JPH10118669A - Oxidizing treatment of organic matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance oxidizing treatment efficiency of decoloration, bleaching or deodorization while reducing treatment cost by supporting activated seeds of hydrogen peroxide on an ion exchange resin and subjecting an objective substance to oxidizing treatment continuously and efficiently by activated hydrogen peroxide. SOLUTION: In oxidizing treatment such as decoloration treatment of industrial waste water issued from a dye manufacturing factory or decoloration/ bleaching treatment of an org. material, hydrogen peroxide or peroxide forming hydrogen peroxide is added to org. matter and this org. matter is brought into contact with an ion exchange resin on which activated seeds of hydrogen peroxide are supported. At this time, as peroxide, a sodium carbonate hydrogen peroxide adduct, a sodium perborate hydrate and sodium perborate tetrahydrate are used and, as activated seeds of hydrogen peroxide, a halogenoide ion compd., that is, a cyanic ion compd. or a thioxyanic ion compd. is used. As the ion exchange resin, a strong or weak basic anion exchange resin is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is used for decolorization of industrial wastewater from dye production factories and dye factories, and for oxidation treatment such as decolorization and bleaching in the production of organic materials and products. Furthermore, it can also be used for the oxidation reaction of organic compounds with hydrogen peroxide.

[0002]

2. Description of the Related Art Oxidation treatment techniques are widely used in all industrial fields from product purification to wastewater treatment, and their applications are also diverse such as decolorization, bleaching, deodorization, and oxidation of organic substances. In the case of wastewater treatment technologies such as decolorization and bleaching, dyeing factories and the like use many types of dyes and chemicals, and the chemicals to be used differ depending on the fiber to be dyed. Is mixed with colored industrial wastewater containing various types of chemicals and dye-containing wastewater.
Laws and regulations, such as the Water Pollution Law, are applied to this wastewater, and there are also cases in which municipalities have established chromaticity regulations for wastewater as "additional wastewater standards" for coloring. Regarding the wastewater in such a case, COD value (chemical oxygen demand) and B
Even if the OD value (biological oxygen demand) is below the regulation level, if the wastewater itself is colored, it gives a sense of pollution or a sense of contamination from human visual judgment. Is growing. In the deodorization technology,
Since the Odor Control Law was promulgated, the regulatory standards have become stricter year by year, and further advanced technology is required.

[0003] Regarding such a drainage treatment technique, the following methods and the like have conventionally been used. As a method for separating coloring components, a method of adding an inorganic coagulant and its auxiliary agent to coagulate and separate coloring components from wastewater, a method of separation by coagulation adsorption or adsorption of carrier (activated carbon), and a method of dissolving coloring components by microorganisms Biological techniques have been the focus of decolorization techniques, but often contain COD and color components that cannot be removed by such physicochemical or biological treatments. For the treatment of these components, chemical oxidation treatment methods have been devised, and in fact, some of the methods described below are techniques, and some of them are actually industrialized.

[0004] First, a number of oxidation methods using a chlorine-based oxidizing agent such as hypochlorite have been known in the past, but the use of chlorine-based chemicals should be avoided due to the danger of generating harmful chlorine to the environment. And its use is not preferable.

Next, as a method of oxidative decolorization using a non-chlorine oxidizing agent, a method of treating with a persulfate as disclosed in JP-A-6-121991, or a method of adding a hydrogen peroxide such as percarbonate or perborate There is a method in which a radical is generated by using a bath containing chromophore to attack a chromophore or the like of a dye for treatment. JP-A-8-08369 discloses that a metal salt or an ammonium salt of cyanic acid is used as an activating species in the presence of hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution.
Methods for decolorizing dyes are described. However, these methods produce salts with oxidants depending on the target substance,
It causes sludge generation. In addition, since the reaction is a low-concentration batch reaction in a bath, the efficiency is poor and unreacted substances remain, and the wastewater cannot be continuously oxidized. Especially when using cyanate as an activated species, there is a problem in handling when handling a large amount because it is a solid, and when preserving in an aqueous solution, the cyanate has hydrolyzability, so it is difficult to use an aqueous solution. Is not suitable for long-term storage.

[0006] As other hydrogen peroxide activators, JP-A-48-54279 discloses urea, sulfamic acid and sulfamate in the bleaching of fibrous substances. There is a drawback that it is limited and the pH must be adjusted, and is not suitable for a strongly acidic dye.

