JP2003093866A - Method and apparatus for treating dye waste liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treatment method capable of satisfactorily treating dye waste liquid containing dyes and a treatment apparatus suitable for executing the treatment method. SOLUTION: The dye waste liquid containing the dyes is decomposed by a hydrothermal reaction under a subcritical water condition or a supercritical water condition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a dye-based waste liquid containing a dye such as a hair dye or a dye for clothes, and
The present invention relates to a processing apparatus suitable for carrying out this processing method.

[0002]

2. Description of the Related Art Generally, incineration treatment and chemical oxidative decomposition treatment are known as treatment methods for waste liquid containing a dye.

[0003]

However, in the incineration process, harmful substances such as dioxins may be generated as exhaust gas. Further, in the chemical oxidative decomposition treatment, the treatment space tends to be large and the treatment time tends to be long.

The present invention has been made in view of the above circumstances, and an object thereof is a treatment method capable of favorably treating a dye waste liquid containing a dye, and a treatment suitable for carrying out this treatment method. To provide a device.

[0005]

In the method for treating a dye-based waste liquid according to the present invention, a hydrothermal reaction treatment for decomposing a dye-based waste liquid containing a dye by hydrothermal reaction under subcritical water conditions or supercritical water conditions. The provision of the steps was taken as a means for solving the above problems.

According to this treatment method, the organic waste contained in the dye can be satisfactorily decomposed by decomposing the dye-based waste liquid by hydrothermal reaction under subcritical water or supercritical water.

In this case, a wet oxidation treatment step of subjecting the decomposed hydrothermal reaction treated product to a wet oxidation treatment may be provided.

In this case, the organic matter contained in the dye is decomposed more favorably by the wet oxidation.

The dye waste liquid treatment apparatus of the present invention comprises a hydrothermal reaction treatment device for decomposing a dye waste liquid containing a dye by hydrothermal reaction under subcritical water conditions or supercritical water conditions. It was used as a solution to the problem.

According to this processing apparatus, since the above processing method can be carried out, the organic components contained in the dye can be decomposed satisfactorily.

In this case, a wet oxidation treatment device for performing wet oxidation treatment on the decomposed hydrothermal reaction treatment product may be provided.

In this case, the organic component contained in the dye is decomposed more favorably by the wet oxidation.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
FIG. 1 is a schematic configuration diagram for explaining an embodiment of an apparatus for treating a dye-based waste liquid according to the present invention. Reference numeral 1 in FIG. 1 is a treatment apparatus for a dye-based waste liquid. This processing device 1
It is suitable for treating a dye-based waste liquid containing a dye such as a hair dyeing liquid or a dye for clothes, and is provided with a hydrothermal reaction treatment device 2 for decomposing the dye-based waste liquid.

The hydrothermal reaction treatment device 2 treats the waste liquid sent into the reaction chamber by a pump or the like under subcritical water conditions or supercritical water conditions, specifically, 150 to 374 ° C., for example.
0.48-22MPa subcritical water condition or 22MP
a or more supercritical water conditions, more preferably 200 to 28
The composition is decomposed by a hydrothermal reaction at 0 ° C. and 1.55 to 6.42 MPa. The hydrothermal reaction treatment device 2 is a step-up pump as a pressurizing means for pressurizing the dye-based waste liquid and sending it to the reaction chamber, a flow rate control device for controlling the flow rate of the dye-based waste liquid that has been boosted, and for promoting the hydrothermal reaction. In addition, a stirring device for stirring the waste dye solution in the reaction chamber, a heating device that heats the reaction chamber by induction heating, etc., a heat exchange that cools the hydrothermal reaction product after decomposition to a temperature at which it can be discharged downstream. It is configured to include a cooling device (not shown) such as a container.

Further, in this example, the processing apparatus 1 is provided with a hydrothermal wet oxidation processing apparatus 3 for performing hydrothermal wet oxidation processing on the hydrothermal reaction processed product decomposed by the hydrothermal reaction processing apparatus 2. . When the dye-based waste liquid is sufficiently decomposed only by the hydrothermal reaction treatment device 2, the hydrothermal wet oxidation treatment device 3 may not be provided. Whether or not the hydrothermal wet oxidation treatment apparatus 3 is necessary is appropriately determined according to the dye waste liquid to be treated.

The hydrothermal wet oxidation treatment apparatus 3 heats and pressurizes the treated material after the hydrothermal reaction treatment to make it a subcritical water condition or a supercritical water condition, and causes a hydrothermal reaction based on such a reaction condition. The reaction chamber is filled with a material such as Raschig ring or berl saddle in order to enhance the reactivity. Further, the reaction chamber is filled with a catalyst effective for reducing COD, that is, a catalyst (for example, a platinum group element) appropriately selected depending on the object to be treated, between the packings or as the packing itself. . When the processed product after the hydrothermal reaction process has a sufficiently high temperature and pressure, the energy may be used as it is, and the heating / pressurizing means may be omitted or simplified.

