl-5-
Mercapto-tetrazole, 2-mercapto-benzimidazole-5-sulfonic acid sodium salt and other mercapto-based compounds, 5-nitroindazole and other indazole-based compounds, 5-methylbenztriazole and other benztriazole-based compounds such as antifoggants Well, Re
search Disclosure Volume 176, No. 17643, XX
Development accelerators described on page I (December issue, 1978), and if necessary, toning agents, surfactants, defoaming agents,
It may contain a water softener, an amino compound described in JP-A-56-106244, and the like.

In the present invention, the developer may contain a silver stain preventing agent, for example, the compounds described in JP-A-56-24347.

Further, the developing solution is described in JP-A-56-1062.
No. 44, and European Patent No. 0136582, it may contain an amino compound such as an alkanolamine. In addition, various chelating agents which are added to the developer as an anti-sedimentation agent for calcium or magnesium or for improving the stability of the developer are included. Typical examples thereof include the above-mentioned aluminum polycarboxylic acid and aminopolyphosphonic acid. These chelating agents can be added as needed.
Sometimes more than one species may be used in combination.

The developing solution contains various development accelerators.
As the development accelerator, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-
Examples thereof include aminophenols, amine compounds, polyalkylene oxides, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, thione compounds, and imigazoles.

The developing solution often contains bromine ions for the purpose of preventing fog, but a developing solution containing no bromine ions may be used for a light-sensitive material mainly containing silver chloride. is there. In addition, a compound that gives a chlorine ion such as NaCl or KCl may be contained as an inorganic antifoggant. If desired, various organic antifoggants may be contained. The organic antifoggant may contain, for example, adenines, benzimidazoles, benztriazoles and tetrazoles. The content of these antifoggants is 0.010 to 2 g per liter of the developing solution. These antifoggants include those which are eluted from the light-sensitive material during processing and accumulated in the developer. Further, if necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, fatty acid carboxylic acid and aromatic carboxylic acid may be contained.

In photographic processing, a bleaching process is usually carried out after development, and the bleaching process may be carried out simultaneously with the fixing process by one-bath bleach-fixing (Brix). The method of the present invention can be applied to such a processing waste liquid. The bleaching solution contains EDTA of iron (III) or Co (III) as an oxidizing agent, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diaminopropanetetraacetic acid salt, phosphonocarboxylic acid salt and other persulfates, quinones, etc. It is included. In addition, alkali bromide, a rehalogenating agent such as ammonium bromide, borate salts, carbonates, and nitrates may be optionally contained.
The fixer or the bleach-fixer may contain thiosulfate (sodium salt, ammonium salt), acetate, borate, ammonium or potassium alum sulfite.

In carrying out the method of the present invention, known fungicides and antibacterial agents can be used in the waste liquid, if necessary, so that stable work can be performed for a long period of time. For example, the method of the present invention can be applied to the following waste liquids. 1) Printing plate making factory: various discharge liquids such as black and white color developing solution, fixing solution, bleaching solution, etching solution, reducing solution, paints, inks, organic solvents, tank cleaning solution. These can be collectively processed. 2) Color developer: Black and white color developer, fixing solution, bleaching solution, bleach-fixing solution, image stabilizing bath, discharge liquid of other processing baths. In a preferred embodiment, the effluent from each of the above baths is collected and treated, and the rinsing water is allowed to flow. When the countercurrent multi-stage water-saving type water washing or the method in which the stabilizing bath also serves as water washing, all the discharged liquids can be mixed and treated.

[0044]

EXAMPLES The present invention will be described in more detail based on examples. Example 1 The results of treating the EDTA aqueous solution under various conditions are shown in Table 1. The treatment is carried out in a batch method using an auto-grave with enhanced pressure resistance, and oxygen is 10 Nm ³ per 1 liter of waste liquid.
Was added. The conditions of maximum temperature and maximum pressure were maintained for 5 minutes.

[0045]

[Table 1]

Under the conditions of the present invention as in Experiment 5, treated water having a high TOC removal rate and containing no heavy metal can be obtained.

