JP2020203270A - Treatment agent of drainage water - Google Patents

Abstract

To provide a method for aggregating, precipitating and separating various water pollution regulation substances that may be discharged from a factory and a business site to a public water when the substances are treated, and an agent used in the same.SOLUTION: There are provided an agent which aggregates and concentrates a plurality of water pollution regulation substances in drainage water containing various water pollution regulation substances, in a method for treating the drainage water, in a process of adding a water-soluble substance for generating a sol state of a colloidal solution into the drainage water to form a gel-like state; and a treatment method of the same.

Description

The present invention relates to a method for treating wastewater and a chemical used in the treatment method.

Coupled with the tightening of industrial wastewater regulations, treatment measures are essential for inorganic and organic wastewater treatment to meet the standards. Among them, the treatment is a problem. For inorganic wastewater, copper plating solution, nickel plating solution, chrome plating solution, zinc plating solution, which are discharged from various plating factories, printed substrate factories, and chemical deposition factories. Examples thereof include tin plating solution, brass plating solution, solder plating solution, electroless copper plating solution, electroless nickel plating solution, resist peeling drainage, and etching drainage. Some of these wastewaters contain components that are difficult to treat, such as ammonia, zinc, copper, nickel, and boron fluorine. When gluconic acid, ethylenediaminetetraacetic acid, carboxylic acid compound, ammonia, amine compound, etc. are used, solid-liquid separation cannot be performed by ordinary alkali neutralization treatment. In addition, there is a problem in dealing with boron and fluorine-containing wastewater, which is difficult to treat easily in the ceramic industry, inn industry, livestock industry, etc., when the provisional standard is abolished. In each case, a small-scale and simple standard value achievement processing technology is required.

In general, a method of coagulating and separating a multi-component heavy metal ion as a hydroxide using an alkaline solution in wastewater is widely used and used as a neutralization sedimentation separation method, but it is used as an anion in an aqueous solution such as fluorine or boron. It is difficult to perform a precipitation separation treatment of a gluconic acid, ethylenediaminetetraacetic acid, a carboxylic acid compound, an ammonia, an amine compound, or the like which is a chelate compound with a metal. It is desired for small and medium-sized factories and business establishments to reduce the cost burden of treatment equipment as much as possible when discharging these treated wastewater to public water bodies.

As shown in (Patent Document 1), as a water treatment agent for phosphorus recovery, those obtained by forming powder as an adsorption treatment agent containing silicon and silica have been used so far. Since the form for adsorption is a powder having a large surface area, when it absorbs water after a lapse of time after production, it joins with each other to form a lump, the diffusion rate of the component to be adsorbed decreases, and the treatment effect decreases. Therefore, there is a drawback that the warranty period that can be used is shortened.

In (Patent Document 2), a pH-adjusted phosphoric acid solution is added to a granulated product containing heavy calcium carbonate powder, and the heavy calcium carbonate powder is reacted with phosphoric acid to cause hydroxy on the surface of the heavy calcium carbonate powder. A method for producing a fluoroion adsorbent by precipitating apatite is disclosed. If the powder is not sufficiently dispersed, the diffusion rate of the component to be adsorbed decreases and the treatment effect decreases, so that there is a drawback that the warranty period of the powder that can be used is shortened.

In (Patent Document 3), in the method for treating boron-containing wastewater, a precipitate of a boron-containing compound is formed by adjusting the pH to 8 or more in the coexistence of a peroxide and a polyvalent metal compound, and then the precipitate is formed. A wastewater treatment method for reducing the boron concentration in wastewater by separating or recovering the substance from the wastewater is disclosed, but it is dispersible when a polyvalent metal compound and a chelate-bonding component coexist. It was difficult to treat without using good chemicals.

In (Patent Document 4), in order to highly capture heavy metal ions in wastewater, metal ions are used as a solid-liquid separator for water treatment in addition to a flocculant containing iron ions in the wastewater in advance during wastewater treatment with metal ions. By dissolving the contained inorganic oxygen compound, heavy metal ions are aggregated, the sedimentation rate is increased, and heavy metal ions are eluted into the wastewater by utilizing the coprecipitation effect of the flocculant containing the dissolved iron ions. A method of suppressing the above is disclosed. However, a highly dispersible agent for simultaneously treating a plurality of items such as boron, fluorine, phosphorus, ammonia, etc. in wastewater and heavy metal ion concentration is not used.

In (Patent Document 5), a novolak-type phenol resin is dissolved in an alkaline solution, and then aldehydes are added to cause an addition condensation reaction to reduce low molecular weight components during aggregation treatment and to contribute to improvement of aggregation effect. Methods of increasing the ingredients are provided, but no penetrating agents are used during production.

In (Patent Document 6), wastewater and sludge containing organic acids, crystalline aluminosilicates, aluminum salts, magnesium salts, calcium salts, and sodium salts as purification treatment agents for wastewater and sludge in which aggregated heavy metals hardly re-elute. Although it provides a water purification agent, there is no description about improving solubility at the time of preparation.

(Patent Document 7) provides a sludge settling agent capable of coagulating and precipitating with one liquid and facilitating separation after settling sludge by producing a polyacrylamide-based water-absorbent polymer, but it has a diffusion effect during use. No surfactant is used.

(Patent Document 8) is a water treatment method characterized in that, in the water treatment apparatus supplied to the osmosis membrane treatment apparatus, the treatment agent containing a polymer as a main component is a cationic polymer and an anionic polymer. However, it is not manufactured using a drug with good dispersibility.

Japanese Unexamined Patent Publication No. 2013-188726 Japanese Unexamined Patent Publication No. 2014-188432 JP-A-2007-283216 Japanese Unexamined Patent Publication No. 2012-250226 Japanese Unexamined Patent Publication No. 2011-056496 Japanese Unexamined Patent Publication No. 2004-0457740 Japanese Unexamined Patent Publication No. 2012-219173 Japanese Unexamined Patent Publication No. 2008-059824

The problem to be solved by the invention is to separate a water pollutant from an aqueous solution by using a solid gel, and to take in a water pollutant with a different charge in the process of growing the gel from the aqueous solution in a sol state. Is an issue.

As an industrial application field of the drug, for example, the drug can be used in a wastewater treatment facility provided in a very small space that can be barely operated by one worker in a small site of a small or medium-sized factory or a business place. A concentrated solution is needed to reduce the volume as much as possible.

During the production of the solution, the closer the solution concentration is to saturation, the longer it takes to dissolve the solid drug. Therefore, in order to dissolve the powder in a short time, the surface of the powder to be dissolved in water easily permeates. Need to be.

At the time of adding wastewater treatment, when the concentrated chemical is added, it is necessary to improve the dispersibility in the wastewater to prevent lumping and take in water pollutants.