Next, the method for treating the dye-based waste liquid of the present invention will be described based on the method for treating the dye-based waste liquid by the treating apparatus 1 having the above-mentioned structure. First, the dye waste liquid to be treated is introduced into the hydrothermal reaction treatment device 2. In the hydrothermal reaction treatment device 2, subcritical water conditions or supercritical water conditions, for example, 150 to 400 ° C., 4.9 to 220 atm subcritical pressure conditions or 220 atm supercritical pressure conditions, More preferably 200 to 280 ° C., 1.55
Hydrothermal reaction is performed at 6.42 MPa to decompose the composition of the dye-based waste liquid. By this hydrothermal reaction, the bond of the polymer of the organic compound contained in the dye is cut and the molecular weight is lowered.

Next, the treated product from the hydrothermal reaction treatment device 2 is introduced into the hydrothermal wet oxidation treatment device 3. Then, the treated matter introduced here is subjected to a hydrothermal wet oxidation treatment to further decompose the organic components contained in the dye, and reduce the COD (chemical oxygen demand amount) thereof to a concentration equal to or lower than the discharge standard concentration. After that, if necessary, the treated product is discharged to meet the discharge standard, and then the treated product is discharged into general sewage or a river.

In such a treatment apparatus 1 for a dye-based waste liquid and a treatment method using the same, the dye-based waste liquid is decomposed by hydrothermal reaction under subcritical water conditions or supercritical water conditions. The organic components contained in the dye can be decomposed well. Further, by subjecting the treated product subjected to the hydrothermal reaction treatment to the hydrothermal wet oxidation treatment, the organic components contained in the dye can be completely decomposed and discharged as waste water.

That is, in this example, the dye-based waste liquid is changed to a state in which it is easily decomposed by the hydrothermal wet oxidation treatment by performing the hydrothermal reaction treatment, and the dye-based waste liquid is subjected to the hydrothermal wet oxidation treatment so as to be contained in the dye. It is possible to surely decompose the organic components to be decomposed. Further, the dye-based waste liquid can be decolorized by the decomposition of the organic components contained in the dye.

(Experimental example) Next, as a dye-based waste liquid,
(1) The waste liquid containing a large amount of dye (M1) and (2) the waste liquid containing a large amount of fixing liquid (M2) are subjected to hydrothermal reaction treatment,
The concentration of organic components after the treatment was examined. The obtained results are shown in Table 1 and FIGS. Regarding the hydrothermal reaction treatment,
A batch type supercritical water / hydrothermal reaction test device (autoclave) was used as a test device. The specifications of this hydrothermal reaction test device are as follows. "Specifications" -Maximum operating temperature: 500 ° C-Maximum operating pressure: 50 MPa-Reaction vessel; Material: Carbon steel with Hastelloy lining (capacity: 45 ml) -Heating method: Induction heating method (heating rate 50 ° C / mi)
n) -Stirring method; Stirring by heating furnace rocking (stirring ball) "Test conditions" -Processing temperature; 180, 200, 230, 250, 2
80, 300, 350 ℃ ・ Solid-liquid ratio ； as raw materials ・ Processing time ； 30 minutes, 10 minutes (processing temperature 280 ℃ only) ・ Gas phase part ； Argon

[0022]

[Table 1]

Regarding the dye-based waste liquid (M1), Table 1 and FIG.
And from the results shown in FIG. 3, CODm after hydrothermal reaction treatment
n and CODcr have processing temperatures of 180 ° C and 200 ° C
Showed a tendency to increase compared to before treatment. It is considered that this is because the hardly decomposable organic matter was decomposed by the hydrothermal reaction and changed into a form that was easily decomposed. Further, CODmn and CODcr tended to decrease thereafter as the treatment temperature increased. However, when the treatment temperature exceeded 300 ° C., both CODmn and CODcr tended to increase. Further, the SS (suspension) content tended to increase little by little as the treatment temperature increased. In particular, when the processing temperature of 230 ° C. was used as a boundary and the processing temperature was higher than that, the SS content tended to increase.

From these results, it was found that the treatment temperature is preferably 250 to 280 ° C. and the treatment time is 30 minutes in order to reduce CODmn and CODcr of the dye waste liquid (M1). Also, SS content is 1000 mg
It has been found that it is desirable to set the treatment temperature to about 250 ° C. or less in order to suppress the temperature to 1 / l or less.

