JP2007014947A - Method for treating waste water and agent therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for concentrating and drying waste water containing various pollutants via distillation, capable of always easily taking a distillation residue out of a distiller without the residue adhering to the surface of the distiller, and an agent for use in the method. <P>SOLUTION: The method for treating the waste water containing the various pollutants comprises adding to the waste water a water-soluble material producing a gel-like substance, and concentrating and drying the waste water in the presence of the gel-like substance. As for the water-soluble material, the following can be used: carboxymethyl cellulose or its salt; alginic acid or its salt; pectin, pectic acid or its salt; polyacrylic acid or its salt; a copolymer of acrylamide and acrylic acid or its salt; or the like. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

For waste water (drainage) containing relatively low concentrations of pollutants, many treatment technologies corresponding to individual pollutants have been developed, and effective treatment is often performed. In contrast, waste liquids containing high-concentration pollutants are almost always disposed of as industrial waste because normal wastewater treatment is hardly applicable. Combustible waste liquids mainly composed of organic substances can be concentrated and burned, but there is also a concern about the production of secondary pollutants such as dioxins. Therefore, since the initial cost when introducing the combustion apparatus including the countermeasures increases, the combustion process is not functioning as a general process except in special cases. Furthermore, disposal of waste liquids that contain toxic heavy metals that cannot be combusted is particularly problematic. These waste liquids are concentrated and solidified, and then disposed of at the waste disposal site.Recently, the disposal costs have increased as the remaining years of the disposal site have decreased, and the water content of the concentrated sludge has been reduced as much as possible. It is necessary to reduce the amount of waste. In addition, there are waste liquids that generate bad odors or generate harmful gases during concentration, and in order to treat these waste liquids, a separate deodorizing device or harmful gas recovery device is required. Since it cannot concentrate, processing cost will increase. Some of these waste liquids contain a lot of valuable metals such as copper, and reuse is also required from the viewpoint of effective use of resources, but in this case as well, by reducing the moisture content of the concentrated residue and increasing the dryness, The value as a resource can be increased. For this reason, there is a need for a method for concentrating and drying high-concentration waste liquid that is low in cost and has a low environmental impact.
On the other hand, some waste liquids mainly composed of organic substances are combusted like pulp cooking waste liquids, but waste liquids that do not contain harmful substances such as food factories are reused as feed from the viewpoint of environmental conservation. In order to reduce the amount of waste. In this case, the operation of concentrating and drying finally is indispensable, and here too, establishment of a concentrating and drying method with low cost and low environmental load is required.

Concentrated waste liquids differ in terms of emissions and their components, but it is not an exaggeration to say that they are discharged from all types of industry, and coupled with the tightness of industrial waste disposal sites, it is becoming a serious problem. Among these, disposal is a problem, such as electroless copper plating solution, electroless nickel plating solution, resist stripping waste solution, etching waste solution, etc. discharged from various plating factories and printed circuit board factories. These waste liquids contain high-value metals such as copper and nickel, but most of the waste liquids are disposed of as industrial waste.
Organic waste liquids that do not contain toxic substances include waste liquids discharged from various food factories, waste liquids and filtrates discharged during the manufacturing process of beer, shochu, and sake, and sludge generated during wastewater treatment. There are things.

  On the other hand, even waste liquids containing relatively low-concentration pollutants that can be treated with ordinary waste water, such as EDTA waste liquid discharged from printed circuit board factories, etc., are usually difficult to treat. If it flows into a general wastewater treatment system, it will interfere with the wastewater treatment system itself. Therefore, measures such as diluting from 100 times to 1000 times are taken regardless of the low concentration waste liquid. Various methods, such as chemical oxidation, have been developed for such waste liquid, and the existing waste water treatment has been developed. However, in reality, the waste liquid is actually diluted. Such difficult-to-process low-concentration wastewater generally has a small amount of discharge, and therefore, a method of evaporating to dryness is often effective.

Concentrated waste liquid is considered to be more rational than normal wastewater treatment because of the high concentration of pollutant components. In addition, for wastewater that has no other effective treatment method even with relatively low-concentration wastewater, a method of concentrating and solidifying the wastewater is effective. For this reason, patents relating to methods and apparatuses for concentration have already been published. For example, Patent Document 1 discloses an invention of a vacuum distillation type waste liquid treatment apparatus.
Concentration and drying operations are widely used as a general processing technique, and some apparatuses are actually operating in factories. Such an apparatus includes, for example, a drum dryer, and an attempt to concentrate and dry the waste liquid has been made.
JP 2001-162265 A

When performing concentration by distillation, it is preferable that the water content is reduced as much as possible, but the distillation residue adheres firmly to the surface of the distillation vessel by treating the water content too low or at a high temperature, and the residue Often it becomes difficult to take out. In addition, a high-boiling substance is included in the distillation residue, and an extremely viscous residue is generated, which often makes subsequent operations difficult. Also in Patent Document 1, it is pointed out that when the water content becomes 5% or less, the viscosity increases and the natural fall does not occur. In an actual distillation operation, it is desirable to obtain a distillation residue having a moisture content as low as possible in a state where it can be easily removed without being fixed to the surface of the distillation vessel. Have difficulty.
In addition, waste liquid treatment using a drying device such as a drum dryer has been attempted. In many cases, however, the dried product adheres to the drying surface of the drum or the like and cannot be easily peeled off. There are many examples that have not been put to practical use.

Therefore, in the present invention, when the waste liquid is distilled and concentrated to dryness, the method for making it possible to easily remove the distillation residue from the distillation vessel at all times without particularly worrying about the end of the distillation, and the method therefor The purpose is to provide a drug.
In addition, for the purpose of providing a method for preventing a problem such that a dried product adheres to a drying device such as a drum and cannot be peeled off when the waste liquid is processed by a drying device such as a drum dryer, and a drug for that purpose. Yes.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

  That is, according to the present invention, in a method of treating a waste liquid containing various pollutant components, a water-soluble substance that generates a gel-like substance is added to the waste liquid, and the waste liquid is removed in a state where the gel-like substance is present. It is characterized by being concentrated to dryness. The method for concentrating and drying the waste liquid may be any method that can disperse the water in the waste liquid and dry the residue, and may be any method such as sun drying or heat drying. In addition, when performing heat drying, any heating method can be adopted, and it is best to appropriately determine whether or not it contains a malodorous component or a harmful volatile component, processing ability, economical efficiency, etc. You can adopt the method that you think.

The waste liquid here refers to those containing high-concentration pollutants that are not applicable to general water treatment, including blood-containing waste liquids, various food factory waste liquids, waste liquids and yeast discharged from the production process of beer and sake. Liquid, concentrated waste liquid of shochu distiller, emulsified oil waste liquid, used waste liquid of electroless plating liquid, etching waste liquid, resist waste liquid, etc., but it contains heavy metals or generates harmful substances when burned, etc. The effect is particularly great for waste liquids not suitable for combustion treatment. It is also effective for wastewater and wastewater having a relatively low concentration that are difficult to apply to general water treatment. Note that the waste liquid here does not only refer to what is disposed of as industrial waste, but it is a concentrated liquid such as filtrate from the manufacturing process, and its effective usage has been established. Also included are those that perform solid operations.
Further, drying means not simply concentrating the waste liquid but removing water in the waste liquid until a solid residue is obtained.