As another method, Japanese Patent Application Laid-Open No. 6-254575
Ozone oxidation described in Japanese Patent Application Laid-open No.
There is known a treatment described in US Pat. No. 2,362 or the like using a combination of hydrogen peroxide and ultraviolet irradiation, and a Fenton method using hydrogen peroxide and a ferric salt. However, in ozone oxidation, the generation efficiency of ozone is low, a large amount of power is consumed for ozone generation, and it cannot be said that it is economically effective. This is the same in the case of ultraviolet irradiation. In addition, in the Fenton method, the amount of generated sludge is large,
It is necessary to adjust wastewater treatment, which is effective for wastewater treatment, but there are many economic problems such as sludge disposal costs. Examples of the deodorizing technology include, in addition to the above-described adsorption method and deodorization by microorganisms, a method of burning malodorous substances at a high temperature, a deodorizing treatment using a catalyst, and a chemical cleaning method. Some of these have problems in terms of cost such as operating cost and deodorization efficiency in a low concentration range.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems such as difficult operability, efficiency of oxidation treatment such as decolorization, bleaching, and deodorization, and cost for the treatment. Another object of the present invention is to provide a simple and economically advantageous method for oxidizing an organic substance serving as a contamination source contained in an aqueous solution by using activated hydrogen peroxide. Another object of the present invention is to provide a method for oxidizing an organic compound using hydrogen peroxide.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, as a result, anion-exchange resin is loaded with halogenoid ions such as cyanate ion and thiocyanate ion, and the resin is used as an object. Hydrogen peroxide was added to and brought into contact with a solution containing the substance to be activated to efficiently activate the hydrogen peroxide, and a method capable of improving the oxidation treatment of the target substance was found, and the present invention was completed. That is, the present invention relates to a method of supporting an activated species of hydrogen peroxide on an ion exchange resin and continuously and efficiently oxidizing the target substance with the activated hydrogen peroxide.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS When the present invention is used for decolorization of an aqueous dye solution, the dye in the target aqueous solution is not limited, and includes an intermediate in the production of the dye. In particular, the effect is remarkable when the method of the present invention is applied to a water-soluble dye. The dye contained in the aqueous solution may be a single compound alone or a mixture of two or more compounds. The dye concentration in the aqueous solution is not particularly limited, but is preferably 0.1% by weight or less. The reason for this is that while it is generally difficult to decolorize an aqueous solution containing a low-concentration dye, according to the present invention, decolorization can be performed efficiently. In addition, the temperature of the wastewater during the dehydration treatment is not limited, and has a capability of sufficiently decoloring at room temperature.

The peroxide (hereinafter referred to as "hydrogen peroxide") which generates hydrogen peroxide in the aqueous solution used in the present invention includes hydrogen peroxide, sodium tripolyphosphate which is an organic and inorganic hydrogen peroxide adduct. hydrogen peroxide adduct, sodium pyrophosphate peroxide adduct, urea peroxide _{adduct, 4Na 2 SO 4 · 2H 2} O 2 · NaCl, sodium carbonate hydrogen peroxide adduct, sodium perborate monohydrate , Sodium perborate tetrahydrate, sodium peroxide,
Calcium peroxide and the like are exemplified. Among them, sodium carbonate hydrogen peroxide adduct, sodium perborate monohydrate, and sodium perborate tetrahydrate are preferred. Further, the amount of hydrogen peroxide or the like to be used for decolorization of the aqueous dye solution depends on the type of the dye, but is preferably 0.1 to 100 times the weight of the dye compound in the aqueous solution, and more preferably 0.1 to 100 times. The amount is 5 to 50 times the weight. When a compound that forms an adduct with hydrogen peroxide is used, the amount is such that the amount of hydrogen peroxide generated by dissociation of the adduct in water is within the above range. If the amount of hydrogen peroxide or the like is larger than this, the COD value may increase due to the residual hydrogen peroxide or the like during the treatment, and the use of an excessive amount is not preferable.

