Processing method of waste acids and medicament

Abstract

To provide a method for treating a waste acid which has a pH of 2.0 or under, shows marked corrosiveness, and has a possibility of being dumped as a special management waste from factories and enterprises to obtain a gelatinous compound and controlling the pH to be over 2.0 to be excluded from conditions of a special management waste and a medicament to be used therein.SOLUTION: In a method of elevating pH of a waste acid where organic materials or inorganic materials are dissolved, a water-soluble substance forming a sol state of a colloidal solution is used, and in a process of forming a gelatinous form, a medicament for coagulation condensation of a plurality of water pollution controlled substances in the waste acid and its processing method are characterized, and dissolved components in the waste acid is included in the gel by intermolecular forces, and / or coupled as the gelatinous compound with the pH exceeding 2.0 via one or more coupling schemes.

Description

[Technical Field]

[0001] The present invention relates to a method for treating waste acid and to an agent for use in said treatment method. [Background technology]

[0002] Under the Waste Management and Public Cleansing Act, waste acids with a pH of 2.0 or less, which are highly corrosive, are designated as specially controlled industrial waste, meaning that they "have properties that could potentially cause harm to human health or the living environment." Businesses are required to either dispose of them themselves in accordance with the specially controlled industrial waste disposal standards or entrust their transportation or disposal to a licensed specially controlled industrial waste contractor. High-concentration inorganic waste acids, such as acid plating waste, activated acid waste, pickling waste, resist stripping waste, and etching waste, are particularly problematic. These waste acids are often discharged from metal surface treatment plants, printed circuit board plants, and chemical vapor deposition plants. Some of these waste acids contain ionic components such as iron, aluminum, zinc, copper, nickel, chromium, fluorine, and boron. Conventional alkaline neutralization processes are ineffective due to the heat generated by neutralization, so many waste acids are outsourced to licensed specially controlled industrial waste contractors. Therefore, a simpler, less hazardous treatment method is needed.

[0003] Generally, the method of neutralizing strong acid waste using a strong alkaline solution is not used because it involves the risk of boiling at high temperatures. Businesses are hoping to minimize the cost of disposing of such waste acid.

[0004] As shown in the water treatment process of Patent Document 1, a method is used to remove silica from natural water or wastewater containing silica and scale-forming ions by using a weakly acidic silica compound, which is contained in the lattice of the layered double hydroxide as an interlayer anion and / or is bound to the layered double hydroxide through one or more bonding modes. However, this method has the disadvantage that it is not a strong acid treatment and the pH must be maintained at 8 or above.

[0005] Patent Document 2 discloses a method for producing an organic acid salt with high optical purity, which comprises neutralizing an optically active organic acid having a concentration of 30 to 70% by weight with an aqueous alkaline solution having a concentration of 30 to 60% by weight at a reaction temperature of 35°C or less, but does not disclose any treatment of a strong acid to form a gel-state compound.

[0006] Patent Document 3 describes a method for adjusting pH in wastewater treatment, and mentions that by adding a strong base and a weak base or a strong acid and a weak acid in combination, it is possible to accurately adjust the amount of chemicals added with small amounts, but there is no mention of turning a strong acid into a gel-state compound. [Prior art documents] [Patent documents] [Patent Document 1] Special Publication No. 2020-533163 [Patent Document 2] Japanese Patent Application Publication No. 04-145043 [Patent Document 3] Japanese Patent Publication No. 52-109756 Summary of the Invention [Problem to be solved by the invention]

[0007] The problem that the invention aims to solve is to use a solid gel to incorporate dissolved substances from a highly concentrated strong acid waste acid solution into the gel, and the challenge is to incorporate dissolved substances of different charges during the process of growing the gel from a sol-state aqueous solution.

[0008] In the industrial application of this treatment, for example, it is necessary to achieve gelation at a low temperature in a short time without any danger so that it can be carried out in a workplace.

