JP3082891B2 - Industrial water sterilization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for sterilizing various types of industrial water. For more information, preservation of papermaking process water in the paper and pulp industry, cooling water for various industries, washing water, drainage, etc.
The present invention relates to an industrial sterilization method useful for sterilization and bacteriostasis.

[0002]

2. Description of the Related Art Conventionally, slime due to bacteria and fungi has been generated in papermaking process water in the paper and pulp industry and in cooling water systems in various industries, and there are obstacles such as deterioration in product quality and production efficiency. It has been known. Many fungicides have been used to prevent damage by these microorganisms. Dichloroglyoxime, one of the active ingredients of the present invention, has an inhibitory effect on the growth of typical gram-negative and gram-positive bacteria, while its homologs, glyoxime and dimethylglyoxime, have an inhibitory effect on growth. (Dirasat 13 (7) .185-188 (1986)
].

[0003]

[0010] Industrial water that requires a sterilization treatment often contains a reducing substance. For example, white water in the paper and pulp manufacturing process must be sterilized, but recycled waste paper can be used as a raw material,
A reducing substance typified by a sulfite ion is contained along with the bleaching treatment or the like. In some cases, hydrogen sulfide is contained due to decay of organic substances. In the case of industrial water in which such a reducing substance is present, particularly in industrial water in which sulfite ions are present in an amount of 5 mg / l or more, particularly 10 mg / l or more, when known industrial germicides are used, their bactericidal efficacy is reduced. Significantly decreased, and as a result, it was not possible to effectively prevent the damage caused by the slime described above.

The present invention has been made under such circumstances, and it is an object of the present invention to provide a novel sterilizing method which has a remarkable effect in industrial water containing a reducing substance. As a result of various studies, the inventor of the present invention has surprisingly found that glyoxime dihalide has an excellent bactericidal action in a reducing environment, and has completed the present invention.

[0005]

Thus, according to the present invention, after washing the paper / pulp manufacturing process, the operation is resumed,
In a paper / pulp manufacturing process water in which a reducing substance is present in an amount of 10 mg / l or more as a sulfite ion, a general formula [I] as an active ingredient:

Embedded image (Wherein, X represents a halogen atom). A method for disinfecting water in a paper / pulp production process , characterized by adding a dihalogenated glyoxime derivative represented by the following formula:

The sterilizing method of the present invention exhibits excellent sterilizing power even in a reducing environment, for example, an environment in which a reducing substance is present in an amount of 5 mg / l, especially 10 mg / l (equivalent to sulfite ion) or more. In the general formula [I], examples of the halogen atom represented by X include a chlorine, bromine, fluorine or iodine atom, and a chlorine or bromine atom is particularly preferable. Specific examples of the dihalogenated glyoxime include dichloroglyoxime, dibromoglyoxime, difluoroglyoxime and diiodoglyoxime, and dichloroglyoxime is particularly preferred.

The dihalogenated glyoxime derivative represented by the above general formula [I] can be easily synthesized by halogenating the glyoxime derivative.

The active ingredient of the present invention is preferably used in the form of a liquid preparation. However, the present invention is not limited thereto, and may be directly or a solid diluent (for example, kaolin, clay, bentonite, CMC, etc.) depending on the use object.
May be used in the form of a powder or the like diluted with. When preparing a liquid preparation, the active ingredient can be prepared by dissolving the active ingredient in a hydrophilic organic solvent and further adding a surfactant, if necessary.

It is also possible to use an aqueous solvent in which a hydrophilic organic solvent (eg, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, polyethylene glycol, propylene carbonate, dimethyl glutarate, etc.) and water are mixed. As the surfactant, a cationic, anionic, nonionic or amphoteric surfactant is suitable, and a nonionic surfactant is preferable in terms of stability as a preparation.