Example 2 Description of Waste Liquid Used Commercially available photographed multilayer color negative film Fuji Color SU
PER HG (hereinafter SHG-) 100, SHG-200, SH
G-400, SHG-1600, REALA (above trade name, manufactured by Fuji Photo Film Co., Ltd.), Kodacolor GOLD (hereinafter (GOLD-) 100, GOLD-200, GOLD)
-400, GOLD-1600, Hector 25, Hector 125, Hector 1000 (trade name Eastman Kodak Co., Ltd.), Conicolor GX (hereinafter GX-) 10
0, GX-200, GX-400, GX-3200, Conicolor GXII (hereinafter GX11-) 100, GX-100
M (above trade name, manufactured by Konica Corp.), without any particular distinction, mixed and mixed in sequence with a minilab film processor FP900AL (trade name, manufactured by Fuji Photo Film Co., Ltd.) as a processing solution for color negative developer CN- 16
Q (trade name, manufactured by Fuji Photo Film Co., Ltd.) was used. At this time, the overflow solution of the developing bath and the washing bath was used as the color negative developing system waste solution, and the overflow solution of the bleaching bath and the fixing bath were used as the color negative bleaching / fixing system waste solution.
In addition, commercially available color paper (Fuji Color Paper SU
PER, FA Fuji Photo Film Co., Ltd.) is printed from a color negative, and the printer processor PP1800 of Fuji Mini Lab Champion FA-170 is printed.
B (above trade name, manufactured by Fuji Photo Film Co., Ltd.) was treated with CP-43FA (above trade name, manufactured by Fuji Photo Film Co., Ltd.) as a processing liquid. The overflow solution of the developing bath at this time was used as a color paper developing system waste solution, and the overflow solutions of the bleach-fixing bath and the washing bath were used as a color paper bleach-fixing system waste solution.

A 1: 1 mixture of the color negative development waste liquid and the color paper development waste liquid is used as a color development waste liquid, and the color negative bleaching / fixing waste liquid and the color paper bleaching / fixing waste liquid are mixed 1: 1. Was used as a color bleaching / fixing system waste liquid.

Commercially available black and white negative film, Neopan SS, Neopan 400 PRESTO, Neopan 1600 SU
Without distinguishing PER PRESTO (these product names, made by Fuji Photo Film Co., Ltd.) in particular, the waste solutions processed by using various types of developer Fujidor and fixer Fuji Fix (the product names made by Fuji Photo Film Co., Ltd.) 5 liters of each were printed on a commercially available black-and-white paper (Fujibro WP Fuji Photo Film Co., Ltd.) from the negative, and processed using a developer collectol and a fixer Fuji Fix (trade name, manufactured by Fuji Photo Film Co., Ltd.). 5 liters of waste liquid each, medical X ray sensitive material, MI-SF
And MI-SFII (above trade name, manufactured by Fuji Photo Film Co., Ltd.) with developer RD-3 and fixer Fuji-F (above trade name, manufactured by Fuji Photo Film Co., Ltd.), each containing 10 liters of waste liquid. Printing material system Fuji GRAD
EX system developer GR-D1 and fixer GR-F1 (these product names, manufactured by Fuji Photo Film Co., Ltd.) are each 1 waste liquid.
0 liter each was mixed separately into a developing solution and a fixing solution to make 30 liters, which were used as a black-and-white developing system waste solution and a black-and-white bleaching / fixing system waste solution. The color developing system waste liquid and the black and white developing system waste liquid were mixed at a ratio of 1: 1 to obtain a developing system waste liquid. A 1: 1 mixture of color bleaching / fixing waste liquid and black-white bleaching / fixing waste liquid was used as a photographic processing waste liquid. This solution contains 6 mMol / liter of EDTA and 35 mM of Br.
Includes l / l.

Table 2 shows the results of heating and pressurizing the photographic waste liquid under various conditions. The waste liquid before processing is COD 45P0.
00ppm, Toc 20,000ppm and Fe and Ag
Contains. The treatment was carried out by a batch method using an autoclave, and oxygen was added at 50 Nm ³ per liter of waste liquid.

[0051]

[Table 2]

Experiments 8 and 9 in Table 2 show C of treated water.
Both OD and TOC values are extremely small and Cr, Mo
Since there is no detection of metal that is not contained before the treatment, it can be said that this is the most effective condition for waste liquid treatment.

[0053]

By carrying out the waste liquid treatment under the conditions of the present invention, not only organic substances and inorganic oxidizable substances in the treated water can be decomposed almost completely, but also heavy metal contamination due to the treatment can be prevented.

Claims (3)

[Claims] 1. An aqueous waste liquid containing 0.1 mmol / liter or more of an organic substance capable of forming a water-soluble complex with a metal ion is used at a temperature of 375 ° C. using a container made of titanium with oxygen or whose inner wall is coated with titanium. Above, partial pressure of water 230
A waste liquid treatment method characterized in that heating and pressurization are performed so as to become atm or more. 2. The waste liquid treatment method according to claim 1, wherein the waste liquid contains halogen ions in an amount of 5 mmol / liter or more. 3. The waste liquid processing method according to claim 1, wherein the waste liquid is a silver halide photographic processing waste liquid.