[0009] During waste acid treatment, the higher the acid concentration, the longer it takes for the water-soluble substance that forms the gel-like substance to gel. Therefore, in order to gel it in a short time, something that makes it easier to gel is needed.

[0010] When the agent is added during waste acid treatment, it is necessary to incorporate dissolved substances before they form large lumps in order to gel in the waste acid. [Means for solving the problem]

[0011] The present invention provides a method for treating high-concentration waste acid containing various dissolved substances, in which a sol-state substance is added to the waste acid and the dissolved components are gelled in the process of forming a gel-like substance. The chemicals used in the method are characterized by comprising a water-soluble substance that forms a gel-like substance, an alkali metal and / or alkaline earth metal compound, and an aqueous solution of a coagulation aid, and a treatment method therefor. [Effects of the Invention]

[0012] The aggregating aid used in the present invention for the production of pharmaceuticals facilitates the incorporation of dissolved components into the surface of the water-soluble substance that forms the gel-like substance during treatment, thereby enabling gelation in a short period of time.

[0013] The agglomeration aid used in the present invention during the production of pharmaceuticals has the effect of making it easier to disperse the sol-state pharmaceutical added to the waste acid during the process of forming a gel-like substance while absorbing dissolved substances, thereby preventing the sol-state pharmaceutical from agglomerating into clumps without absorbing the dissolved substances in the waste acid immediately after addition.

[0014] In the waste acid treatment method containing dissolved substances, alkali metal and / or alkaline earth metal compounds are added to the water-soluble substances, and when the gel-like substance in the resulting liquid forms fine particles, compounds containing carbon, nitrogen, oxygen, sulfur, phosphorus, halogens, boron, and heavy metals dissolved in the waste acid can be recovered and concentrated. Examples of heavy metal ions that can be suitably removed during this treatment include ions of iron, aluminum, manganese, nickel, copper, zinc, cadmium, lead, chromium, arsenic, mercury, selenium, etc. DETAILED DESCRIPTION OF THE INVENTION

[0015] The energy generated when electrostatic interactions such as hydrogen bonds and van der Waals interactions acting on hydrated ions surrounding water-soluble substances in a sol state disappear when the sol changes to a gel state is utilized, and the energy generated when the water-soluble negative charge of the sol and the surrounding hydrated ions of alkali metal and / or alkaline earth metal compounds polarize and electron exchange occurs with the water-soluble substances, thereby adsorbing multiple types of dissolved substances with different charges and growing them into a gel state.

[0016] Ions are attracted to each other by intermolecular forces and Coulomb forces, but in a neutralization reaction, ions collide with surrounding objects, converting their velocity energy into heat and generating heat, so heat generation can be suppressed by using a weak acid, which has lower energy than the products.

[0017] Among positively and negatively charged ions dissolved in water, for example, a water-soluble substance that forms a gel state attracts positively charged substances, and an alkali metal and / or alkaline earth metal compound attracts negatively charged substances, thereby simultaneously incorporating substances of different charges and growing into a gel. This provides a method for separating dissolved substances of different charges from an aqueous solution by forming a solid gel, and a drug for use therein.

[0018] In order to minimize the volume of chemicals, concentrated solutions are made with high viscosity and a large specific gravity, so when they are dissolved in waste acid, they do not completely disperse and form clumps that settle to the bottom of the treatment tank. A flocculation aid is used to prevent the chemicals from clumping and flocculating.