  The gel is described as “a polymer having a three-dimensional network structure insoluble in any solvent and its swelling body” according to “Gel Handbook” (1997, NTS Corporation). “Polymers having a three-dimensional network structure” have a cross-linked structure, and thus exhibit a finite swelling property. And it changes from a viscous liquid to a fairly hard solid. In addition, the generation of the crosslinked structure is not necessarily caused by a chemical reaction, and can be performed by a secondary bond such as a hydrogen bond between specific units of different chains. In this way, the gel has a three-dimensional network structure by crosslinking the polymer, absorbs the solvent in the solvent, swells to a certain limit volume but does not dissolve, and takes a state belonging to the middle of the solid and liquid. It is a substance.

  The “gel-like substance” in the present invention may have such a property of the gel itself, or may be a substance similar to the gel. Further, it may be a semi-gel-like substance that does not have a sufficient cross-linking structure and does not form a complete three-dimensional network structure, or a part of the substance may be in a gel state.

  The generation of the “gel substance” in the present invention may be a weak bond such as a hydrogen bond, or may be caused by a chemical reaction such as an ionic bond or further an esterification bond, and is not particularly limited. Any binding mode that produces the substance may be used.

  When the water-soluble substance added to the waste liquid is a water-soluble substance that produces a gel substance alone, the water-soluble substance alone or two or more of the water-soluble substances may be added. When polyvalent metal ions are required or when it is preferable that polyvalent metal ions are present, it is desirable to add a polyvalent metal compound that generates polyvalent metal ions in water. In addition, when an inorganic polyvalent anion is required for the formation of a gel substance, or when it is preferable that an inorganic polyvalent anion is present, an inorganic polyvalent anion generator that generates an inorganic polyvalent anion in water is used in combination. It is desirable.

  In the present invention, any water-soluble substance can be used as long as it generates a gel-like substance. However, polyvinyl alcohol, carrageenan, agar, chitosan, which easily and easily form a gel-like substance, can be used. Carboxymethylcellulose or a salt thereof, pectin, pectic acid or a salt thereof, alginic acid or a salt thereof, polyacrylic acid or a salt thereof, a copolymer of acrylamide and acrylic acid or a salt thereof, sodium tripolyphosphate, dimethylaminoethyl polyacrylate It is desirable to use any one of esters and polydimethylmethacrylic acid dimethylaminoethyl ester, or those composed of two or more thereof. The gel-like material may be an aluminum hydroxide gel or a highly water-absorbent resin.

  In the present invention, it is effective to use a polyvalent metal compound that acts on gelation of a water-soluble substance that forms a gel-like substance. The polyvalent metal compound is not particularly limited as long as it acts on the gelation of the water-soluble substance, and among these, any of magnesium compounds, calcium compounds, copper compounds, aluminum compounds, iron compounds, or two or more of these compounds It is good to use suitably selecting from the mixture which becomes.

  In the present invention, it is effective to use an inorganic polyvalent anion generator that acts on gelation of a water-soluble substance that forms a gel-like substance. The inorganic polyvalent anion generator is not particularly limited as long as it acts on the gelation of the water-soluble substance. Among them, a carbonate compound that generates carbonate ions, a sulfate compound that generates sulfate ions, and a phosphate ion are generated. A phosphoric acid compound is mentioned.

In this invention, the chemical | medical agent used when a waste liquid is concentrated and dried is provided. Examples of the drug include (1) water-soluble substance carboxymethyl cellulose or a salt thereof, alginic acid or a salt thereof, polyacrylic acid or a salt thereof, a copolymer of acrylamide and acrylic acid or a salt thereof, tripolylin Any one of sodium acid or two or more of these and a polyvalent metal compound, and (2) Polyvinyl alcohol, carrageenan, agar, chitosan or any of these two or more and inorganic Containing polyvalent anion generator, and (3) carboxymethylcellulose or its water-soluble substance that can be swollen with water, polyvinyl alcohol, carrageenan, agar, alginic acid or its salt, polyacrylamide, acrylamide and acrylic With acid Polymer or a salt thereof, polyacrylic acid dimethylaminoethyl ester, polymethacrylic acid dimethylaminoethyl ester, or any the like made of two or more thereof.
In the present invention, the chemical used when the waste liquid is concentrated and dried may be liquid or solid. If a solid is used, the increase in the volume of the waste liquid can be reduced.

  Unlike waste water from factories, waste liquids containing high concentrations of pollutants cannot be processed by ordinary waste water treatment, but are concentrated and disposed of at waste disposal sites. However, there is a significant increase in disposal costs and a shortage of disposal sites. It was a problem. For this reason, in order to reduce the volume of the concentrate as much as possible, it is desirable to reduce the water content, that is, to dry, but there is a problem that the residue firmly adheres to the drying device and cannot be easily removed. It was.

  According to the method of the present invention, when the waste liquid is concentrated and dried, the concentrated residue can be easily taken out from the drying apparatus. As a result, it is possible to obtain a waste having a lower moisture content than before, and as a result, it is possible to contribute to the reduction of waste disposal costs and the extension of the life of the waste disposal site.

  In the present invention, a water-soluble substance that generates a gel substance is added to the waste liquid, and the waste liquid is concentrated and dried in a state where the gel substance is present.

  Any water-soluble substance that generates a gel substance can be used as long as it generates a gel substance. As such, polyvinyl alcohol, polyacrylic acid or a salt thereof, a copolymer of acrylamide and acrylic acid or a salt thereof, polyacrylamide, polydimethylaminoethyl ester of polyacrylate, polydimethylaminoethyl ester of polymethacrylate, polyacrylamide Cationized modified product, polyethyleneimine, polyethylene oxide, polyvinylpyrrolidone, viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose acetate or salt thereof, cellulose acetate phthalate or salt thereof, cellulose acetate propionate or salt thereof, Carboxymethylcellulose or its salt, dextrin, curdlan, soluble starch, carboxymethyl starch, di Rudehydr starch, candied starch, potato starch, tapioca starch, wheat starch, corn starch, galactomannan, konjac, funori, carrageenan, agar, farseleran, alginic acid or its salt, alginate propylene glycol ester, chitin, chitosan, troloaoi, tragacanth gum, gum arabic gum , Guar gum, xanthan gum, locust bean gum, gellan gum, pectin, pectic acid or salt thereof, tamarind seed polysaccharide, latex, glue, gelatin, casein, collagen, gluten, soybean glue, sodium silicate, sodium tripolyphosphate, etc. Starch-acrylic acid graft copolymer, saponified vinyl acetate-acrylic acid ester copolymer, polyacrylate salt Things, carboxymethyl cellulose cross-linked polymer and the like.

  One form of the drug used for concentrating and drying the waste liquid of the present invention is a drug composed of a mixture of a water-soluble substance that generates a gel substance and a polyvalent metal compound.