In a method for treating wastewater containing various water pollution control substances, in a method for treating wastewater in which dissolved components are coagulated, settled and separated in the process of adding a substance that produces a sol state to the wastewater and forming a gel-like substance. As an agent to be used, a treatment agent comprising a water-soluble substance for producing a sol-like substance, a polyvalent metal compound, an anion generator, a penetrant and an aqueous solution of a dispersant, and a treatment method thereof are provided.

The penetrant used in the present invention during the production of a drug can dissolve the powder in a short time by facilitating the permeation of water into the surface of the powder during production.

The dispersant used in the production of a drug used in the present invention makes it easy to disperse the sol-like substance in the process of forming a gel-like substance while the drug that produces a sol state added in wastewater takes in a water pollutant. Therefore, there is an effect of preventing agglomerates from agglomerating without taking in water pollutants in wastewater immediately after addition.

In the wastewater purification method containing water pollution control substances, the above water-soluble substances and polyvalent metal compounds are added, and when the gel-like substances in the liquid formed as a result form fine particles, carbon dissolved in the wastewater. , Nitrogen, phosphorus, fluorine, boron, heavy metals can be recovered and concentrated. Examples of heavy metal ions that can be suitably removed during the purification include ions such as iron, aluminum, manganese, nickel, copper, zinc, cadmium, lead, chromium, arsenic, mercury, and selenium.

Using the energy when the electrostatic action such as hydrogen bond and van der Waals force acting on the hydrated ion surrounding the water-soluble substance in the sol state disappears when the sol changes to the gel state, from the anion generator The generated anion uses the energy generated to polarize the hydrated ions surrounding the polyvalent metal compound and exchange electrons with water-soluble substances to adsorb multiple types of water pollution control substances with different charges. To grow into a gel state.

Of the positive and negative charges dissolved in water, for example, a water-soluble substance that produces a gel state attracts a positively charged substance, and a polyvalent metal compound attracts a negatively charged substance, so that substances with different charges are simultaneously attracted. Grow into a gel while taking up. As a result, a method for separating water pollution-regulating substances having different charges from an aqueous solution as a solid gel and a drug to be used are provided.

Since the concentrated solution has a high viscosity and a large specific gravity in order to reduce the volume of the drug as much as possible, when it is dissolved in waste water, it does not disperse but becomes a lump and settles at the bottom of the treatment tank. Penetrants and dispersants are used to prevent the drug from agglomerating and agglomerating.

Any water-soluble substance can be used as long as it is a gel-like substance produced in wastewater containing a water pollution controlling substance, but polyvinyl is used as a water-soluble substance that easily produces a gel-like substance at a relatively low cost. Alcohol, polyacrylic acid or a salt thereof, copolymer of acrylamide and acrylic acid or a salt thereof, polyacrylamide, polyacrylic acid dimethylaminoethyl ester, polymethacrylic acid dimethylaminoethyl ester, cationized modified product of polyacrylamide, polyethylene Immin, polyethylene oxide, polyvinylpyrrolidone, biscous, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate or its salt, phthalate acetate or its salt, propionate acetate cellulose or its salt, carboxymethyl cellulose or its salt, Dextrin, curdran, soluble starch, carboxymethyl starch, dialdehyde starch, citrus starch, potato starch, tapioca starch, wheat starch, corn starch, galactomannan, konjac, funori, carrageenan, agar, farcerelan, acrylic acid or its salts, propylene alginate Glycolester, chitin, chitosan, trolley aoi, tragant gum, arabic gum, guagam, xanthan gum, locust bean gum, gellan gum, pectin, pectic acid or a salt thereof, tamarind seed polysaccharide, latex, sardine, gelatin, casein, collagen, gluten, soybean Glue, sodium tripolyphosphate, starch-acrylic acid graft copolymer of highly water-absorbent resin, vinyl acetate-acrylic acid ester copolymer saponified product, polyacrylic acid cross-linked product, carboxymethyl cellulose cross-linked polymer, zinc oxygen compound or The salt, cadmium oxygen compound or its salt, aluminum oxygen compound or its salt, gallium oxygen compound or its salt, indium oxygen compound or its salt, ittrium oxygen compound or its salt, cerium oxygen compound or its salt, titanium oxygen compound or its Salt, zirconium oxygen compound or salt thereof, tin oxygen compound or salt thereof, iron oxygen compound or salt thereof, cobalt oxygen compound or salt thereof, nickel oxygen compound or salt thereof, vanadium oxygen compound or salt thereof, niobium oxygen compound or The salt, tungsten oxygen compound or its salt, chromium oxygen compound or its salt, molybdenum oxygen compound or its salt, manganese oxygen compound or its salt, copper oxygen compound or its salt, antimony oxygen compound or its salt, silicon oxygen compound or its It is desirable to use a salt, a calcium oxygen compound or a salt thereof, a magnesium oxygen compound or a salt thereof, or one consisting of two or more of these.

The amount of the water-soluble substance that produces the gel-like substance to be added to the wastewater is 0.01 to 400 parts by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the water pollution control substance dissolved in the wastewater. Is the ratio of.

It is effective to use a polyvalent metal compound that acts on the gelation of an aqueous substance that produces a gel-like substance. Polyvalent metal compounds include barium, calcium, strontium, magnesium, zinc, cadmium, aluminum, indium, yttrium, cerium, titanium, zirconium, tin, cobalt, nickel, vanadium, niobium, tungsten, chromium, molybdenum, manganese, iron, It is advisable to appropriately select and use any one of copper, silver and antimony, or a mixture consisting of two or more of these.
As the polyvalent metal compound, for example, as the calcium compound, a water-soluble calcium salt is preferable, and calcium chloride, calcium nitrate, calcium carbonate and the like can be mentioned. As the magnesium compound, a water-soluble magnesium salt is preferable, and examples thereof include magnesium sulfate, magnesium carbonate, magnesium chloride, magnesium nitrate and the like. Examples of the barium compound include barium chloride and barium nitrate salt. As the titanium compound, a water-soluble titanium salt is preferable, and examples thereof include titanium chloride, titanium sulfate, and titanium nitrate. As the aluminum compound, a water-soluble aluminum compound is preferable, and examples thereof include aluminum chloride, aluminum sulfate, aluminum nitrate, polyaluminum chloride, and sodium aluminate. As the iron compound, a water-soluble iron salt is preferable, and one or more of ferrous chloride, ferrous chloride, ferrous sulfate, ferrous sulfate, ferrous nitrate, and ferrous nitrate. It is advisable to appropriately select and use from the mixture containing.

These polyvalent metal compounds exhibit an action of reacting with a water-soluble substance that produces a gel-like substance to form a gel-like substance. The proportion of the polyvalent metal compound used is not particularly limited, but generally 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the water-soluble substance that produces the gel-like substance. It is the ratio of parts by weight.