[0019] Any water-soluble substance can be used as long as it forms a gel-like substance in the waste acid containing dissolved substances. Examples of water-soluble substances that are relatively inexpensive and easily form a gel-like substance include polyvinyl alcohol, polyacrylic acid or its salts, copolymers of acrylamide and acrylic acid or their salts, polyacrylamide, polyacrylic acid dimethylaminoethyl ester, polymethacrylic acid dimethylaminoethyl ester, cationized modified polyacrylamide, polyethyleneimine, polyethylene oxide, polyvinylpyrrolidone, viscose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate or its salts, cellulose acetate phthalate or its salts, cellulose acetate propionate or its salts, carboxymethyl cellulose or its salts, dextrin, curdlan, soluble starch, carboxymethyl starch, dialdehyde starch, sweet potato starch, potato starch, tapioca starch, wheat starch, corn starch, galactomannan, konjac, funori, carrageenan, agar, furcellaran, alginic acid or its salts, Salt, propylene glycol alginate, chitin, chitosan, Abelmoschus abies, tragacanth gum, gum arabic, guar gum, xanthan gum, locust bean gum, gellan gum, pectin, pectinic acid or its salts, tamarind seed polysaccharide, latex, glue, gelatin, casein, collagen, gluten, soybean glue, sodium tripolyphosphate, etc., and superabsorbent resins such as starch-acrylic acid graft copolymer, saponified vinyl acetate-acrylic acid ester copolymer, crosslinked polyacrylate, carboxymethyl cellulose crosslinked polymer, zinc oxygenated oxygen compounds or their salts, cadmium oxygen compounds or their salts, aluminum oxygen compounds or their salts, gallium oxygen compounds or their salts, indium oxygen compounds or their salts, yttrium oxygen compounds or their salts, cerium oxygen compounds or their salts, titanium oxygen compounds or their salts, zirconium oxygen compounds or their salts, tin oxygen compounds or their salts, iron oxygen compounds or their salts, cobalt oxygen compounds or their salts, nickel oxygen compounds or their salts, vanadium oxygen compounds or their salts, niobium oxygen compounds or their salts,It is desirable to use any one of tungsten oxygen compounds or their salts, chromium oxygen compounds or their salts, molybdenum oxygen compounds or their salts, manganese oxygen compounds or their salts, copper oxygen compounds or their salts, antimony oxygen compounds or their salts, silicon oxygen compounds or their salts, calcium oxygen compounds or their salts, magnesium oxygen compounds or their salts, etc., or a combination of two or more of these.

[0020] The amount of the water-soluble substance that forms a gel-like substance to be added to the waste acid is 0.01 to 400 parts by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the dissolved substance in the waste acid.

[0021] The combined use of an alkali metal and / or alkaline earth metal compound that acts to gel the aqueous substance to produce a gel-like substance is effective. The alkali metal and / or alkaline earth metal compound may be selected from lithium, sodium, potassium, barium, calcium, strontium, magnesium, or a mixture of two or more of these. As examples of the alkali metal and / or alkaline earth metal compounds, the sodium compounds are preferably water-soluble sodium salts, such as sodium chloride, sodium nitrate, sodium carbonate, and sodium hydroxide, and the calcium compounds are preferably water-soluble calcium salts, such as calcium chloride, calcium nitrate, calcium carbonate, and calcium hydroxide. The magnesium compounds are preferably water-soluble magnesium salts, and may be appropriately selected from any one of these or a mixture containing two or more of them.

[0022] These alkali metal and / or alkaline earth metal compounds react with the water-soluble substance that forms a gel to form a gel. The proportion of the alkali metal and / or alkaline earth metal compounds used is not particularly limited, but is generally 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the water-soluble substance that forms the gel.

[0023] As a flocculation aid used in the production of the drug in the present invention, a nonionic surfactant may be appropriately selected from glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, ethylene oxide alkylphenols, polyoxyethylene-polyoxypropylene condensates, alkyl alcohol alkoxylates, alcohol ethoxylates, alkyl ethoxylates, alkyl polyethoxylates, fatty acid methyl ester ethoxylates, polyoxyalkylene glyceryl ethers, polyoxyethylene polyoxypropylene glycols, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, phenol ethoxylates, fatty acid diethanolamides, and polyethylene glycols, or a mixture containing two or more of these.

[0024] The amount of the nonionic surfactant-based aggregation aid used is 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, per 1000 parts by weight of the water-soluble substance that forms the gel-like substance.