  In the present invention, carboxymethyl cellulose or a salt thereof, alginic acid or a salt thereof, pectin, pectinic acid or a salt thereof, polyacrylic acid or a salt thereof, co-polymerization of acrylamide and acrylic acid, which is inexpensive and relatively easily produces a gel-like substance. It is desirable to use a combination or a salt thereof, sodium tripolyphosphate, or a combination thereof.

  The amount of the water-soluble substance that forms a gel substance added to the waste liquid is 0.01 to 500 parts by weight, preferably 0.05 to 50 parts by weight, per 100 parts by weight of the solid content (after drying) in the waste liquid. More preferably, the proportion is 0.1 to 10 parts by weight. If it is 0.01 parts by weight or less, the effect of the present invention does not appear, and even if it is added by 500 parts by weight or more, there is no difference in effect, and the processing cost increases.

  The agent of the present invention is preferably used in combination with a polyvalent metal compound that dissolves in an aqueous solution and generates a polyvalent metal ion.

  The polyvalent metal compound is not particularly limited as long as it acts on the gelation of a water-soluble substance that forms a gel-like substance, and among them, any of a magnesium compound, a calcium compound, a copper compound, an aluminum compound, an iron compound, or A mixture of these two or more may be appropriately selected and used.

  The magnesium compound is preferably a water-soluble magnesium salt, and examples thereof include magnesium sulfate, magnesium carbonate, magnesium chloride, and magnesium nitrate. The calcium compound is preferably a water-soluble calcium salt, and examples include calcium chloride, calcium nitrate, and calcium carbonate. The copper compound is preferably a water-soluble copper salt, and examples thereof include copper chloride, copper sulfate, and copper nitrate. The aluminum compound is preferably a water-soluble aluminum compound, and examples include aluminum chloride, aluminum sulfate, aluminum nitrate, polyaluminum chloride, and sodium aluminate. The iron compound is preferably a water-soluble iron salt, and examples thereof include ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, ferrous nitrate, ferric nitrate, and polyiron.

  These polyvalent metal compounds have an action of reacting with a water-soluble substance that generates a gel substance to generate a gel substance. The use ratio of the polyvalent metal compound is not particularly limited, but is generally 1 to 20000 parts by weight, preferably 1 to 5000 parts by weight, with respect to 100 parts by weight of the water-soluble substance that forms the gel substance. The ratio is preferably 2 to 2000 parts by weight, more preferably 10 to 1000 parts by weight. If it is 1 part by weight or less, an effective gel-like substance cannot be produced, and even if it is used in combination with 20000 parts by weight or more, further improvement of the effect is not recognized and the processing cost increases, which is not preferable.

In the practice of the present invention, it is desirable to perform an operation of adding a drug composed of a water-soluble substance that generates a gel-like substance and a polyvalent metal compound to the waste liquid, and concentrating to dryness. In the case where sufficient polyvalent metal ions are present to form a gel-like substance, the water-soluble substance alone may be added, or the amount of polyvalent metal compound added can be reduced.
The drug to be added may be liquid or solid. Alternatively, both liquid and solid, or a mixture thereof may be used.
The order of adding the water-soluble substance and the polyvalent metal compound that generate the gel substance to the waste liquid may be the former added first and the latter added later, or vice versa. Moreover, both may be added simultaneously and a mixture of both may be added.

  Another form of the drug used for concentrating and drying the waste liquid of the present invention is a drug comprising a water-soluble substance that generates a gel substance and an inorganic polyvalent anion generator that generates an inorganic polyvalent anion. .

  Any water-soluble substance that generates a gel substance can be used as long as it generates a gel substance. In the present invention, it is desirable to use any one of polyvinyl alcohol, carrageenan, agar, chitosan, or a combination of two or more thereof, which can form a gel-like substance relatively easily in the presence of a polyvalent anion.

  The amount of the water-soluble substance that forms a gel substance added to the waste liquid is 0.01 to 500 parts by weight, preferably 0.05 to 50 parts by weight, per 100 parts by weight of the solid content (after drying) in the waste liquid. More preferably, the proportion is 0.1 to 10 parts by weight. If it is 0.01 parts by weight or less, the effect of the present invention does not appear, and even if it is added by 500 parts by weight or more, there is no difference in effect, and the processing cost increases.

  The inorganic polyvalent anion generator is not particularly limited as long as it acts on the gelation of a water-soluble substance that generates a gel substance. Among them, sulfate compounds that generate sulfate ions, carbonate compounds that generate carbonate ions, phosphorus compounds Examples thereof include phosphoric acid compounds that generate acid ions. Examples of the sulfuric acid compound include sodium sulfate, potassium sulfate, ferrous sulfate, ferric sulfate, aluminum sulfate, magnesium sulfate, sulfuric acid and the like. Examples of the carbonate compound include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium carbonate and the like. Examples of phosphoric acid compounds include sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, phosphoric acid, sodium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, acidic sodium metaphosphate, sodium hexametaphosphate, etc. Is included. These inorganic polyvalent anion generators have an action of reacting with a water-soluble substance that generates a gel substance to generate a gel substance. The use ratio of the inorganic polyvalent anion generator is not particularly limited, but is generally 1 to 20000 parts by weight, preferably 1 to 5000 parts by weight, more preferably 2 parts per 100 parts by weight of the water-soluble substance. It is the ratio of -2000 weight part, More preferably, it is 10-1000 weight part. If it is 1 part by weight or less, an effective gel-like substance cannot be produced, and even if it is used in combination with 20000 parts by weight or more, further improvement of the effect is not recognized and the processing cost increases, which is not preferable.

In the practice of the present invention, it is desirable to add a chemical comprising a water-soluble substance that generates a gel substance and an inorganic polyvalent anion generator to the waste liquid, and perform concentration and drying. In the case where there are sufficient inorganic polyvalent anions to form a gel-like substance from the active substance, only the water-soluble substance may be added, or the amount of the inorganic polyvalent anion generator added may be reduced. I can do it.
The drug to be added may be liquid or solid. Alternatively, both liquid and solid, or a mixture thereof may be used.
The order of adding the water-soluble substance that generates a gel substance and the inorganic polyvalent anion generator to the waste liquid may be the former added first and the latter added later, or vice versa. Moreover, both may be added simultaneously and a mixture of both may be added.

  Yet another form of the drug used for concentrating and drying the waste liquid of the present invention is a drug characterized by comprising a water-soluble substance that can be swollen with water.

  Any water-soluble substance can be used as long as it easily swells in water to form a gel-like substance, but in the present invention, it swells in water relatively easily to produce a gel-like substance. Carboxymethyl cellulose or a salt thereof, polyvinyl alcohol, carrageenan, agar, alginic acid or a salt thereof, polyacrylamide, polyacrylic acid or a salt thereof, a copolymer of acrylamide and acrylic acid or a salt thereof, polydimethylaminoethyl ester of polyacrylic acid, It is desirable to use polydimethylmethacrylic acid dimethylaminoethyl ester, sodium silicate, a superabsorbent resin, or a combination of two or more of these. The concentration when swollen with water is 0.1 to 50% by weight, preferably 1 to 50% by weight, and more preferably 5 to 20% by weight.