Halogenoid ions having the function of activating hydrogen peroxide and supported on an anion exchange resin include cyanide ion, thiocyanate ion, selenocyanate ion, tellurocyanate ion, cyanate ion, and isocyanate ion. Illustrative examples include, preferably, cyanate ion and thiocyanate ion, and as the compound, an alkali metal salt or an ammonium salt, such as potassium cyanate, ammonium cyanate, potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate. And the like.

The anion exchange resin used in the present invention is not particularly limited as long as it is a resin carrying halogenoid ions. For example, a strong base having a quaternary ammonium group as an ion exchange group can be used. Representative examples include Diaion PA-318 manufactured by Mitsubishi Chemical Corporation and IRA-900 manufactured by Rohm & Haas Co., Ltd., which are conductive resins. The concentration of the aqueous solution used in preparing the anion exchange resin carrying these halogenoid ions is not limited, but preferably an aqueous solution of 0.5 to 2.0 N is preferable, and the aqueous solution passed through the resin layer is preferably used. Space velocity (SV) is 1 to 100 / h,
Preferably, the range of 1 to 20 / h is appropriate. As this preparation method, for example, when a cylindrical column is filled with an ion exchange resin together with pure water and an aqueous solution of potassium cyanate is passed, an anion exchange resin having a cyanate terminal at the end can be prepared. This prepared resin can be recycled and used repeatedly.

When the present invention is used for decolorization of an aqueous dye solution, the decolorization of the dye is not affected by the pH of the aqueous dye-containing solution when cyanate ions are loaded on an ion exchange resin as an activating species. When the thiocyanate ion is supported on the ion exchange resin, the pH of the dye-containing aqueous solution is usually pH 8 because decolorization is remarkably promoted on the alkali side.
~ 14, preferably 9 ~ 13.

In the present invention, when the pH is adjusted as required, an alkali metal hydroxide or an alkali silicate is used as an alkali agent. As the alkali metal hydroxide or alkali metal silicate, it is desirable to use an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide, or an alkali silicate such as sodium silicate or potassium silicate. In addition, the amount of the alkali agent can be reduced for those which show alkalinity by themselves, such as sodium carbonate hydrogen peroxide adduct and sodium perborate, as the peroxide.

When the method of the present invention is carried out for wastewater treatment, it is carried out in combination with other general wastewater treatment methods, for example, a coagulation sedimentation method, a microorganism treatment method, an activated carbon adsorption method, an ozone oxidation method and the like. Can be. For example, treating the wastewater by performing the method of the present invention after removing most of the high-concentration contaminants contained in the wastewater by coagulation sedimentation treatment is a feature of the present invention that the wastewater is continuously passed through the wastewater. Since it is possible to perform a liquid treatment, the efficiency is high, and this is one of the preferred embodiments of the present invention. In addition, the present invention can be carried out in the same manner as described above even when the solution is bleached or deodorized. In the field of organic synthesis, the present invention is used in an organic synthesis such as an epoxidation reaction using hydrogen peroxide as an oxidizing agent. can do.

[0017]

EXAMPLES Hereinafter, decolorization of an aqueous dye solution in the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 20 ml of a strong basic resin having a quaternary ammonium group (trade name: Diaion PA-318, manufactured by Mitsubishi Chemical Corporation) as an anion exchange resin was packed together with pure water into a cylindrical column having a capacity of 100 ml. A cyanic acid type anion exchange resin prepared by passing a 1N aqueous solution of potassium cyanate from the upper end of the column at SV = 10 / h for 1 hour was used. As a dye sample, the color difference of a 0.05% by weight aqueous solution of eriochrome black T, one of the acidic mordant dyes, was measured and found to be 100.2. To this dye-containing aqueous solution, hydrogen peroxide was added so that the aqueous solution became 1.2%, and the aqueous solution was added to the ion exchange resin 2 prepared above.
When the solution was passed through 0 ml at SV = 10 / h, the color difference of the aqueous solution after passing was 6.17, and the decolorization rate was 93.84%.
Met. The color difference was measured by the following method. Using a color difference meter, the lightness index (L *) and the chroma takeness index (a *, b *) were measured for each of the measurement liquid and pure water. Next, △ L *, △ a *, ＊ b *, which is the difference between L *, a *, and b * of the measurement liquid and pure water, were obtained, and were determined by the square root of the sum of the squares of each. The decolorization rate was determined by the following equation. Decolorization ratio (%) = (color difference before processing−color difference after processing) / color difference before processing × 100 Comparative Example 1 Example 1 except that a chlorinated strong basic resin having a commercially available ionic terminal was used. The decolorization rate of the aqueous solution of Eriochrome Black T was 0.1%
Met.