[0025] As the coagulation aid for the drug used in the present invention, in organic solvent systems, alcohols, ketones, polyvinyl alcohol, polyacrylic acid or its salts, copolymers of acrylamide and acrylic acid or its salts, polyacrylamide, polyacrylic acid dimethylaminoethyl ester, polymethacrylic acid dimethylaminoethyl ester, cationized modified polyacrylamide, polyethyleneimine, polyethylene oxide, ethylene oxide alkylphenol, polyoxyethylene-polyoxypropylene condensate, alkyl alcohol alkoxylate, alcohol ethoxylate, alkyl ethoxylate, alkyl polyethoxylate, fatty acid methyl ester ethoxylate, polyoxyalkylene glyceryl ether, polyoxyethylene polyoxypropylene glycol, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, phenol ethoxylate, fatty acid diethanolamide, polyethylene glycol, or a mixture containing two or more thereof may be appropriately selected and used.

[0026] The amount of the solvent-based flocculation aid is used at a ratio of 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, per 1000 parts by weight of the water-soluble substance that forms the gel substance.

[0027] Add a water-soluble substance and an alkali metal, or / and an alkaline earth metal compound that form a gel substance during waste acid treatment, and stir and mix well. As long as the stirring and mixing method can mix sufficiently, any method usually used for stirring and mixing can be used.

[0028] The gel substance of the embodiment is a component that forms porous particles containing a composition represented by the compositional formula (M, MO)α·(MCO3)β·γ(Si, Al, Ti)Om·(OH)n,δ(H2O) (0≦α≦10, 0≦β≦10, 0.1≦γ≦20, 0<δ≦10, 0<m≦10, 0≦n≦10, M: including at least one of lithium, sodium, gallium, calcium, strontium, barium, magnesium, zinc, cadmium, aluminum, indium, yttrium, cerium, titanium, zirconium, tin, cobalt, nickel, vanadium, niobium, tungsten, chromium, molybdenum, manganese, iron, copper, silver, antimony).

Example

[0032] A mixed solution was prepared for 30 minutes by mixing 4 parts by weight of magnesium chloride hexahydrate, for example, from among the alkali metal and / or alkaline earth metal compounds described in claim 1 or 3, and 1 part by weight of calcium chloride hexahydrate, for example, from among the alkali metal and / or alkaline earth metal compounds described in claim 1 or 3, with 0.001 parts by weight of polyoxyalkylene glyceryl ether and 0.001 parts by weight of octylphenol ethoxylate, for example, from among the flocculation aids described in claim 1 or 4, with 5 parts by weight of water. This was designated as Treatment Solution (III) in Production Example 1.

[0033] The treatment liquid (II) and treatment liquid (III) were mixed and the mixture was designated as treatment liquid (IV) of Production Example 1, thereby obtaining a mixed solution.

[0034] (Production Example 1-2) In order to compare the production time using the above-mentioned flocculation aid with that without the use of the flocculation aid, 10 parts by weight of a 10% aqueous solution of polyaluminum chloride, 11 parts by weight of calcium chloride hexahydrate, 14 parts by weight of magnesium chloride hexahydrate, 10 parts by weight of a 10% aqueous solution of aluminum sulfate, and 5 parts by weight of water were mixed and prepared. It took more than one hour for the mixture to dissolve into a colorless, transparent solution, which means that the use of the flocculation aid was more than twice as effective.

[0035] (Processing example of manufacturing example 1) 100 mL of the processing solution (IV) of manufacturing example 1 was added to 100 mL of waste acid from a plating factory A (nickel ion concentration 1,000 mg / L, nitric acid concentration 1.3 mol / L), and as described in claim 3, for example, sodium carbonate was added to adjust the pH to 5, and the mixture was stirred for 5 minutes, causing a colloidal solution of the water-soluble substance in a sol state and an alkali metal and / or alkaline earth metal compound to grow into a gel state without forming heterogeneous lumps, which occurs when no flocculation aid is used.