Chloride ion, chlorate ion, chlorite ion, hypochlorite ion, perchlorate ion, bromide ion, iodide ion, nitrate ion, sulfamic acid as an anion generator during the production of the drug used in the present invention. Ion, borate ion, phosphate ion, sulfate ion, sulfite ion, thiosulfate ion, persulfate ion, hydroxide ion, carbonate ion, hydrogen carbonate ion, sulfide ion, citrate ion, acetate ion, oxalate ion , Carboxylate ion, amino acid ion, ferrocyanion ion, or ferrician ion, whichever is used to generate an anion, or a mixture containing two or more of them may be appropriately selected and used.

The amount of the anion generator 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 produces the gel-like substance.

Nonionic surfactants such as glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, ethylene oxide alkylphenol, polyoxyethylene-polyoxypropylene condensate, and alkyl alcohol as penetrants during the production of the drug used in the present invention. Alchol ethoxylate, 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 diethanol amide, polyethylene glycol, or a mixture containing two or more thereof may be appropriately selected and used.

The amount of the penetrant 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 produces the gel-like substance.

As a dispersant for the drug used in the present invention, alcohols, ketones, polyvinyl alcohol, polyacrylic acid or a salt thereof, a copolymer of acrylamide and acrylic acid or a salt thereof, polyacrylamide, polyacrylic acid dimethylaminoethyl ester , Polymethacrylate dimethylaminoethyl ester, cationized modified product of 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 diethanol amide, polyethylene glycol, Alternatively, it may be appropriately selected and used from a mixture containing two or more kinds.

The amount of the dispersant 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 produces the gel-like substance.

A water-soluble substance and a polyvalent metal compound that generate a gel-like substance during wastewater treatment are added, and the mixture is well stirred and mixed. As long as the stirring / mixing method can be sufficiently mixed, any method used for normal stirring / mixing can be used.

The gel-like substance of the embodiment has a composition 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: lithium, sodium, gallium, calcium, strontium, barium, magnesium, zinc, cadmium, Compositions represented by aluminum, indium, yttrium, cerium, titanium, zirconium, tin, cobalt, nickel, vanadium, niobium, tungsten, chromium, molybdenum, manganese, iron, copper, silver, antimony). It is characterized by being a component that forms a porous particle containing.

Next, a production example and a processing example will be described in detail based on the solution of the present invention.

(Production Example 1) Of the water-soluble substances according to claim 1 or 2, for example, 15 parts by weight of sodium silicate No. 1 and a 1% aqueous solution of a copolymer of acrylamide and acrylic acid with 15 parts by weight of sodium metasilicate. 70 parts by weight of the 1% sodium carbonate aqueous solution according to claim 1 or 4 was added to 1 part by weight and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 1 Treatment Solution (I).

Of the water-soluble substances according to claim 1 or 2, for example, calcium chloride hexahydrate among the polyvalent metal compounds according to claim 1 or 3 with respect to 10 parts by weight of a 10% aqueous solution of polyaluminum chloride. 10 parts by weight, 10 parts by weight of magnesium chloride hexahydrate, and 10 parts by weight of an aqueous solution of 10% aluminum sulfate were added and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 1 Treatment Solution (II).

Among the polyvalent metal compounds according to claim 1 or 3, for example, 4 parts by weight of magnesium chloride hexahydrate, and among the polyvalent metal compounds according to claim 1 or 3, for example, calcium chloride hexahydrate 1. Of the penetrant according to claim 1 or 5, for example, 0.001 part by weight of polyoxyalkylene glyceryl ether and 0.001 part by weight of octylphenol ethoxylate are mixed with 5 parts by weight of water with respect to parts by weight. A mixed solution (colorless, transparent) was prepared. This is designated as Production Example 1 Treatment Solution (III).

The treatment solution (II) and the treatment solution (III) were mixed and used as the treatment solution (IV) of Production Example 1 to obtain a mixed solution (colorless, transparent) in a preparation time of about 30 minutes.

(Production Example 1-2) In order to compare the production time with the penetrant and the production time without the penetrant, 10 parts by weight of a 10% aqueous solution of polyaluminum chloride, 11 parts by weight of calcium chloride hexahydrate, and magnesium chloride. When 14 parts by weight of hexahydrate, 10 parts by weight of an aqueous solution of 10% aluminum sulfate, and 5 parts by weight of water were mixed and prepared, it took more than 1 hour to dissolve in a colorless and transparent state. Therefore, when a penetrant was used. Was more than double the effect.

(Production Example 1 Treatment Example) A plating factory wastewater (zinc ion concentration 1,000 mg / L, ammonium ion concentration 1,000 mg / L, boron concentration 50 mg / L, fluoride ion concentration 100 mg / L, pH 3) to 1,000 mL Production Example 1 Treatment Solution (I) 1,000 mg / L and Production Example 1 Treatment Solution (IV) 1,000 mg / L are added, and among the anion generators according to claim 1 or 4, for example, sodium hydroxide. Was added to adjust the pH to 9, and the mixture was stirred for 5 minutes to grow a colloidal solution of a water-soluble substance in a sol state and a polyvalent metal compound into a gel state without forming a non-uniform lump that occurs when no penetrant was used. Ion. This solution was allowed to stand for 1 hour to coagulate and settle.

(Production Example 1 Evaluation Example) In the above treatment, the concentration of the pollutant controlling substance in the subsequent supernatant was 10 mg / L for zinc ion concentration, 400 mg / L for ammonium ion concentration, 20 mg / L for boron concentration, and fluoride without agglomeration. Since an ion concentration of 4 mg / L was obtained, it was possible to reduce the zinc ion concentration to 1/100, the ammonium ion concentration to 1 / 2.5, the boron concentration to 1 / 2.5, and the fluoride ion concentration to 1 / 2.5. did it.

(Production Example 2) Of the water-soluble substances according to claim 1 or 2, for example, 15 parts by weight of sodium silicate No. 4 and 15 parts by weight of sodium metasilicate according to claim 1 or 4 are compared with hydrogen carbonate according to claim 1 or 4. 70 parts by weight of a 1% sodium aqueous solution was added and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 2 Treatment Solution (I).

Among the water-soluble substances according to claim 1 or 2, for example, the polyvalent metal compound according to claim 1 or 3 with respect to 10 parts by weight of a 10% aqueous solution of polyaluminum chloride and 10 parts by weight of an aqueous solution of 10% aluminum sulfate. For example, 10 parts by weight of magnesium chloride hexahydrate, 10 parts by weight of calcium chloride hexahydrate, and 0.001 part by weight of the polyethylene glycol according to claim 1 or 5 are added and mixed, and a mixed solution (colorless, transparent) is added. Was prepared. This is referred to as Production Example 2 Treatment Solution (II).

Among the polyhydric metal compounds according to claim 1 or 3, for example, 3 parts by weight of magnesium chloride hexahydrate and 2 parts by weight of calcium chloride hexahydrate, and among the penetrants according to claim 1 or 5, for example, A mixed solution (colorless, transparent) was prepared by mixing 5 parts by weight of water with 0.001 part by weight of the secondary alcohol alkoxylate and 0.001 part by weight of polyoxyethylene polyoxypropylene glycol. This is referred to as Production Example 2 Treatment Solution (III).