The amount of the water-soluble substance to be added to the waste liquid is 0.01 to 500 parts by weight, preferably 0.05 to 50 parts by weight, more preferably 0.8 parts by weight per 100 parts by weight of the solid content (after drying) in the waste liquid. It is a ratio of 1 to 10 parts by weight. If it is 0.01 parts by weight or less, the effect of the present invention does not appear, and even if it is added by 500 parts by weight or more, there is no difference in effect, and the processing cost increases.
The drug to be added may be liquid or solid. If a solid is used, the increase in the volume of the waste liquid can be reduced.

  In order to carry out the present invention, a water-soluble substance or the like that generates a gel-like substance may be added to the waste liquid so that the gel-like substance is present and concentrated to dryness.

  Add a water-soluble substance that generates a gel-like substance to the waste liquid and mix well. As long as mixing and mixing can be performed sufficiently, any method used for normal stirring and mixing can be performed.

In the present invention, after the gel substance is present in the waste liquid, a fiber substance such as a pulverized paper may be added and concentrated to dryness. When the fiber material is added, the dried product does not adhere to the surface of the container when solidified, and peeling becomes easy.
The fiber material in the present invention is natural fiber such as paper, pulp, wood powder, sawdust, silkworm, cotton, hemp, silk, wool, etc., synthetic fiber, chemical fiber such as synthetic fiber, cellulose powder, cellulose fiber, waste paper recycling process Screen ridges coming out of, and crushed and crushed materials thereof. A pulverized waste paper is preferable because it is easily available and inexpensive.
The amount of the fiber material added is 0.1 to 30% by weight, preferably 1 to 10% by weight, based on the solid content (after drying) in the waste liquid.

  As a method of concentrating and drying the waste liquid, any method may be used as long as it can disperse the water in the waste liquid and dry the residue, and any method such as sun drying or heat drying may be used. In addition, when performing heat drying, any heating method can be adopted, and it is best to appropriately determine whether or not it contains a malodorous component or a harmful volatile component, processing ability, economical efficiency, etc. You can adopt the method that you think.

  However, when it is not preferable to dry the waste liquid in a state where it is opened to the atmosphere, or when separating the contaminating components and water in the waste liquid and considering the reuse of water, the distillation method is preferably employed.

  In the case of carrying out the present invention by the distillation method, the apparatus for carrying out the present invention is not limited as long as it can distill waste liquid, a commercially available distillation apparatus may be used, and the apparatus is assembled so that the waste liquid can be distilled. You may go.

  In carrying out the present invention, there is no particular problem with a normal distillation method. However, when the waste liquid contains a high-boiling substance or when it is concentrated to dryness at a lower temperature, it is preferably carried out by vacuum distillation.

  In the case of carrying out the present invention by vacuum distillation, the apparatus for carrying out may be any apparatus that can be distilled under reduced pressure, a commercially available vacuum distillation apparatus may be used, and the apparatus is assembled so that distillation can be performed under reduced pressure. You may go. The distillation temperature is determined by the degree of decompression, but is not particularly limited, and may be determined in consideration of the moisture content and economic efficiency required for the concentrated and dried sludge. If the distillation temperature is too low, a high degree of vacuum is required and a distillation time is required. In order to reduce the moisture content of the concentrated and dried residue to 10% or less, it is preferable to set it to 70 ° C. or higher. The higher the degree of vacuum is, the lower the distillation temperature can be. However, in the present invention, 380 Torr (mmHg) or less, preferably 100 Torr or less, in order to reduce the moisture content of the concentrated and dried residue to 10% or less, It is desirable to carry out at 50 Torr or less.

  Next, based on the Example of this invention, it demonstrates still in detail. In the following examples,% means% by weight.

(Production Example 1)
A mixed solution (colorless, transparent) was prepared by mixing 1.2 parts by weight of an aqueous magnesium chloride solution (1M) and 10 parts by weight of an aqueous solution (1%) of sodium carboxymethyl cellulose (CMC) (manufactured by Wako Pure Chemical Industries, Ltd., for chemical use). ) Was prepared. This is designated as treating agent (I).

(Production Example 2)
A mixed solution was prepared by mixing 1 part by weight of an aqueous calcium chloride solution (2.7 M) and 10 parts by weight of an aqueous solution (1%) of sodium carboxymethylcellulose (CMC) (manufactured by Wako Pure Chemical Industries, Ltd., for chemical use). This is treated agent (II).

(Production Example 3)
4 parts by weight of calcium chloride dihydrate (CaCl ₂ · 2H ₂ O) powder and 1 part by weight of sodium carboxymethylcellulose (CMC) (manufactured by Wako Pure Chemical Industries, Ltd., chemical) powder were mixed in a mortar. Let this mixed powder be processing agent (III).

(Production Example 4)
1 part by weight of sodium alginate powder (Argitex H manufactured by Kimitsu Chemical Co., Ltd.) and 2 parts by weight of copper sulfate pentahydrate (powder) were mixed in a mortar. Let this mixed powder be processing agent (IV).

(Production Example 5)
1 part by weight of sodium alginate powder (Argitex H manufactured by Kimitsu Chemical Co., Ltd.) and 4 parts by weight of calcium chloride dihydrate (CaCl ₂ · 2H ₂ O) powder were mixed in a mortar. Let this mixed powder be a processing agent (V).

(Production Example 6)
4 parts by weight of calcium chloride dihydrate (CaCl ₂ · 2H ₂ O) powder, 4 parts by weight of magnesium chloride hexahydrate (MgCl ₂ · 6H ₂ O) powder and sodium carboxymethylcellulose (CMC) (Wako Pure Chemical Industries, Ltd.) 1 part by weight of powder manufactured by Chemical Co., Ltd. and 1 part by weight of sodium alginate powder (Argitex H manufactured by Kimitsu Chemical Co., Ltd.) were mixed in a mortar. Let this mixed powder be processing agent (VI).

(Production Example 7)
A mixture of 24 parts by weight of a magnesium chloride aqueous solution (1M) and 1 part by weight of a superabsorbent resin Sunwet 1M-5000D (manufactured by Sanyo Chemical Industries, Ltd., starch-acrylic acid graft copolymer) was prepared. This is designated treatment agent (VII).

(Production Example 8)
A mixed solution (colorless and transparent) was prepared by mixing 1.2 parts by weight of a magnesium chloride aqueous solution (1M) and 10 parts by weight of a 1% aqueous solution of pectin (manufactured by Nacalai Tesque, raw material citrus). This is designated treatment agent (VIII).

(Production Example 9)
A mixed solution (colorless) was prepared by mixing 1.2 parts by weight of an aqueous magnesium chloride solution (1M) and 10 parts by weight of an aqueous solution (2%) of sodium carboxymethylserose (CMC) (manufactured by Wako Pure Chemical Industries, Ltd., chemical) , Transparent). This is designated treating agent (IX).

(Production Example 10)
A mixed solution was prepared by mixing 1 part by weight of an aqueous sodium sulfate solution (1.86 M) and 20 parts by weight of an aqueous solution (0.5%) of copper carrageenan (manufactured by Chuo Kasei Co., Ltd.). This is referred to as a processing agent (X).