[0036] (Evaluation example of manufacturing example 1) In the above treatment, no clumping occurred, and the concentration of the pollution control substance in the supernatant liquid was a nickel ion concentration of 100 mg / L, meaning that the nickel ion concentration could be reduced to 1 / 100. [Example]

[0037] (Production Example 2) Of the water-soluble substances described in claim 1 or 2, for example, 70 parts by weight of 1% aqueous sodium hydrogen carbonate solution described in claim 1 or 3 was added to 30 parts by weight of carboxymethyl cellulose and mixed to prepare a mixed solution, which is designated as Treatment Solution (I) in Production Example 2.

[0038] A mixed solution was prepared by adding and mixing, for example, 10 parts by weight of a 10% aqueous solution of polyaluminum chloride and 10 parts by weight of a 10% aqueous solution of aluminum sulfate from among the water-soluble substances described in claim 1 or 2, 10 parts by weight of an alkali metal and / or alkaline earth metal compound described in claim 1 or 3, 10 parts by weight of magnesium chloride hexahydrate, 10 parts by weight of calcium chloride hexahydrate, and 0.001 parts by weight of polyethylene glycol described in claim 1 or 4. This is designated as Treatment Solution (II) in Production Example 2.

[0039] A mixed solution was prepared by mixing 5 parts by weight of water with, for example, 3 parts by weight of magnesium chloride hexahydrate and 2 parts by weight of calcium chloride hexahydrate among the alkali metal and / or alkaline earth metal compounds described in claim 1 or 3, and, for example, 0.001 part by weight of secondary alcohol alkoxylate and 0.001 part by weight of polyoxyethylene polyoxypropylene glycol among the flocculation aids described in claim 1 or 4. This is designated as Treatment Solution (III) in Production Example 2.

[0040] The treatment liquids (II) and (III) were mixed to give treatment liquid (IV) of Production Example 2, and a mixed solution (colorless, transparent) was obtained after a mixing time of about 30 minutes.

[0041] (Production Example 2-2) In order to compare the production time of the above treatment liquid production example with that of a method not using a flocculation aid, in a method in which 10 parts by weight of a 10% aqueous solution of polyaluminum chloride, 10 parts by weight of a 10% aqueous solution of aluminum sulfate, 13 parts by weight of magnesium chloride hexahydrate, and 12 parts by weight of calcium chloride hexahydrate were mixed with 5 parts by weight of water, the concentration was close to the saturated concentration, so it took more than one hour for the solution to become colorless and transparent, and therefore when a flocculation aid was used, the effect was more than twice as great.

[0042] (Production Example 2 Treatment Example) 500 mg / L of Production Example 2 Treatment Solution (I) and 500 mg / L of Production Example 2 Treatment Solution (IV) were added to 1,000 mL of waste acid from a plating factory B (zinc ion concentration 200 mg / L, ammonium ion concentration 200 mg / L, boron concentration 30 mg / L, fluoride ion concentration 50 mg / L, pH 2). The pH was adjusted to 5 by adding, for example, sodium bicarbonate, as described in claims 1 or 3, and the mixture was stirred for 15 minutes. This resulted in a gel-like growth of a colloidal solution of the sol-state water-soluble substance and alkali metal and / or alkaline earth metal compounds, without the formation of heterogeneous lumps that occurs when no flocculation aid is used. The resulting solution was then left to stand for 1 hour to allow flocculation and sedimentation.