The above treatment solution (II) and treatment solution (III) were mixed and used as Production Example 2 treatment solution (IV) to obtain a mixed solution (colorless, transparent) in a preparation time of about 30 minutes.

(Production Example 2-2) In order to compare the production time between the above treatment liquid production example and the method without using a penetrant, 10 parts by weight of a 10% polyaluminum chloride aqueous solution, 10 parts by weight of a 10% aluminum sulfate aqueous solution, and magnesium chloride 6 In the method of mixing 5 parts by weight of water with 13 parts by weight of hydrate and 12 parts by weight of calcium chloride hexahydrate, it took 1 hour or more to dissolve in colorless and transparent because the concentration was close to the saturated concentration. Therefore, when the penetrant was used, the effect was more than doubled.

(Production Example 2 Treatment Example) B plating factory wastewater (zinc ion concentration 200 mg / L, ammonium ion concentration 200 mg / L, boron concentration 30 mg / L, fluoride ion concentration 50 mg / L, pH 3) Production Example 2 treatment to 1,000 mL Liquid (I) 500 mg / L and Production Example 2 treatment liquid (IV) 500 mg / L were added, and among the anion generators according to claim 1 or 4, for example, sodium hydroxide was added to adjust the pH to 9. After stirring for 15 minutes, a colloidal solution of a water-soluble substance in a sol state and a polyvalent metal compound was grown in a gel state without forming a non-uniform mass that occurs when no penetrant was used. This solution was allowed to stand for 1 hour to coagulate and settle.

(Production Example 2 Evaluation Example) As for the pollution control substance concentration of the supernatant after the above treatment, zinc ion concentration 2 mg / L, ammonium ion concentration 100 mg / L, boron concentration 10 mg / L, and fluoride ion concentration 3 mg / L were obtained. Therefore, it was possible to reduce the zinc ion concentration to 1/100, the ammonium ion concentration to 1/2, the boron concentration to 1/3, and the fluoride ion concentration to 1/17.

(Production Example 3) Of the water-soluble substances according to claim 1 or 2, for example, 30 parts by weight of sodium silicate No. 3, 5 parts by weight of a 0.1% aqueous solution of dimethylaminoethyl ester polyacrylate, and claim 1. Alternatively, 65 parts by weight of the 0.1% aqueous sodium hydroxide solution described in 4 was added and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 3 Treatment Solution (I).

Of the water-soluble substances according to claim 1 or 2, for example, calcium chloride hexahydrate among the polyvalent metal compounds according to claim 1 or 3 with respect to 20 parts by weight of a 10% aqueous solution of polyaluminum chloride. 20 parts by weight was added and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 3 Treatment Solution (II).

Among the polyvalent metal compounds according to claim 1 or 3, for example, 5 parts by weight of magnesium chloride hexahydrate, and among the penetrants according to claim 1 or 5, for example, polyoxyethylene polyoxypropylene glycol 0. A mixed solution (colorless, transparent) was prepared by mixing 5 parts by weight of water with 0.001 part by weight of 001 parts by weight of polyoxyethylene sorbitan monooleate. This is designated as Production Example 3 Treatment Solution (III).

The treatment solution (II) and the treatment solution (III) were mixed and used as the treatment solution (IV) of Production Example 3 to obtain a mixed solution (colorless, transparent) in a preparation time of about 30 minutes.

(Production Example 3-2) In order to compare the production time between the above treatment liquid production example and the method without using a penetrant, 20 parts by weight of a 10% aqueous solution of polyaluminum chloride, 20 parts by weight of calcium chloride hexahydrate, and magnesium chloride In the method of mixing 5 parts by weight of hexahydrate and 5 parts by weight of water, since the concentration was close to the saturated concentration, it took more than 1 hour to dissolve in colorless and transparent, so when a penetrant was used, 2 It was more than double the effect.

(Production Example 3 Treatment Example) C plating factory wastewater (zinc ion concentration 200 mg / L, ammonium ion concentration 200 mg / L, pH 3) 1,000 mL, the above Production Example 3 treatment solution (I) 400 mg / L, and Production Example 3 It occurs when 400 mg / L of the treatment solution (IV) is added, and among the anion generators according to claim 1 or 4, for example, sodium hydroxide is added to adjust the pH to 9, and the mixture is stirred for 15 minutes without using a penetrant. A colloidal solution of a water-soluble substance in a sol state and a polyvalent metal compound was grown in a gel state without forming a non-uniform mass. This solution was allowed to stand for 1 hour to coagulate and settle.

(Production Example 3 Evaluation Example) Since the pollution control substance concentration of the supernatant after the above treatment was reduced to a zinc ion concentration of 2 mg / L and an ammonium ion concentration of 100 mg / L, the zinc ion concentration was 1/100. The ammonium ion concentration could be reduced to 1/2.

The present invention relates to chemicals used to treat wastewater.

Coupled with the tightening of industrial wastewater regulations, treatment measures are essential for inorganic and organic wastewater treatment to meet the standards. Among them, the treatment is a problem. For inorganic wastewater, copper plating solution, nickel plating solution, chrome plating solution, zinc plating solution, which are discharged from various plating factories, printed substrate factories, and chemical deposition factories. Examples thereof include tin plating solution, brass plating solution, solder plating solution, electroless copper plating solution, electroless nickel plating solution, resist peeling drainage, and etching drainage. Some of these wastewaters contain components that are difficult to treat, such as ammonia, zinc, copper, nickel, and boron fluorine. When gluconic acid, ethylenediaminetetraacetic acid, carboxylic acid compound, ammonia, amine compound, etc. are used, solid-liquid separation cannot be performed by ordinary alkali neutralization treatment. In addition, there is a problem in dealing with boron and fluorine-containing wastewater, which is difficult to treat easily in the ceramic industry, inn industry, livestock industry, etc., when the provisional standard is abolished. In each case, a small-scale and simple standard value achievement processing technology is required.

In general, a method of coagulating and separating a multi-component heavy metal ion as a hydroxide using an alkaline solution in wastewater is widely used and used as a neutralization sedimentation separation method, but it is used as an anion in an aqueous solution such as fluorine or boron. It is difficult to perform a precipitation separation treatment of a gluconic acid, ethylenediaminetetraacetic acid, a carboxylic acid compound, an ammonia, an amine compound, or the like which is a chelate compound with a metal. It is desired for small and medium-sized factories and business establishments to reduce the cost burden of treatment equipment as much as possible when discharging these treated wastewater to public water bodies.

As shown in (Patent Document 1), as a water treatment agent for phosphorus recovery, those obtained by forming powder as an adsorption treatment agent containing silicon and silica have been used so far. Since the form for adsorption is a powder having a large surface area, when it absorbs water after a lapse of time after production, it joins with each other to form a lump, the diffusion rate of the component to be adsorbed decreases, and the treatment effect decreases. Therefore, there is a drawback that the warranty period that can be used is shortened.