(Production Example 11)
Completely saponified polyvinyl alcohol (first grade manufactured by Wako Pure Chemical Industries, Ltd., average polymerization degree 1500-1800, saponification degree 98 + mol%) is immersed in water at room temperature to swell (concentration 10%) ) Was prepared. This is referred to as a processing agent (XI).

(Production Example 12)
Copper carrageenan (manufactured by Chuo Kasei Co., Ltd.) was immersed in water at room temperature and swollen (concentration: 1%). This is designated treating agent (XII).

(Production Example 13)
Sodium carboxymethyl cellulose (CMC) (manufactured by Wako Pure Chemical Industries, Ltd., for chemical use) was immersed in water at room temperature and swollen (concentration: 3%). This is designated treating agent (XIII).

(Production Example 14)
A sodium alginate powder (Argitex H manufactured by Kimitsu Chemical Co., Ltd.) was immersed in water at room temperature and swollen (concentration: 3%). This is referred to as a processing agent (XIV).

(Production Example 15)
A nonionic polymer flocculant NP-500 (manufactured by Daianitrix Co., Ltd., polyacrylamide) was immersed in water at room temperature and swollen (concentration: 0.5%). This is designated as processing agent (XV).

(Production Example 16)
An anionic polymer flocculant AP-335 (manufactured by Daianitrix Co., Ltd., a copolymer of acrylamide and acrylic acid) was immersed in water at room temperature and swollen (concentration 0.5%). did. This is designated as processing agent (XVI).

(Production Example 17)
A cationic polymer flocculant KP-1207B (manufactured by Daianitrix Co., Ltd., dimethylaminoethyl acrylate) was immersed in water at room temperature to swell (concentration: 0.5%). This is designated treatment agent (XVII).

(Production Example 18)
Sodium carboxymethylcellulose (CMC) (manufactured by Nippon Paper Chemical Co., Ltd., F600LC) powder and water glass (sodium silicate solution) (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed and immersed in water at room temperature to swell Prepared (concentrations of 2.5% and 2%, respectively). This is designated treating agent (XVIII).

Example 1
A factory waste liquid (copper concentration 2150 mg / L, total evaporation residue 63300 mg / L, pH 10.5) 40 mL of CuSO ₄ · 5H ₂ O powder was added to a household mill (Zojirushi BM-FT08 type) The mixture was stirred at 12000 rpm for 1 minute, 0.4 g of sodium carboxymethylcellulose (CMC) powder (Nippon Paper Chemical Co., Ltd. F600LC) was added, and the mixture was stirred at 12000 rpm for 2 minutes. A highly viscous liquid was obtained. This solution was placed in a 500 mL eggplant-shaped flask and distilled under reduced pressure close to normal pressure using a rotary vacuum evaporator (EYELA N-1000V type manufactured by Tokyo Rika Kikai Co., Ltd.). According to this operation, the liquid can be made almost the same state as being concentrated and dried at normal pressure while flowing. The rotation speed of the flask is 130 rpm. The temperature of the cooling water in the condenser (cooler) was about 5 ° C., and the pressure was reduced with a circulation aspirator (WJ-15 manufactured by Shibata Kagaku). First, the bath temperature was raised to 100 ° C. without reducing pressure, and then distilled under reduced pressure close to normal pressure (−38 mmHg = vacuum degree 722 mmHg). Since it almost solidified in about 40 minutes, it was made into high pressure reduction (vacuum degree about 20 mmHg), and it was made to dry. This dried product hardly adhered to the vessel wall and could be peeled off.

(Example 2)
In Example 1, it operated like Example 1 except having used the galactomannan (Chuo Kasei Co., Ltd.) powder instead of CMC powder. After stirring with a mill, it became a highly viscous liquid. The dried product hardly adhered to the vessel wall and could be peeled off.

(Example 3)
In Example 1, operation was performed in the same manner as in Example 1 except that locust bean gum (manufactured by Wako Pure Chemical Industries, Ltd.) powder was used instead of CMC powder. After stirring with a mill, it became a highly viscous liquid. The dried product hardly adhered to the vessel wall and could be peeled off.

Example 4
In Example 1, it operated like Example 1 except having used xanthan gum (Chuo Kasei Co., Ltd.) powder instead of CMC powder. After stirring with a mill, it became a highly viscous liquid. The dried product hardly adhered to the vessel wall and could be peeled off.

(Example 5)
In Example 1, except for using CuSO ₄ · 5H ₂ O powder and treating agent (IV) 1.2 g instead of CMC powder was operated in the same manner as in Example 1. After stirring with a mill, it became a highly viscous liquid. The dried product hardly adhered to the vessel wall and could be peeled off.

(Example 6)
In Example 1, the amount of CMC added was 0.2 g. After the addition of CMC, 0.2 g of waste paper pulverized cellulose fiber (NP fiber manufactured by Nippon Paper Wood Co., Ltd.) was added, and 1. The same operation as in Example 1 was performed except that the mixture was stirred for 5 minutes. The dried product could be easily peeled off.

(Example 7)
The CMC powder used in Example 1 was added to the A factory waste liquid in an amount of 0.25% of the waste liquid amount and stirred. A 20% solution of CuSO ₄ was added at 100 mL / L and stirred. This liquid was put into a double drum dryer (DD315 × 0.6 type) and dried at a temperature of 130 ° C. Drum rotation speed 10rpm. The dried product did not adhere to the drum surface and could be easily peeled off with a scraper.

(Comparative Example 1)
In Example 7, when the waste liquid was put into a drum dryer as it was and dried, the dried solid adhered to the drum surface, and peeling was impossible.

  Since the evaluation of the sticking property of the evaporative solidified product can be performed using either a rotary vacuum evaporator or a drum dryer, the following examples show the results of drying with an easy-to-use rotary vacuum evaporator. .

(Example 8)
Add 0.8 g of CaCl ₂ · 2H ₂ O powder to 40 mL of B factory waste liquid (Awamori distillery waste liquid, suspended substance concentration 89700 mg / L, total evaporation residue 135000 mg / L, pH 2.8) The mixture was stirred at 12000 rpm for 1 minute with ZOJIRUSHI BM-FT08, 0.4 g of sodium carboxymethylcellulose (CMC) powder (F600LC manufactured by Nippon Paper Chemical Co., Ltd.) was added, and the mixture was stirred at 12000 rpm for 3 minutes. A highly viscous liquid was obtained. This liquid was put into a 500 mL eggplant-shaped flask, and after performing vacuum distillation near normal pressure in the same manner as in Example 1 using a rotary vacuum evaporator, vacuum distillation was performed. First, the bath temperature was raised to 100 ° C. without reducing pressure, and then distilled under reduced pressure close to normal pressure (−38 mmHg = vacuum degree 722 mmHg). Since it almost solidified in about 40 minutes, it was made into high pressure reduction (vacuum degree about 20 mmHg), and it was made to dry. This dried product could be peeled off.

(Comparative Example 2)
In Example 8, when only the waste liquid was distilled under reduced pressure, it was difficult to remove the sludge that had been dried and fixed to the flask surface, and could not be taken out from the distillation flask in a dry state.