[0043] (Evaluation example of manufacturing example 2) The concentrations of pollution control substances in the supernatant after the above treatment were zinc ion concentration 2 mg / L, ammonium ion concentration 100 mg / L, boron concentration 10 mg / L, and fluoride ion concentration 3 mg / L, which means that the zinc ion concentration was reduced to 1 / 100, the ammonium ion concentration to 1 / 2, the boron concentration to 1 / 3, and the fluoride ion concentration to 1 / 17. [Example]

[0044] (Production Example 3) 5 parts by weight of a 0.1% aqueous solution of orthoboric acid according to claim 1 or 2, and, for example, 30 parts by weight of polyvinyl alcohol and 65 parts by weight of a 0.1% aqueous solution of polyacrylic acid dimethylaminoethyl ester, among the water-soluble substances according to claim 1 or 4, were mixed to prepare a mixed solution (colorless, transparent). This is referred to as the treatment liquid (I) of Production Example 3.

[0045] A mixed solution (colorless, transparent) was prepared by adding 20 parts by weight of, for example, calcium chloride hexahydrate, one of the alkali metal and / or alkaline earth metal compounds described in claim 1 or 3, to 20 parts by weight of a 10% aqueous solution of, for example, polyaluminum chloride, one of the water-soluble substances described in claim 1 or 2. This is designated as Treatment Solution (II) in Production Example 3.

[0046] A mixed solution (colorless, transparent) was prepared by mixing 5 parts by weight of water with, for example, 5 parts by weight of magnesium chloride hexahydrate, which is an alkali metal and / or alkaline earth metal compound according to claim 1 or 3, and 0.001 parts by weight of polyoxyethylene polyoxypropylene glycol and 0.001 parts by weight of polyoxyethylene sorbitan monooleate, which is an aggregating aid according to claim 1 or 4. This is designated as Treatment Solution (III) in Production Example 3.

[0047] The treatment liquids (II) and (III) were mixed to give treatment liquid (IV) of Production Example 3, and a mixed solution (colorless, transparent) was obtained after a mixing time of about 30 minutes.

[0048] (Production Example 3-2) In order to compare the production time of the above treatment liquid production example with that of a method not using a flocculation aid, in a method in which 20 parts by weight of a 10% aqueous solution of polyaluminum chloride, 20 parts by weight of calcium chloride hexahydrate, 5 parts by weight of magnesium chloride hexahydrate, and 5 parts by weight of water were mixed, the concentration was close to the saturated concentration, so it took more than one hour for the solution to become colorless and transparent, and when a flocculation aid was used, the effect was more than twice as great.

[0049] (Production Example 3 Treatment Example) A mixture of 100 g / L of the above-mentioned Production Example 3 Treatment Solution (I) and 100 g / L of Production Example 3 Treatment Solution (IV) was added to 1,000 mL of waste acid from a plating factory (nickel ion concentration 2,000 mg / L, sulfuric acid concentration 0.2 mol / L). The pH was adjusted to 5 by adding, for example, sodium hydroxide, as described in claims 1 or 3, and the mixture was stirred for 15 minutes. A colloidal solution of the sol-state water-soluble substance and alkali metal and / or alkaline earth metal compounds grew into a gel state, without the formation of heterogeneous lumps that occurs when no flocculation aid is used. The solution was then left to stand for 1 hour to allow flocculation and sedimentation.

[0050] (Evaluation Example of Production Example 3) The concentration of the pollution control substance in the supernatant after the above treatment was reduced to a nickel ion concentration of 20 mg / L, and the nickel ion concentration could be reduced to 1 / 100.

Claims

1. In a method for treating waste acid, in which a sol-like substance and a coagulation aid are added to the waste acid to turn the waste acid containing various dissolved substances into a gel state, and the dissolved components are incorporated into the gel-like compound for treatment, the treatment agent and the treatment method are characterized by comprising a water-soluble substance that produces a gel-like substance, an alkali metal and / or alkaline earth metal compound, and an aqueous solution of the coagulation aid.