These preparations preferably contain 1 to 50 parts by weight of an active ingredient, 0 to 5 parts by weight of a surfactant, and the remainder water or an aqueous solvent. The compounding ratio of the active ingredient in the preparation is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight. Such preparations are used to prevent contamination of various industrial waters by microorganisms. In particular, by adding to various industrial waters, for example, papermaking process water in the paper and pulp industry, cooling water for various industries, washing water, river water, various wastewaters, etc., a remarkable bactericidal action is exhibited, and further reduction is achieved. In industrial water systems in which the active substance is present in an amount of 5 mg / l (equivalent to sulfite ion) or more, particularly 10 mg / l or more, these preparations exhibit a remarkable bactericidal effect as compared with known industrial bactericides. It is the most useful in the system (see Test Example 1). Here, sterilization means killing slime-constituting bacteria constituting slime. In this invention, killing means remarkably sterilizing slime-constituting bacteria, and generally means reducing the number of bacteria to the order of 10 ³ cells / ml or less.

The appropriate amount of such an industrial target system varies depending on the type of target system and incidental conditions such as the degree of generation of microorganisms, but the amount of the active ingredient of the present invention is usually 0.01. 10 to 10 mg / l, preferably 0.05 to 5 mg / l
5 mg / l is suitable. In the fungicide of the present invention,
Additives (for example, various surfactants, water-soluble polymers, defoamers, etc.) may be contained in such an amount that the effects of the present invention are not impaired. The invention is illustrated by the following examples.

[0012]

【Example】

Reference synthesis example. [Synthesis of glyoxime] 39.0 g of hydroxylamine sulfate was dissolved and mixed in 70 ml of water, and 29.0 g of a 40% glyoxal solution was dropped and mixed. Further, the mixture was neutralized by adding a 40% aqueous sodium hydroxide solution, and after 30 minutes, the precipitated white crystals were recrystallized from water to obtain 10.6 g of the title compound (mp178).
° C).

Synthesis Example 1 [Synthesis of chloroglyoxime and dichloroglyoxime] 8.8 g of glyoxime obtained by the method of Reference Synthesis Example is dissolved and mixed in 100 ml of methanol. A small amount of chlorine gas was blown into and mixed therein. At this time, the temperature in the system is 10 to 1
It was kept at 2 ° C. When the reaction product was measured over time by HPLC, chloroglyoxime was first formed (reaction A).
Then, dichloroglyoxime was produced (reaction B).

[0014]

Embedded image The reaction was stopped with A, and after removing the solvent, recrystallization from water gave white crystals of chloroglyoxime (mp 156 ° C).
[I] was obtained (36% yield). The reaction was stopped at B, the solvent was removed, and the residue was recrystallized from methanol to obtain white crystals of dichloroglyoxime (mp 199 ° C) [II] (yield: 55%).

Formulation Example Dichloroglyoxime 5 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Water 5 parts by weight

Test Example 1 [Test for confirming bactericidal effect in the presence of reducing substances] Bacteria isolated from pink slime generated in a certain paper mill
(Flavobacterium species) was used to conduct a confirmation test of the bactericidal efficacy in the presence of a reducing substance. Sodium sulfite was used as a reducing substance. The measurement method is such that the number of viable cells is 10 ⁶ cells / ml or more in a pH 7.0 buffer solution prepared as a SO ₃ ^2- concentration of a bacterial solution pre-cultured in a bouillon medium at a concentration of 0, 10, or 50 mg / l. In addition to the above, a drug was added thereto, and the mixture was shaken at 30 ° C. for 60 minutes. Thereafter, the number of surviving bacteria was measured, and the minimum concentration at which 99.9% or more of the initial number of bacteria was killed was determined. The results are shown in Table 1 together with Comparative Examples.