Example 9
Add 1.08 g of CaCl ₂ · 2H ₂ O powder to 60 mL of beer production waste liquid (total evaporation residue 44200 mg / L, TOC 32800 mg / L), stir to dissolve, and carboxymethylcellulose sodium (CMC) powder (Nippon Paper Industries) 0.54 g of Chemical Co., Ltd. (F600LC) was added, and the mixture was stirred at 12000 rpm for 3 minutes with a household mill (Zojirushi BM-FT08 type). It became a viscous white emulsion. This liquid was put into a 500 mL eggplant-shaped flask, and after performing vacuum distillation near normal pressure in the same manner as in Example 1 using a rotary vacuum evaporator, vacuum distillation was performed. First, the bath temperature was raised to 100 ° C. without reducing pressure, and then distilled under reduced pressure close to normal pressure (−38 mmHg = vacuum degree 722 mmHg). Since it almost solidified in about 26 minutes, the pressure was reduced to high pressure (vacuum degree: about 20 mmHg), and it was dried. This dried product hardly adhered to the vessel wall and could be easily peeled off.

(Comparative Example 3)
In Example 9, when only the waste liquid was distilled under reduced pressure, it was difficult to remove the sludge that had been dried and fixed to the flask surface, and could not be taken out from the distillation flask in a dry state.

(Example 10)
1.08 g of CaCl ₂ · 2H ₂ O powder was added to 60 mL of sake liquor waste liquid (total evaporation residue 37500 mg / L, suspended material 5500 mg / L, TOC 72000 mg / L), stirred and dissolved, and sodium carboxymethylcellulose ( CMC) powder (Nippon Paper Chemical Co., Ltd. F600LC) 0.54g was added, and it stirred at 12000rpm for 3 minutes with a household mill (Zojirushi BM-FT08 type). A white suspension was formed. This liquid was put into a 500 mL eggplant-shaped flask, and after performing vacuum distillation near normal pressure in the same manner as in Example 1 using a rotary vacuum evaporator, vacuum distillation was performed. First, the bath temperature was raised to 100 ° C. without reducing pressure, and then distilled under reduced pressure close to normal pressure (−38 mmHg = vacuum degree 722 mmHg). Since it gradually became a viscous liquid and was almost solidified in about 22 minutes, it was dried under high vacuum (vacuum degree: about 20 mmHg). This dried product hardly adhered to the vessel wall and could be easily peeled off.

(Comparative Example 4)
In Example 10, when only the waste liquid was distilled under reduced pressure, it was difficult to remove the sludge that had been dried and fixed to the flask surface, and could not be taken out from the distillation flask in a dry state.

(Example 11)
Copper concentration 4860mg / L, hydrogen peroxide concentration about 10%, TOC 12700mg / L, suspended matter 15.8g / L, total evaporation residue 195g / L, pH-0.5 etching waste solution 250mL to sodium hydroxide aqueous solution (48%) was added to pH 3.5 (there was a large amount of foaming).
This solution was put into a distillation flask (volume 1 L eggplant-shaped flask), 1 mL of calcium chloride aqueous solution (2.7 M) (108 mg as Ca) and sodium carboxymethylcellulose (CMC) (manufactured by Wako Pure Chemical Industries, Ltd., for chemical use) 10 mL of 1% aqueous solution was added and distilled under reduced pressure using a rotary vacuum evaporator (EYELA N-1000V type).
The number of revolutions of the distillation flask was 130 rpm, the degree of vacuum was about 20 mmHg, the temperature was about 50 ° C., the cooling water temperature of the cooler was about 5 ° C., and the pressure was reduced with a circulation aspirator (WJ-15 manufactured by Shibata Kagaku).
About 1 hour later, the distillate in the distillation flask was dried to leave a greenish white sludge layer having a thickness of about 3 mm. This sludge could be easily peeled off and recovered almost completely.

(Comparative Example 5)
In Example 11, when only the waste liquid was distilled under reduced pressure, it was difficult to peel off the sludge that had been dried and fixed to the flask surface, and could not be taken out from the distillation flask in a dry state.

(Example 12)
In Example 11, when it processed similarly to Example 11 except having added 11 mL of processing agents (II) instead of the added calcium chloride aqueous solution and CMC aqueous solution, the result similar to Example 11 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 13)
In Example 11, when it processed like Example 11 except having added 0.5 g of processing agents (III) instead of the calcium chloride aqueous solution and CMC aqueous solution which were added, the result similar to Example 11 was obtained. . This sludge could be easily peeled off and recovered almost completely.

(Example 14)
In Example 11, when it processed like Example 11 except having added 0.5 g of processing agents (V) instead of the calcium chloride aqueous solution and CMC aqueous solution which were added, the result similar to Example 11 was obtained. . This sludge could be easily peeled off and recovered almost completely.

(Example 15)
In Example 11, the amount of added calcium chloride aqueous solution (concentration 0.9 M) was 1.2 mL (43 mg as Ca), and 10 mL of 1% aqueous solution of pectin (manufactured by Nacalai Tesque, raw material citrus) was added instead of CMC aqueous solution. Except for this, the same processing as in Example 11 was performed, and the same results as in Example 11 were obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 16)
In Example 15, when it processed like Example 15 except having added 10 mL of 1% aqueous solution of pectic acid (made by Nacalai Tesque) instead of the added pectin, the result similar to Example 15 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 17)
In Example 11, instead of the added calcium chloride aqueous solution and CMC aqueous solution, treatment was performed in the same manner as in Example 11 except that 11.2 mL of treating agent (I) (29.2 mg as Mg) was added. Similar results to 11 were obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 18)
In Example 11, instead of the added calcium chloride aqueous solution and CMC aqueous solution, the same treatment as in Example 11 was performed except that 1.25 g of the treating agent (VII) was added. It was. This sludge could be easily peeled off and recovered almost completely.

Example 19
In Example 11, when it processed similarly to Example 11 except having added 10.5 mL of processing agent (X) instead of the added calcium chloride aqueous solution and CMC aqueous solution, the result similar to Example 11 was obtained. . This sludge could be easily peeled off and recovered almost completely.

(Example 20)
In Example 11, it processed similarly to Example 11 except having added 1 mL of processing agents (XI) instead of the added calcium chloride aqueous solution and CMC aqueous solution, and the result similar to Example 11 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 21)
In Example 20, when it processed similarly to Example 20 except having added 10 mL of processing agents (XII) instead of the added processing agent (XI), the result similar to Example 20 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 22)
Suspended substance 2.65 g / L, Si concentration 290 mg / L, TOC 1300 mg / L, IC (inorganic carbon) 2000 mg / L, total evaporation residue 17.2 g / L, pH 14 resist waste liquid 500 mL and sulfuric acid (20.5 N ) 7.5 mL was added to pH 7. The SO ₄ ²⁻ concentration is 14.6 g / L.