2. The method of claim 1, wherein the water-soluble substance is any one of a copolymer of acrylamide and acrylic acid or a salt thereof, polyacrylic acid or a salt thereof, alginic acid or a salt thereof, pectinic acid, pectin or a salt thereof, carboxymethylcellulose or a salt thereof, boron oxygen compound or a salt thereof, aluminum oxygen compound or a salt thereof, gallium oxygen compound or a salt thereof, indium oxygen compound or a salt thereof, yttrium oxygen compound or a salt thereof, cerium oxygen compound or a salt thereof, titanium oxygen compound or a salt thereof, zirconium oxygen compound or a salt thereof, tin oxygen compound or a salt thereof, iron oxygen compound or a salt thereof, cobalt oxygen compound or a salt thereof, vanadium oxygen compound or a salt thereof, niobium oxygen compound or a salt thereof, tungsten oxygen compound or a salt thereof, molybdenum oxygen compound or a salt thereof, manganese oxygen compound or a salt thereof, antimony oxygen compound or a salt thereof, silicon oxygen compound or a salt thereof, calcium oxygen compound or a salt thereof, magnesium oxygen compound or a salt thereof, strontium oxygen compound or a salt thereof, and barium oxygen compound or a salt thereof, or two or more of these.

3. 2. The method according to claim 1, wherein the alkali metal and / or alkaline earth metal compound is any one of lithium, sodium, potassium, barium, strontium, calcium, and magnesium, or a compound containing two or more of these.

4. When the flocculation aid is a nonionic surfactant, it may be an ether type, an ester type, a diester type, a sorbitan ester type, a sorbitan ester-ethylene oxide adduct type, a monoglyceride type, a monoglyceride-ethylene oxide adduct type, a triglyceride-ethylene oxide adduct type, a sorbit ester-ethylene oxide adduct type, a polyglycerin alkyl ester type, a polyethylene glycol-polypropylene glycol-block ether type, a polyetheramine type, an alkanolamide type, an alkanolamide-ethylene oxide adduct type, an amine oxide type, a glycerin fatty acid ester, a sorbitan fatty acid ester, a sucrose fatty acid ester, an ethylene oxide alkylphenol, a polyoxyethylene-polyoxypropylene condensate, an alkyl alcohol alkoxylate, an alcohol ethoxylate, an alkyl ethoxylate, an alkyl polyethoxylate, a fatty acid methyl ester ethoxylate, a polyoxyethylene polyoxypropylene glycol, a sorbitan alkyl ester, a polyoxyethylene sorbitan alkyl ester, a phenol ethoxylate, a fatty acid diethanolamide, a poly ethylene glycol, in organic solvent systems, alcohols, ketones, in anionic surfactant systems, alkyl sulfate type, alkyl ether sulfate type, amide ether sulfate type, methyl taurine type, amino acid type, dialkyl sodium sulfosuccinate type, alkyl benzene sulfonate type, fatty acid soap, as water repellents, in cationic surfactant systems, amine salt type, trimethyl type, dialkyl type, benzyl type, perfluoroalkyl cyclohexane sulfonic acid or its salt, in fluorine systems, trifluoromethanesulfonic acid or its salt, nonafluorobutanesulfonic acid or its salt, pentafluoroethanesulfonic acid, pentafluoropropanesulfonic acid or its salt, polyvinyl alcohol, polyacrylic acid or its salt, a copolymer of acrylamide and acrylic acid or its salt, polyacrylamide, polyacrylic acid dimethylaminoethyl ester, polymethacrylic acid dimethylaminoethyl ester, cationized modified polyacrylamide, polyethyleneimine, polyethylene oxide, ethylene oxide alkylphenol, polyoxyethylene-polyoxypropylene condensate,The method according to claim 1, wherein the surfactant contains any one or more of alkyl alcohol alkoxylates, alcohol ethoxylates, alkyl ethoxylates, alkyl polyethoxylates, fatty acid methyl ester ethoxylates, polyoxyalkylene glyceryl ethers, polyoxyethylene polyoxypropylene glycols, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, phenol ethoxylates, fatty acid diethanolamides, and polyethylene glycols.