[0017]

[Table 1]

Test Example 2 [Test for confirming the bactericidal effect in the presence of a reducing substance] A bacterium ( Pseudo) isolated from a slime generated at a certain paper mill.
monas sp.), a test for confirming the bactericidal efficacy in the presence of a reducing substance. Sodium sulfite was used as a reducing substance. The test method was as follows: a bacterial solution pre-cultured in a broth medium was used as a sulfite ion concentration of 0.5, 1, 1
The viable cell count is 1 in a pH 7.0 buffer solution adjusted to 0,100 mg / l.
Added to a 0 ⁶ 10 ⁷ cells / ml, which was added to the drug, shaking for 60 minutes at 30 ° C., then measured number of viable cells were suspended, or 99.9% of the initial number of bacteria are killed The minimum concentration was determined. The results are shown in Table 2 together with Comparative Examples.

[0019]

[Table 2]

[Consideration of Test Example 2] Additional experiment : DCG was added to the buffer solution of pH 7.0 (adjusted to a sulfite ion concentration of 10 mg / l) used in Test Example 2 so as to be 10 mg / l. DC in buffer after shaking at 60 ° C for 60 minutes
When the residual concentration of G was measured by HPLC (high performance liquid chromatography), none was detected (less than 0.01 mg / l).

Discussion : From the results of the additional experiment, it was found that DCG
Is decomposed by the sulfite ion in the buffer solution. Nevertheless, as is clear from Test No. 1 of Test Example 2, bactericidal activity was observed at a low concentration of 0.5 to 2 mg / l. From these test results, it is considered that DCG has a very high rate of killing bacteria and has an action of killing bacteria before being decomposed by sulfite ions. Therefore, when DCG is used as a slime control agent in water for the production of paper and pulp containing sulfite ions, the bacteria are quickly killed and then the active ingredient is decomposed. Is considered less.

Test Example 3 [Example of use as a slime control agent in a paper mill] In a paper making process in a certain paper mill, a DBNPA slime control agent [DBNPA (2,2-dibromo-3-nitrilopropionamide) 20%; Diethylene glycol 80%] was added to the white water pit three times a day for 30 minutes so that the water concentration was 10 ppm (active ingredient concentration).
However, the occurrence of eyeballs and paper breaks due to slime increased from the fourth day, and on the seventh day, the increase in the number of paper breaks and the deterioration of product quality forced the operation to be stopped and the processes to be cleaned.

After this, the process is washed and the operation is resumed.
The concentration of G-based slime control agent (DCG 10%, diethylene glycol 90%) in white water pit is 3ppm in water.
(Active ingredient concentration) was added three times a day for 30 minutes, no slime was adhered to each part of the process even after 20 days from the start of operation, and high quality products could be made. Was. Table 3 shows the results of measuring the daily number of paper breaks, the slime contamination of the white water pit, the reducing ion (SO ₃ ^2- conversion) concentration in the white water, and the number of viable bacteria in the white water before and after the addition of the drug. Shown in

[0024]

[Table 3]

[0025]

According to the sterilization method of the present invention, in various industrial waters containing a reducing substance, the reducing ion is preferably 5 mg.
In a system containing more than 1 / l, a remarkable bactericidal effect is obtained, which is not seen in the method using a known bactericide.

Claims (4)

(57) [Claims] 1. Operation after washing paper and pulp manufacturing process
Was resumed, and the reducing substance was converted to 10 mg /
1 or more of the paper / pulp manufacturing process water , as an active ingredient, represented by the general formula [I]: (Wherein, X represents a halogen atom). A method for disinfecting paper / pulp production process water , comprising adding a dihalogenated glyoxime derivative represented by the following formula: 2. A general type sterilization method according to claim 1 halogen atom dihalogenated glyoxime derivative represented by the [I] is a chlorine atom or a bromine atom. 3. The sterilization method according to claim 1, wherein the dihalogenated glyoxime derivative represented by the general formula [I] is dichloroglyoxime. 4. A bactericidal effective concentration of 0.01 to 10 mg / l.
The sterilization method according to any one of claims 1 to 3 , wherein