When this solution was put into a distillation flask (1 L capacity eggplant-shaped flask) and 10 mL of a 0.5% aqueous solution of copper carrageenan (manufactured by Chuo Kasei Co., Ltd.) was added, a fibrous floc was formed. Distillation under reduced pressure was performed using a rotary vacuum evaporator (EYELA N-1000V type).
The number of revolutions of the distillation flask was 130 rpm, the degree of vacuum was about 20 mmHg, the temperature was about 50 ° C. at first, almost evaporated to dryness (about 1 hour), and then raised to 80 ° C. to completely dry. The cooling water temperature of the cooler was about 5 ° C., and the pressure was reduced with a circulation aspirator (WJ-15 manufactured by Shibata Kagaku).

The distillate in the distillation flask was dried to leave a sludge layer having a thickness of about 1 mm (about 70% white, others bluish white). This sludge could be easily peeled off and recovered almost completely.
Copper carrageenan produces a sulfate group and a gel, but since this waste liquid already contains a large amount of sulfate group, it is not necessary to add it again.

(Comparative Example 6)
In Example 22, when only the waste liquid was distilled under reduced pressure, it was difficult to remove the sludge that had been dried and fixed to the flask surface, and could not be taken out from the distillation flask in a dry state.

(Example 23)
In Example 22, the same treatment as in Example 22 was performed except that 11.2 mL of the treating agent (I) (29.2 mg as Mg) was added instead of the added aqueous solution of copper carrageenan. Results were obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 24)
In Example 23, instead of the added treatment agent (I), 0.5 mL of an aluminum chloride aqueous solution (1.24 M) (16.2 mg as Al) and CMC (manufactured by Wako Pure Chemical Industries, Ltd., for chemical use) When the same treatment as in Example 23 was performed except that 10 mL of a 1% aqueous solution was added, the same result as in Example 23 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 25)
In Example 24, the same treatment as in Example 24 was performed except that 0.5 mL of ferric chloride aqueous solution (1M) (28 mg as Fe) was added instead of the added aluminum chloride aqueous solution. Results were obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 26)
In Example 23, when it processed similarly to Example 23 except having added 1.25g of processing agents (VII) instead of the added processing agent (I), the result similar to Example 23 was obtained. . This sludge could be easily peeled off and recovered almost completely.

(Example 27)
In Example 23, when it processed similarly to Example 23 except having added 11.2 mL of processing agents (VIII) instead of the added processing agent (I), the result similar to Example 23 was obtained. . This sludge could be easily peeled off and recovered almost completely.

(Example 28)
In Example 23, instead of the added treatment agent (I), 2 mL of magnesium chloride aqueous solution (1M) (48.6 mg as Mg) and anionic polymer flocculant AP-335 (manufactured by Daianitrix Co., Ltd.) (A copolymer of acrylamide and acrylic acid) The same treatment as in Example 23 was performed except that 15 mL of a 0.2% aqueous solution was added. This sludge could be easily peeled off and recovered almost completely.

(Example 29)
In Example 23, when it processed like Example 23 except having added processing agent (VI) 0.5g instead of the added processing agent (I), the result similar to Example 23 was obtained. . This sludge could be easily peeled off and recovered almost completely.

(Example 30)
In Example 23, 10 mL of an aqueous solution (1%) of polyvinyl alcohol (first grade made by Wako Pure Chemical Industries, partially saponification type, average polymerization degree 2500 to 3100, saponification degree 86 to 90 mol%) was used instead of the added treatment agent (I). Except for the addition, the same treatment as in Example 23 was performed, and the same result as in Example 23 was obtained. This sludge could be easily peeled off and recovered almost completely.
Polyvinyl alcohol forms sulfate radicals and gels, but since this waste liquid already contains a large amount of sulfate radicals, there is no need to add it again.

(Example 31)
In Example 30, treatment was carried out in the same manner as in Example 30 except that 10 mL of 0.1N hydrochloric acid solution (concentration 0.5%) of chitosan (manufactured by Nacalai Tesque) was added instead of the added aqueous polyvinyl alcohol solution. Similar results to 30 were obtained. This sludge could be easily peeled off and recovered almost completely.
Chitosan forms a sulfate group and a gel, but since this waste liquid already contains a large amount of sulfate group, there is no need to add it again.

(Example 32)
In Example 23, when it processed similarly to Example 23 except having added 3 mL of processing agents (XIII) instead of the added processing agent (I), the result similar to Example 23 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 33)
In Example 23, when it processed similarly to Example 23 except having added 3 mL of processing agents (XIV) instead of the added processing agent (I), the result similar to Example 23 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 34)
In Example 23, when it processed similarly to Example 23 except having added 10 mL of processing agents (XV) instead of the added processing agent (I), the result similar to Example 23 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 35)
In Example 23, when it processed similarly to Example 23 except having added 10 mL of processing agents (XVI) instead of the added processing agent (I), the result similar to Example 23 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 36)
In Example 23, when it processed similarly to Example 23 except having added 10 mL of processing agents (XVIII) instead of the added processing agent (I), the result similar to Example 23 was obtained. This sludge could be easily peeled off and recovered almost completely.

(Example 37)
Copper EDTA concentration 5g / L (copper concentration 800mg / L), sulfate ion 16g / L, total evaporation residue 28.7g / L, pH8 copper EDTA model waste liquid 200mL is put into a distillation flask (volume 1L eggplant type flask) Then, 4 mL of calcium chloride aqueous solution (2.7 M) (432 mg as Ca) and 10 mL of CMC (Wako Pure Chemical Industries, Ltd., chemical) aqueous solution (2%) were added. Distillation under reduced pressure was performed using a rotary vacuum evaporator (EYELA N-1000V type).

The number of revolutions of the distillation flask was 130 rpm, the degree of vacuum was about 20 mmHg, the temperature was initially about 50 ° C., and after almost evaporating to dryness, the temperature was raised to 80 ° C. and completely dried. The cooling water temperature of the cooler was about 5 ° C., and the pressure was reduced with a circulation aspirator (WJ-15 manufactured by Shibata Kagaku).
The distillate in the distillation flask was dried to leave a sludge layer (blue white) having a thickness of about 1 mm. This sludge could be easily peeled off and recovered almost completely.

(Comparative Example 7)
When only the waste liquid was distilled under reduced pressure in Example 37, it was difficult to peel off the sludge that had been dried and fixed to the flask surface, and could not be taken out from the distillation flask in a dry state.

(Example 38)
In Example 37, treatment was performed in the same manner as in Example 37 except that 11.2 mL of the treatment agent (IX) was added instead of the added calcium chloride aqueous solution and CMC aqueous solution, and the same result as in Example 37 was obtained. It was. The generated sludge could be easily peeled off and recovered almost completely.

(Example 39)
In Example 38, instead of the added treating agent (IX), 3 mL of an aqueous calcium chloride solution (2.7 M) (324 mg as Ca) and an anionic polymer flocculant AP-350 (manufactured by Daianitrix Co., Ltd.) The same results as in Example 38 were obtained when the same treatment as in Example 38 was performed except that 30 mL of an aqueous solution (polyacrylic acid) (0.2%) was added. The generated sludge could be easily peeled off and recovered almost completely.

(Example 40)
In Example 38, when it processed similarly to Example 38 except having added 10 mL of processing agents (XVII) instead of the added processing agent (IX), the result similar to Example 38 was obtained. The generated sludge could be easily peeled off and recovered almost completely.