In (Patent Document 2), a pH-adjusted phosphoric acid solution is added to a granulated product containing heavy calcium carbonate powder, and the heavy calcium carbonate powder is reacted with phosphoric acid to cause hydroxy on the surface of the heavy calcium carbonate powder. A method for producing a fluoroion adsorbent by precipitating apatite is disclosed. If the powder is not sufficiently dispersed, the diffusion rate of the component to be adsorbed decreases and the treatment effect decreases, so that there is a drawback that the warranty period of the powder that can be used is shortened.

In (Patent Document 3), in the method for treating boron-containing wastewater, a precipitate of a boron-containing compound is formed by adjusting the pH to 8 or more in the coexistence of a peroxide and a polyvalent metal compound, and then the precipitate is formed. A wastewater treatment method for reducing the boron concentration in wastewater by separating or recovering the substance from the wastewater is disclosed, but it is dispersible when a polyvalent metal compound and a chelate-bonding component coexist. It was difficult to treat without using good chemicals.

In (Patent Document 4), in order to highly capture heavy metal ions in wastewater, metal ions are used as a solid-liquid separator for water treatment in addition to a flocculant containing iron ions in the wastewater in advance during wastewater treatment with metal ions. By dissolving the contained inorganic oxygen compound, heavy metal ions are aggregated, the sedimentation rate is increased, and heavy metal ions are eluted into the wastewater by utilizing the coprecipitation effect of the flocculant containing the dissolved iron ions. A method of suppressing the above is disclosed. However, a highly dispersible agent for simultaneously treating a plurality of items such as boron, fluorine, phosphorus, ammonia, etc. in wastewater and heavy metal ion concentration is not used.

In (Patent Document 5), a novolak-type phenol resin is dissolved in an alkaline solution, and then aldehydes are added to cause an addition condensation reaction to reduce low molecular weight components during aggregation treatment and to contribute to improvement of aggregation effect. Methods of increasing the ingredients are provided, but no penetrating agents are used during production.

In (Patent Document 6), wastewater and sludge containing organic acids, crystalline aluminosilicates, aluminum salts, magnesium salts, calcium salts, and sodium salts as purification treatment agents for wastewater and sludge in which aggregated heavy metals hardly re-elute. Although it provides a water purification agent, there is no description about improving solubility at the time of preparation.

(Patent Document 7) provides a sludge settling agent capable of coagulating and precipitating with one liquid and facilitating separation after settling sludge by producing a polyacrylamide-based water-absorbent polymer, but it has a diffusion effect during use. No surfactant is used.

(Patent Document 8) is a water treatment method characterized in that, in the water treatment apparatus supplied to the osmosis membrane treatment apparatus, the treatment agent containing a polymer as a main component is a cationic polymer and an anionic polymer. However, it is not manufactured using a drug with good dispersibility.

Japanese Unexamined Patent Publication No. 2013-188726 Japanese Unexamined Patent Publication No. 2014-188432 JP-A-2007-283216 Japanese Unexamined Patent Publication No. 2012-250226 Japanese Unexamined Patent Publication No. 2011-056496 Japanese Unexamined Patent Publication No. 2004-0457740 Japanese Unexamined Patent Publication No. 2012-219173 Japanese Unexamined Patent Publication No. 2008-059824

The problem to be solved by the invention is to separate a water pollutant from an aqueous solution by using a solid gel, and to take in a water pollutant with a different charge in the process of growing the gel from the aqueous solution in a sol state. Is an issue.

As an industrial application field of the drug, for example, the drug can be used in a wastewater treatment facility provided in a very small space that can be barely operated by one worker in a small site of a small or medium-sized factory or a business place. A concentrated solution is needed to reduce the volume as much as possible.

During the production of the solution, the closer the solution concentration is to saturation, the longer it takes to dissolve the solid drug. Therefore, in order to dissolve the powder in a short time, the surface of the powder to be dissolved in water easily permeates. There is a problem to make.

During the waste water treatment additives, upon addition of concentrated drug, by improving the dispersibility in the waste water, there is a problem that prevents to become massive capture water pollutants.

In a method for treating wastewater containing various water pollution control substances, in a method for treating wastewater in which dissolved components are coagulated, settled and separated in the process of adding a substance that produces a sol state to the wastewater and forming a gel-like substance. As the concentrated agent to be used, a treated concentrated agent comprising a water-soluble substance for producing a sol-like substance, a polyvalent metal compound, an anion generator, a penetrant and an aqueous solution of a dispersant, and a treatment method thereof are provided.

The penetrant used in the present invention during the production of a drug can dissolve the powder in a short time by facilitating the permeation of water into the surface of the powder during production.

The dispersant used in the production of a drug used in the present invention makes it easy to disperse the sol-like substance in the process of forming a gel-like substance while the drug that produces a sol state added in wastewater takes in a water pollutant. Therefore, there is an effect of preventing agglomerates from agglomerating without taking in water pollutants in wastewater immediately after addition.

In the wastewater purification method containing water pollution control substances, the above water-soluble substances and polyvalent metal compounds are added, and when the gel-like substances in the liquid formed as a result form fine particles, carbon dissolved in the wastewater. , Nitrogen, phosphorus, fluorine, boron, heavy metals can be recovered and concentrated. Examples of heavy metal ions that can be suitably removed during the purification include ions such as iron, aluminum, manganese, nickel, copper, zinc, cadmium, lead, chromium, arsenic, mercury, and selenium.

Using the energy when the electrostatic action such as hydrogen bond and van der Waals force acting on the hydrated ion surrounding the water-soluble substance in the sol state disappears when the sol changes to the gel state, from the anion generator The generated anion uses the energy generated to polarize the hydrated ions surrounding the polyvalent metal compound and exchange electrons with water-soluble substances to adsorb multiple types of water pollution control substances with different charges. To grow into a gel state.

Of the positive and negative charges dissolved in water, for example, a water-soluble substance that produces a gel state attracts a positively charged substance, and a polyvalent metal compound attracts a negatively charged substance, so that substances with different charges are simultaneously attracted. Grow into a gel while taking up. As a result, a method for separating water pollution-regulating substances having different charges from an aqueous solution as a solid gel and a drug to be used are provided.

Since the concentrated solution has a high viscosity and a large specific gravity in order to reduce the volume of the drug as much as possible, when it is dissolved in waste water, it does not disperse but becomes a lump and settles at the bottom of the treatment tank. Penetrants and dispersants are used to prevent the drug from agglomerating and agglomerating.