Next, regarding the dye-based waste liquid (M2), from the results shown in Table 1, FIG. 4 and FIG. 5, CODmn and CODcr after hydrothermal reaction treatment were 180 to 280 ° C. as compared with those before treatment. It tended to drop significantly. However, when the treatment temperature was 300 ° C. or higher, both CODmn and CODcr tended to increase. Further, the SS content tended to increase little by little as the treatment temperature increased.

From these results, it was found that it is desirable that the treatment temperature is 250 to 280 ° C. and the treatment time is 30 minutes in order to reduce CODmn and CODcr of the dye waste liquid (M2).

Next, the treated product of the dye-based waste liquid (M1) after the hydrothermal reaction treatment, in which the values of CODmn and CODcr are relatively large, is subjected to hydrothermal wet oxidation treatment, and the concentration of organic components after the treatment is investigated. It was The test conditions for this hydrothermal wet oxidation treatment are as follows. "Test conditions" -Treatment temperature; 220 ° C-Air flow rate; 1.8 l / min-Treatment time; 60 minutes-Catalyst; Metal (Pt) system

As a result of carrying out the hydrothermal wet oxidation treatment, it was confirmed that the dye-based waste liquid (M1) was decomposed to an organic content of almost 100% after the hydrothermal reaction treatment. For example, COD
The cr value was 30250 mg / l before the treatment, whereas the value after the treatment was 357 mg / l.

From these results, it was found that it is possible to almost completely decompose the organic components contained in the dye by subjecting the treated product subjected to the hydrothermal reaction treatment to the hydrothermal wet oxidation treatment. In particular, it has been found that by performing the hydrothermal reaction treatment, the dye-based waste liquid is changed to a state in which it is easily decomposed by the hydrothermal wet oxidation treatment, and the organic component contained in the dye can be reliably decomposed.

The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but it goes without saying that the present invention is not limited to such examples. The shapes, combinations, and the like of the respective constituent members shown in the above-described examples are merely examples, and various changes can be made based on design requirements and the like without departing from the spirit of the present invention.

[0031]

As described above, the method for treating a dye-based waste liquid according to the present invention includes a dye-based waste liquid in a dye by decomposing the dye-based waste liquid by hydrothermal reaction under subcritical water or supercritical water. Organic matter can be decomposed well. Further, since the treatment apparatus for a dye-based waste liquid of the present invention can carry out the above-mentioned treatment method, it can satisfactorily decompose the organic components contained in the dye.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a schematic configuration of an embodiment of an apparatus for treating a dye-based waste liquid according to the present invention.

FIG. 2 is a graph showing the CODmn value of the dye-based waste liquid M1 after hydrothermal reaction treatment.

FIG. 3 is a graph showing the CODcr value after the hydrothermal reaction treatment for the dye-based waste liquid M1.

FIG. 4 is a graph showing the CODmn value after the hydrothermal reaction treatment for the dye-based waste liquid M2.

FIG. 5 is a graph showing the CODcr value after the hydrothermal reaction treatment for the dye-based waste liquid M2.

[Explanation of symbols]

1 Dye-based waste liquid treatment equipment, 2 Hydrothermal reaction treatment equipment, 3 Hydrothermal wet oxidation treatment equipment.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ryuzo Hiraoka             Stone, Shin-Nakahara-cho, Isogo-ku, Yokohama-shi, Kanagawa             Kawashima Harima Heavy Industries Co., Ltd. Machinery and plant opening             In the departure center (72) Inventor Keiichi Miwa             Stone, Shin-Nakahara-cho, Isogo-ku, Yokohama-shi, Kanagawa             Kawashima Harima Heavy Industries Co., Ltd. Machinery and plant opening             In the departure center F term (reference) 4D050 AA13 AB03 BB01 BC01 BC02                       BC06 BD02 CA20

Claims (4)

[Claims] 1. A method for treating a dye-based waste liquid, comprising a hydrothermal reaction treatment step of decomposing a dye-based waste liquid containing a dye by a hydrothermal reaction under subcritical water conditions or supercritical water conditions. 2. The method for treating a dye-based waste liquid according to claim 1, further comprising a wet oxidation treatment step of performing a wet oxidation treatment on the decomposed hydrothermal reaction-treated product. 3. A treatment apparatus for a dye-based waste liquid, comprising a hydrothermal reaction treatment device for decomposing a dye-based waste liquid containing a dye by hydrothermal reaction under subcritical water conditions or supercritical water conditions. 4. The treatment apparatus for a dye-based waste liquid according to claim 3, further comprising a wet oxidation treatment apparatus for performing a wet oxidation treatment on the hydrothermal reaction-treated product decomposed.