Example 2 0.1 of crystal violet, one of the basic dyes.
0.12% of aqueous solution of hydrogen peroxide in 05% by weight aqueous solution
And the aqueous solution was passed through 20 ml of an ion exchange resin prepared in the same manner as in Example 1.
The bleaching rate due to the treatment was 93.57%. Comparative Example 2 The same procedure as in Example 2 was carried out except that a strong basic resin having a terminal ion form of chloro was used. The decolorization rate of the aqueous crystal violet solution was 67.89%.

Example 3 Hydrogen peroxide was added to a 0.05% by weight aqueous solution of orange II, one of the acid dyes, so that the aqueous solution became 1.2%, and the aqueous solution was used in the same manner as in Example 1. When the solution was passed through 20 ml of the ion exchange resin prepared as described above, the decolorization rate due to the treatment was 98.89%.

Example 4 Hydrogen peroxide was added to a 0.05% by weight aqueous solution of pyrocatechol violet, one of the triarylmethane type dye compounds, so that the aqueous solution became 1.2%, and the aqueous solution was added. 20 m of ion exchange resin prepared in the same manner as in Example 1.
1 and the decolorization rate by the treatment was 95.15.
%Met.

Example 5 Example 1 was repeated except that a strongly basic resin having a quaternary ammonium group (trade name: Diaion PA-318, manufactured by Mitsubishi Chemical Corporation) was used as the anion exchange resin, and potassium thiocyanate was used. A thiocyanate type prepared by the same method as in Example 1 was used. Sodium hydroxide was added to the same aqueous solution as in Example 1 so as to be 1.0%, and the pH of the aqueous solution was 11.68. This is the above resin 2
When the solution was passed through 0 ml at SV = 5 / h, the decolorization rate was
79.5%.

Example 6 Sodium percarbonate was added to the same aqueous solution as in Example 3 so that the concentration of hydrogen peroxide contained therein became 1.2%, and the aqueous solution was prepared in the same manner as in Example 5. When the solution was passed through 20 ml of the exchange resin at SV = 10 / h, the decolorization rate due to the treatment was 99.53%.

Example 7 Cyclohexene was epoxidized. The yield is
It was calculated by the internal standard method using gas chromatography. Ion exchange resin 10 prepared in the same manner as in Example 1.
When a methanol solution of 20% by weight of hydrogen peroxide and 5.0% by weight of cyclohexene was passed through the flask at room temperature at SV = 1 / h, the yield of cyclohexane oxide obtained was as follows:
It was 14.3%.

Comparative Example 3 100.0 g of a methanol solution containing 4.0% by weight of hydrogen peroxide, 5.0% by weight of cyclohexene and 5.3% by weight of potassium cyanate was stirred in a 200 ml Erlenmeyer flask at 40 ° C. for 5 hours to obtain a solution. The yield of cyclohexane oxide obtained was 9.
6%.

[0025]

According to the present invention, an oxidizing method can be carried out simply and efficiently by bringing an organic substance containing hydrogen peroxide into contact with an ion-exchange resin carrying activated species of hydrogen peroxide. .

Claims (7)

[Claims] 1. A method for oxidizing an organic substance, wherein hydrogen peroxide or a peroxide that generates hydrogen peroxide is added to the organic substance, and the organic substance is brought into contact with an ion exchange resin carrying an activated species of hydrogen peroxide. 2. The method according to claim 1, wherein the activated species of hydrogen peroxide is a halogenoid ion compound. 3. The method according to claim 2, wherein the halogenoid ion compound is a cyanate ion compound or a thiocyanate ion compound. 4. The method according to claim 1, wherein the ion exchange resin is a strongly basic or weakly basic anion exchange resin. 5. The method according to claim 1, wherein the hydrogen peroxide or the peroxide that produces hydrogen peroxide is hydrogen peroxide, sodium carbonate hydrogen peroxide adduct, or sodium perborate. 6. The method according to claim 1, wherein the organic matter in the waste water is oxidized.
The described method. 7. An ion exchange resin carrying an activated species of hydrogen peroxide used in the method according to claim 1.