Any water-soluble substance can be used as long as it is a gel-like substance produced in wastewater containing a water pollution controlling substance, but polyvinyl is used as a water-soluble substance that easily produces a gel-like substance at a relatively low cost. Alcohol, polyacrylic acid or a salt thereof, copolymer of acrylamide and acrylic acid or a salt thereof, polyacrylamide, polyacrylic acid dimethylaminoethyl ester, polymethacrylic acid dimethylaminoethyl ester, cationized modified product of polyacrylamide, polyethylene Immin, polyethylene oxide, polyvinylpyrrolidone, biscous, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate or its salt, phthalate acetate or its salt, propionate acetate cellulose or its salt, carboxymethyl cellulose or its salt, Dextrin, curdran, soluble starch, carboxymethyl starch, dialdehyde starch, citrus starch, potato starch, tapioca starch, wheat starch, corn starch, galactomannan, konjac, funori, carrageenan, agar, farcerelan, acrylic acid or its salts, propylene alginate Glycolester, chitin, chitosan, trolley aoi, tragant gum, arabic gum, guagam, xanthan gum, locust bean gum, gellan gum, pectin, pectic acid or a salt thereof, tamarind seed polysaccharide, latex, sardine, gelatin, casein, collagen, gluten, soybean Glue, sodium tripolyphosphate, starch-acrylic acid graft copolymer of highly water-absorbent resin, vinyl acetate-acrylic acid ester copolymer saponified product, polyacrylic acid cross-linked product, carboxymethyl cellulose cross-linked polymer, zinc oxygen compound or The salt, cadmium oxygen compound or its salt, aluminum oxygen compound or its salt, gallium oxygen compound or its salt, indium oxygen compound or its salt, ittrium oxygen compound or its salt, cerium oxygen compound or its salt, titanium oxygen compound or its Salt, zirconium oxygen compound or salt thereof, tin oxygen compound or salt thereof, iron oxygen compound or salt thereof, cobalt oxygen compound or salt thereof, nickel oxygen compound or salt thereof, vanadium oxygen compound or salt thereof, niobium oxygen compound or The salt, tungsten oxygen compound or its salt, chromium oxygen compound or its salt, molybdenum oxygen compound or its salt, manganese oxygen compound or its salt, copper oxygen compound or its salt, antimony oxygen compound or its salt, silicon oxygen compound or its It is desirable to use a salt, a calcium oxygen compound or a salt thereof, a magnesium oxygen compound or a salt thereof, or one consisting of two or more of these.

The amount of the water-soluble substance that produces the gel-like substance to be added to the wastewater is 0.01 to 400 parts by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the water pollution control substance dissolved in the wastewater. Is the ratio of.

It is effective to use a polyvalent metal compound that acts on the gelation of an aqueous substance that produces a gel-like substance. Polyvalent metal compounds include barium, calcium, strontium, magnesium, zinc, cadmium, aluminum, indium, yttrium, cerium, titanium, zirconium, tin, cobalt, nickel, vanadium, niobium, tungsten, chromium, molybdenum, manganese, iron, It is advisable to appropriately select and use any one of copper, silver and antimony, or a mixture consisting of two or more of these.
As the polyvalent metal compound, for example, as the calcium compound, a water-soluble calcium salt is preferable, and calcium chloride, calcium nitrate, calcium carbonate and the like can be mentioned. As the magnesium compound, a water-soluble magnesium salt is preferable, and examples thereof include magnesium sulfate, magnesium carbonate, magnesium chloride, magnesium nitrate and the like. Examples of the barium compound include barium chloride and barium nitrate salt. As the titanium compound, a water-soluble titanium salt is preferable, and examples thereof include titanium chloride, titanium sulfate, and titanium nitrate. As the aluminum compound, a water-soluble aluminum compound is preferable, and examples thereof include aluminum chloride, aluminum sulfate, aluminum nitrate, polyaluminum chloride, and sodium aluminate. As the iron compound, a water-soluble iron salt is preferable, and one or more of ferrous chloride, ferrous chloride, ferrous sulfate, ferrous sulfate, ferrous nitrate, and ferrous nitrate. It is advisable to appropriately select and use from the mixture containing.

These polyvalent metal compounds exhibit an action of reacting with a water-soluble substance that produces a gel-like substance to form a gel-like substance. The proportion of the polyvalent metal compound used is not particularly limited, but generally 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the water-soluble substance that produces the gel-like substance. It is the ratio of parts by weight.

Chloride ion, chlorate ion, chlorite ion, hypochlorite ion, perchlorate ion, bromide ion, iodide ion, nitrate ion, sulfamic acid as an anion generator during the production of the drug used in the present invention. Ion, borate ion, phosphate ion, sulfate ion, sulfite ion, thiosulfate ion, persulfate ion, hydroxide ion, carbonate ion, hydrogen carbonate ion, sulfide ion, citrate ion, acetate ion, oxalate ion , Carboxylate ion, amino acid ion, ferrocyanion ion, or ferrician ion, whichever is used to generate an anion, or a mixture containing two or more of them may be appropriately selected and used.

The amount of the anion generator 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 produces the gel-like substance.

Nonionic surfactants such as glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, ethylene oxide alkylphenol, polyoxyethylene-polyoxypropylene condensate, and alkyl alcohol as penetrants during the production of the drug used in the present invention. Alchol ethoxylate, 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 diethanol amide, polyethylene glycol, or a mixture containing two or more thereof may be appropriately selected and used.

The amount of the penetrant 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 produces the gel-like substance.

As a dispersant for the drug used in the present invention, alcohols, ketones, polyvinyl alcohol, polyacrylic acid or a salt thereof, a copolymer of acrylamide and acrylic acid or a salt thereof, polyacrylamide, polyacrylic acid dimethylaminoethyl ester , Polymethacrylate dimethylaminoethyl ester, cationized modified product of 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 diethanol amide, polyethylene glycol, Alternatively, it may be appropriately selected and used from a mixture containing two or more kinds.

The amount of the dispersant 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 produces the gel-like substance.

A water-soluble substance and a polyvalent metal compound that generate a gel-like substance during wastewater treatment are added, and the mixture is well stirred and mixed. As long as the stirring / mixing method can be sufficiently mixed, any method used for normal stirring / mixing can be used.

The gel-like substance of the embodiment has a composition 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: lithium, sodium, gallium, calcium, strontium, barium, magnesium, zinc, cadmium, Compositions represented by aluminum, indium, yttrium, cerium, titanium, zirconium, tin, cobalt, nickel, vanadium, niobium, tungsten, chromium, molybdenum, manganese, iron, copper, silver, antimony). It is characterized by being a component that forms a porous particle containing.

Next, a production example and a processing example will be described in detail based on the solution of the present invention.

(Production Example 1) Of the water-soluble substances according to claim 1 or 2, for example, 15 parts by weight of sodium silicate No. 1 and a 1% aqueous solution of a copolymer of acrylamide and acrylic acid with 15 parts by weight of sodium metasilicate. 70 parts by weight of the 1% sodium carbonate aqueous solution according to claim 1 or 4 was added to 1 part by weight and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 1 Treatment Solution (I).

Of the water-soluble substances according to claim 1 or 2, for example, calcium chloride hexahydrate among the polyvalent metal compounds according to claim 1 or 3 with respect to 10 parts by weight of a 10% aqueous solution of polyaluminum chloride. 10 parts by weight, 10 parts by weight of magnesium chloride hexahydrate, and 10 parts by weight of an aqueous solution of 10% aluminum sulfate were added and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 1 Treatment Solution (II).