(Example 41)
Add 1.08 g of CaCl ₂ · 2H ₂ O powder to 40 mL of model waste liquid of boron 500 mg / L, stir and dissolve, adjust to pH 10 by adding aqueous sodium hydroxide solution, and add sodium carboxymethyl cellulose (CMC) powder 0.54 g (Nippon Paper Chemical Co., Ltd. F600LC) was added, and the mixture was stirred at 12000 rpm for 3 minutes with a household mill (Zojirushi BM-FT08 type). A highly viscous liquid was obtained. This liquid was put into a 500 mL eggplant-shaped flask, and after performing vacuum distillation near normal pressure in the same manner as in Example 1 using a rotary vacuum evaporator, vacuum distillation was performed. First, the bath temperature was raised to 100 ° C. without reducing pressure, and then distilled under reduced pressure close to normal pressure (−38 mmHg = vacuum degree 722 mmHg). Since it gradually became a viscous liquid and was almost dried in about 24 minutes, it was dried under high vacuum (vacuum degree: about 20 mmHg). This dried product hardly adhered to the vessel wall and could be easily peeled off.
The boron concentration in the distillate (condensate) was approximately 0 mg / L.

(Comparative Example 8)
In Example 41, when only the waste liquid was distilled under reduced pressure, it was difficult to remove the sludge that had been dried and fixed to the flask surface, and could not be taken out from the distillation flask in a dry state.

(Example 42)
Add 1.08 g of CaCl ₂ · 2H ₂ O powder to 40 mL of model waste liquid of 500 mg / L of fluorine, stir and dissolve, adjust to pH 10 by adding aqueous sodium hydroxide, and add sodium carboxymethyl cellulose (CMC) powder 0.54 g (Nippon Paper Chemical Co., Ltd. F600LC) was added, and the mixture was stirred at 12000 rpm for 3 minutes with a household mill. A highly viscous liquid was obtained. This liquid was put into a 500 mL eggplant-shaped flask, and after distillation under reduced pressure near normal pressure in the same manner as in Example 41 using a rotary vacuum evaporator, vacuum distillation was performed. First, the bath temperature was raised to 100 ° C. without reducing pressure, and then distilled at a reduced pressure close to normal pressure. Since it gradually became a viscous liquid and was almost solidified in about 25 minutes, the pressure was reduced to high and the liquid was solidified. This dried product hardly adhered to the vessel wall and could be easily peeled off.
The fluorine concentration in the distillate (condensate) was approximately 0 mg / L.

(Comparative Example 9)
In Example 42, when only the waste liquid was distilled under reduced pressure, it was difficult to peel off the sludge that had been dried and fixed to the flask surface, and could not be removed from the distillation flask in a dry state.

(Example 43)
Add 1.08 g of CaCl ₂ · 2H ₂ O powder to 40 mL of model waste liquid with a BF ₄ concentration of 812 mg / L, stir to dissolve, add sodium hydroxide aqueous solution to adjust the pH to 10, carboxymethyl cellulose sodium (CMC ) 0.54 g of powder (Nippon Paper Chemical Co., Ltd. F600LC) was added, and the mixture was stirred for 3 minutes at 12000 rpm in a household mill. A highly viscous liquid was obtained. This liquid was put into a 500 mL eggplant-shaped flask, and after performing vacuum distillation near normal pressure in the same manner as in Example 1 using a rotary vacuum evaporator, vacuum distillation was performed. First, the bath temperature was raised to 100 ° C. without reducing pressure, and then distilled at a reduced pressure close to normal pressure. Since it gradually became a viscous liquid and was almost solidified in about 21 minutes, the pressure was reduced to high pressure and the liquid was solidified. This dried product hardly adhered to the vessel wall and could be easily peeled off.
The boron and fluorine concentrations in the distillate (condensate) were both approximately 0 mg / L.

(Comparative Example 10)
In Example 43, when only the waste liquid was distilled under reduced pressure, it was difficult to remove the sludge that had been dried and fixed to the flask surface, and could not be taken out from the distillation flask in a dry state.

Claims (15)

  In a method for treating a waste liquid containing various pollutant components, a water-soluble substance that generates a gel-like substance is added to the waste liquid, and the waste liquid is concentrated and dried in the presence of the gel-like substance. A method for treating a waste liquid containing a pollutant component.   The water-soluble substance is carboxymethylcellulose or a salt thereof, alginic acid or a salt thereof, pectin, pectinic acid or a salt thereof, polyacrylic acid or a salt thereof, a copolymer of acrylamide and acrylic acid or a salt thereof, or these The method of Claim 1 which consists of 2 or more types of these.   The method according to claim 1, wherein the polyvalent metal compound is present simultaneously with the water-soluble substance that forms the gel substance.   The method according to claim 3, wherein the polyvalent metal compound is a magnesium compound, a calcium compound, a copper compound, an aluminum compound, an iron compound, or two or more thereof.   The method according to claim 1, wherein the water-soluble substance is any one of polyvinyl alcohol, carrageenan, chitosan, or two or more thereof.   The method according to claim 1 or 5, wherein an inorganic polyvalent anion generator is present simultaneously with the water-soluble substance that forms the gel substance.   The method according to claim 6, wherein the inorganic polyvalent anion is a sulfate ion and the inorganic polyvalent anion generator is a sulfate compound.   The method according to claim 1, wherein the waste liquid is distilled under reduced pressure when the waste liquid is concentrated to dryness.   The method according to any one of claims 1 to 8, wherein when the waste liquid is concentrated to dryness, the gel material is present in the waste liquid, and then the fiber substance is added to concentrate to dryness.   The chemical | medical agent used for the processing method of the waste liquid of Claim 1, Comprising: The chemical | medical agent which consists of a water-soluble substance and polyvalent metal compound which produce | generate a gel-like substance.   The water-soluble substance is any one of carboxymethylcellulose or a salt thereof, alginic acid or a salt thereof, polyacrylic acid or a salt thereof, a copolymer of acrylamide and acrylic acid or a salt thereof, or two or more thereof, The drug according to claim 10, wherein the polyvalent metal compound is a magnesium compound, a calcium compound, a copper compound, an aluminum compound, an iron compound, or two or more of these.   The chemical | medical agent used for the processing method of the waste liquid of Claim 1, Comprising: The chemical | medical agent which consists of a water-soluble substance which produces | generates a gel-like substance, and an inorganic polyvalent anion generator.   The drug according to claim 12, wherein the water-soluble substance is any one of polyvinyl alcohol, carrageenan, chitosan, or two or more thereof, and the inorganic polyvalent anion generator is a sulfate compound.   The chemical | medical agent used for the processing method of the waste liquid of Claim 1, Comprising: It consists of a water-soluble substance which can be swollen with water. The water-soluble substance is polyvinyl alcohol, carrageenan, carboxymethylcellulose or a salt thereof, alginic acid or a salt thereof, polyacrylamide, a copolymer of acrylamide and acrylic acid or a salt thereof, or a polyacrylic acid dimethylaminoethyl ester, or these The drug according to claim 13, comprising at least two of the following.