Among the polyvalent metal compounds according to claim 1 or 3, for example, 4 parts by weight of magnesium chloride hexahydrate, and among the polyvalent metal compounds according to claim 1 or 3, for example, calcium chloride hexahydrate 1. With respect to parts by weight, for example, 0.001 part by weight of polyoxyalkylene glyceryl ether among the penetrant according to claim 5, and 0.001 part by weight of octylphenol ethoxylate among the dispersant according to claim 6 . 5 parts by weight of water was mixed to prepare a mixed solution (colorless, transparent). This is designated as Production Example 1 Treatment Solution (III).

The treatment solution (II) and the treatment solution (III) were mixed and used as the treatment solution (IV) of Production Example 1 to obtain a mixed solution (colorless, transparent) in a preparation time of about 30 minutes.

(Production Example 1-2) In order to compare the production time with the penetrant and the production time without the penetrant, 10 parts by weight of a 10% aqueous solution of polyaluminum chloride, 11 parts by weight of calcium chloride hexahydrate, and magnesium chloride. When 14 parts by weight of hexahydrate, 10 parts by weight of an aqueous solution of 10% aluminum sulfate, and 5 parts by weight of water were mixed and prepared, it took more than 1 hour to dissolve in a colorless and transparent state. Therefore, when a penetrant was used. Was more than double the effect.

(Production Example 1 Treatment Example) A plating factory wastewater (zinc ion concentration 1,000 mg / L, ammonium ion concentration 1,000 mg / L, boron concentration 50 mg / L, fluoride ion concentration 100 mg / L, pH 3) to 1,000 mL Production Example 1 Treatment Solution (I) 1,000 mg / L and Production Example 1 Treatment Solution (IV) 1,000 mg / L are added, and among the anion generators according to claim 1 or 4, for example, sodium hydroxide. Was added to adjust the pH to 9, and the mixture was stirred for 5 minutes to grow a colloidal solution of a water-soluble substance in a sol state and a polyvalent metal compound into a gel state without forming a non-uniform lump that occurs when no penetrant was used. Ion. This solution was allowed to stand for 1 hour to coagulate and settle.

(Production Example 1 Evaluation Example) In the above treatment, the concentration of the pollutant controlling substance in the subsequent supernatant was 10 mg / L for zinc ion concentration, 400 mg / L for ammonium ion concentration, 20 mg / L for boron concentration, and fluoride without agglomeration. since the ion concentration 4 mg / L was obtained, zinc ion concentration 1/100, ammonium ion concentration of 1 / 2.5, a boron concentration of 1 / 2.5, it was possible to reduce the fluoride ion concentration of 1/25 ..

(Production Example 2) Of the water-soluble substances according to claim 1 or 2, for example, 15 parts by weight of sodium silicate No. 4 and 15 parts by weight of sodium metasilicate according to claim 1 or 4 are compared with hydrogen carbonate according to claim 1 or 4. 70 parts by weight of a 1% sodium aqueous solution was added and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 2 Treatment Solution (I).

Among the water-soluble substances according to claim 1 or 2, for example, the polyvalent metal compound according to claim 1 or 3 with respect to 10 parts by weight of a 10% aqueous solution of polyaluminum chloride and 10 parts by weight of an aqueous solution of 10% aluminum sulfate. For example, 10 parts by weight of magnesium chloride hexahydrate, 10 parts by weight of calcium chloride hexahydrate, and 0.001 part by weight of the polyethylene glycol according to claim 1 or 5 are added and mixed, and a mixed solution (colorless, transparent) is added. Was prepared. This is referred to as Production Example 2 Treatment Solution (II).

Among the polyvalent metal compounds according to claim 1 or 3, for example, 3 parts by weight of magnesium chloride hexahydrate and 2 parts by weight of calcium chloride hexahydrate, and the penetrant and dispersant according to claim 1 or 5 and 6. Of these, for example, 0.001 part by weight of secondary alcohol alkoxylate and 0.001 part by weight of polyoxyethylene polyoxypropylene glycol are mixed with 5 parts by weight of water to prepare a mixed solution (colorless, transparent). did. This is referred to as Production Example 2 Treatment Solution (III).

The above treatment solution (II) and treatment solution (III) were mixed and used as Production Example 2 treatment solution (IV) to obtain a mixed solution (colorless, transparent) in a preparation time of about 30 minutes.

(Production Example 2-2) In order to compare the production time between the above treatment liquid production example and the method without using a penetrant, 10 parts by weight of a 10% polyaluminum chloride aqueous solution, 10 parts by weight of a 10% aluminum sulfate aqueous solution, and 6 magnesium chloride. In the method of mixing 5 parts by weight of water with 13 parts by weight of hydrate and 12 parts by weight of calcium chloride hexahydrate, it took 1 hour or more to dissolve in colorless and transparent because the concentration was close to the saturated concentration. Therefore, when the penetrant was used, the effect was more than doubled.

(Production Example 2 Treatment Example) B plating factory wastewater (zinc ion concentration 200 mg / L, ammonium ion concentration 200 mg / L, boron concentration 30 mg / L, fluoride ion concentration 50 mg / L, pH 3) Production Example 2 treatment to 1,000 mL Liquid (I) 500 mg / L and Production Example 2 treatment liquid (IV) 500 mg / L were added, and among the anion generators according to claim 1 or 4, for example, sodium hydroxide was added to adjust the pH to 9. After stirring for 15 minutes, a colloidal solution of a water-soluble substance in a sol state and a polyvalent metal compound was grown in a gel state without forming a non-uniform mass that occurs when no penetrant was used. This solution was allowed to stand for 1 hour to coagulate and settle.

(Production Example 2 Evaluation Example) As for the pollution control substance concentration of the supernatant after the above treatment, zinc ion concentration 2 mg / L, ammonium ion concentration 100 mg / L, boron concentration 10 mg / L, and fluoride ion concentration 3 mg / L were obtained. Therefore, it was possible to reduce the zinc ion concentration to 1/100, the ammonium ion concentration to 1/2, the boron concentration to 1/3, and the fluoride ion concentration to 1/17.

(Production Example 3) Among the water-soluble substances according to claim 1 or 2, for example, 30 parts by weight of sodium silicate No. 3, 5 parts by weight of a 0.1% aqueous solution of dimethylaminoethyl ester polyacrylate, and claim 1. Alternatively, 65 parts by weight of the 0.1% aqueous sodium hydroxide solution described in 4 was added and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 3 Treatment Solution (I).

Of the water-soluble substances according to claim 1 or 2, for example, calcium chloride hexahydrate among the polyvalent metal compounds according to claim 1 or 3 with respect to 20 parts by weight of a 10% aqueous solution of polyaluminum chloride. 20 parts by weight was added and mixed to prepare a mixed solution (colorless, transparent). This is referred to as Production Example 3 Treatment Solution (II).

Of claims 1 or 3 polyvalent metal compounds described in, for example, magnesium chloride hexahydrate 5 parts by weight, according to claim 1 or 5, 6 wherein the osmotic agent, of the dispersing agent, for example, polyoxyethylene 0.001 part by weight polyoxypropylene glycol with respect to polyoxyethylene sorbitan monooleate 0.001 part by weight, were mixed with water 5 parts by weight, the mixed solution (colorless, transparent) was prepared. This is designated as Production Example 3 Treatment Solution (III).

The treatment solution (II) and the treatment solution (III) were mixed and used as the treatment solution (IV) of Production Example 3 to obtain a mixed solution (colorless, transparent) in a preparation time of about 30 minutes.

(Production Example 3-2) In order to compare the production time between the above treatment liquid production example and the method without using a penetrant, 20 parts by weight of a 10% aqueous solution of polyaluminum chloride, 20 parts by weight of calcium chloride hexahydrate, and magnesium chloride In the method of mixing 5 parts by weight of hexahydrate and 5 parts by weight of water, since the concentration was close to the saturated concentration, it took more than 1 hour to dissolve in colorless and transparent, so when a penetrant was used, 2 It was more than double the effect.

(Production Example 3 Treatment Example) C plating factory wastewater (zinc ion concentration 200 mg / L, ammonium ion concentration 200 mg / L, pH 3) 1,000 mL, the above Production Example 3 treatment solution (I) 400 mg / L, and Production Example 3 It occurs when 400 mg / L of the treatment solution (IV) is added, and among the anion generators according to claim 1 or 4, for example, sodium hydroxide is added to adjust the pH to 9, and the mixture is stirred for 15 minutes without using a penetrant. A colloidal solution of a water-soluble substance in a sol state and a polyvalent metal compound was grown in a gel state without forming a non-uniform mass. This solution was allowed to stand for 1 hour to coagulate and settle.

(Production Example 3 Evaluation Example) Since the pollution control substance concentration of the supernatant after the above treatment was reduced to a zinc ion concentration of 2 mg / L and an ammonium ion concentration of 100 mg / L, the zinc ion concentration was 1/100. The ammonium ion concentration could be reduced to 1/2.

Claims (6)

In the process of forming a gel-like substance by adding a substance that produces a sol state to wastewater containing various water pollution control substances, the sol-like substance is used in a wastewater treatment method in which dissolved components are coagulated, settled and separated. A treatment agent and a treatment method thereof, which comprises a water-soluble substance, a polyvalent metal compound, an anion generator, a penetrant, and an aqueous solution of a dispersant to be produced. The water-soluble substance is 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, carboxymethyl cellulose or a salt thereof, an aluminum oxygen compound or a salt thereof. , Gallium oxygen compound or its salt, indium oxygen compound or its salt, yttrium oxygen compound or its salt, cerium oxygen compound or its salt, titanium oxygen compound or its salt, zirconium oxygen compound or its salt, tin oxygen compound or its salt, Iron oxygen compound or its salt, cobalt oxygen compound or its salt, vanadium oxygen compound or its salt, niobium oxygen compound or its salt, tungsten oxygen compound or its salt, molybdenum oxygen compound or its salt, manganese oxygen compound or its salt, antimon Oxygen compound or salt thereof, silicon oxygen compound or salt thereof, calcium oxygen compound or salt thereof, magnesium oxygen compound or salt thereof, strontium oxygen compound or salt thereof, barium oxygen compound or salt thereof, or two or more of them. The method according to claim 1. The polyvalent metal compounds are barium, strontium, calcium, magnesium, zinc, cadmium, aluminum, indium, yttrium, cerium, titanium, zirconium, tin, cobalt, nickel, vanadium, niobium, tungsten, chromium, molybdenum, manganese, iron, The method according to claim 1, which comprises any one of copper, silver and antimony, or a compound containing two or more of these. The anion generator is chloride ion, chlorate ion, chlorite ion, hypochlorite ion, perchlorate ion, bromide ion, iodide ion, nitrate ion, sulfamate ion, borate ion, phosphate ion. , Sulfate ion, sulfite ion, thiosulfate ion, persulfate ion, hydroxide ion, carbonate ion, hydrogen carbonate ion, sulfide ion, citrate ion, acetate ion, oxalate ion, carboxylate ion, amino acid ion, fe The method according to claim 1, which is a compound that generates an anion with a Russian ion or a ferrician ion. The penetrant is a nonionic surfactant, ether type, ester type, diester type, sorbitan ester type, sorbitan ester / ethylene oxide addition type, monoglyceride type, monoglyceride / ethylene oxide addition type, triglyceride / ethylene oxide addition type, sorbit. Ester / ethylene oxide addition type, polyglycerin alkyl ester type, polyethylene glycol / polypropylene glycol / block ether type, polyetheramine type, alkanolamide type, alkanolamide / ethylene oxide addition type, amine oxide type, glycerin fatty acid ester, sorbitan fatty acid ester, Polysorbate fatty acid ester, ethylene oxide alkylphenol, polyoxyethylene-polyoxypropylene condensate, alkyl alcohol alkoxylate, alcohol ethoxylate, alkyl ethoxylate, alkyl polyethoxylate, fatty acid methyl ester ethoxylate, polyoxyethylene polyoxypropylene glycol, The method according to claim 1, which comprises any one, or two or more of sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, phenol ethoxylate, fatty acid diethanol amide, and polyethylene glycol. The dispersant of the drug used in the present invention is alcohols, ketones for organic solvents, alkyl sulphate type, alkyl ether sulphate type, amide ether sulfate type, methyl taurine type, amino acid type, dialkyl for anionic surfactants. Sodium sulfosuccinate type, alkylbenzene sulfonic acid type, fatty acid soap, water repellent, amine salt type, trimethyl type, dialkyl type, benzyl type, perfluoroalkylcyclohexanesulfonic acid or its salt, fluorine type , Trifluoromethanesulfonic acid or its salt, nonafluorobutanesulfonic acid or its salt, pentafluoroethanesulfonic acid, pentafluoropropanesulfonic acid or its salt, polyvinyl alcohol, polyacrylic acid or its salt, acrylamide and acrylic acid Polymer or salt thereof, polyacrylamide, polyacrylic acid dimethylaminoethyl ester, polymethacrylate dimethylaminoethyl ester, cationized modified product of polyacrylamide, polyethyleneimine, polyethylene oxide, ethylene oxide alkylphenol, polyoxyethylene-polyoxypropylene Condensates, alkyl alcohol alkoxylates, alcohol ethoxylates, alkyl ethoxylates, alkyl polyethoxylates, fatty acid methyl ester ethoxylates, polyoxyalkylene glyceryl ethers, polyoxyethylene polyoxypropylene glycol, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl The method according to claim 1, which comprises any one or more of ester, phenol ethoxylate, fatty acid diethanol amide, and polyethylene glycol.