JP2020196002A - Agent for treating group 6 to group 16 elements or compounds thereof and method of treating water containing the same - Google Patents

Abstract

To provide a novel treatment agent and a treatment method using the same, which can efficiently treat at least one selected from Group 6 to Group 16 elements in the periodic table, or compounds thereof.SOLUTION: A treatment agent for treating at least one selected from Group 6 to Group 16 elements in the periodic table or compounds thereof, contains a compound represented by the following formula (I): (In the formula, R1 represents a linear or branched polyhydroxyalkyl group containing 4-12 carbon atoms and having 3 or more hydroxyl groups, R2 represents a hydrocarbon group containing 1-22 carbon atoms, and R3 represents a hydrogen atom or a hydrocarbon group containing 1-22 carbon atoms, the number of carbon atoms in R2 being greater than or equal to the number of carbon atoms in R3, and the total number of carbon atoms in R2 and R3 being 10 or more).SELECTED DRAWING: None

Description

The present invention relates to a treatment agent for a Group 6 to Group 16 element or a compound thereof and a method for treating water contained therein.

Separation and recovery of Group 6 to Group 16 elements such as copper, zinc and boron or their compounds from water such as industrial wastewater and business site wastewater to purify and detoxify water, reuse of the elements, etc. Various processes are being performed for this purpose. As the treatment method, for example, reverse osmosis membrane (RO membrane) separation, ion exchange, coagulation precipitation and the like are known. Of these, ion exchange, which is a removal method that has a particularly low running cost and is less likely to generate sludge, is widely used.

However, the RO membrane cannot treat the target element or its compound in a single treatment, and the ion exchange method has a problem that the amount of the ion exchange resin used per unit gram is low and the treatment cost is high. was there.
Further, in the conventional coagulation-precipitation method, a method of adding an aluminum compound such as aluminum sulfate or a calcium compound such as calcium hydroxide to coagulate and precipitate boron is separated, and a large amount of chemicals are used because the efficiency of removing boron is low. There is also a problem that a large amount of sediment (that is, sludge) is generated during the treatment.

Patent Document 1 proposes to use a glucamine-containing phenolic resin as a boron adsorption treatment agent. The boron adsorption performance of alkylglucamine itself is not described, and the amount of adsorption of the resin is lower than that of alkylglucamine.

Patent Document 2 describes a boron-adsorbing composition composed of an ammonium salt derivative represented by the general formula (R ¹ −N ⁺ (−X ⁻ ) −R ² ) (R ¹ is a sugar alcohol residue or a polyhydric alcohol residue. Amino group-containing groups containing groups; R ² is a heterocyclic composition residue excluding N of the nitrogen-containing heterocyclic composition; X ⁻ is an anion coordinated with N) have been proposed. Although it is a boron-treatable composition of a resin powder having a sugar alcohol group, there is room for further improvement such that the treatment amount of the resin treatment agent is generally low per gram.

Patent Document 3 describes boron by adding at least one carboxylic acid compound selected from aldonic acid or uronic acid and a high molecular weight amine compound to waste water containing boron, then adding a salting out agent, and filtering and separating. A technique for removing uronic acid has been proposed. Carboxylic acid compounds have a low boron processing capacity and require a large amount of processing agent.

Patent Document 4 proposes to use a treatment agent containing an N-methylglucamine compound as a treatment agent for immobilizing harmful substances such as boron, fluorine, selenium and arsenic contained in boiler ash. The dimethylglucamic acid exemplified above has a low processing capacity, and there is no description about using an N-methylglucamine compound for the treatment of copper, zinc, and boron-containing water, and the chain is longer than the ethyl group. The effect of alkyl glucamine having an alkyl group is also not described.

Non-Patent Document 1 reports that as a water-insoluble glucamine derivative, a water-insoluble glucamine derivative was synthesized by a Michael addition reaction between an acrylic monomer and N-methylglucamine, and boron in water could be removed. .. However, this water-insoluble glucamine derivative has an ester group in the derivative, and the ester group is easily hydrolyzed in water, so that it may be decomposed during the treatment and the treatment capacity may not be sufficiently exhibited.

Japanese Unexamined Patent Publication No. 2011-083711 Japanese Unexamined Patent Publication No. 2011-56465 Japanese Unexamined Patent Publication No. 2010-17686 JP-A-2009-214018

52nd Annual Meeting of the Japan Society for Water Environment (2017) Abstract of Lecture Page 580 Lecture No. P-E04

The present invention has been made in view of the above circumstances, and is a novel treatment agent capable of efficiently treating Group 6 to Group 16 elements or compounds thereof, and a treatment using the same. The challenge is to provide a method.

To solve the above problems, the present invention is a treatment agent for treating at least one selected from the elements of Groups 6 to 16 of the periodic table or compounds thereof.
It is characterized by containing a compound represented by the following formula (I).

（式中、Ｒ^１は水酸基を３個以上有する炭素数４〜１２の直鎖又は分岐のポリヒドロキシアルキル基を示し、Ｒ^２は炭素数１〜２２の炭化水素基を示し、Ｒ^３は水素原子又は炭素数１〜２２の炭化水素基を示し、Ｒ^２の炭素数がＲ^３の炭素数以上であり、Ｒ^２とＲ^３の総炭素数が１０以上である）。

(In the formula, R ¹ represents a linear or branched polyhydroxyalkyl group having 4 to 12 carbon atoms having 3 or more hydroxyl groups, R ² represents a hydrocarbon group having 1 to 22 carbon atoms, and R ³ is hydrogen. atom or a hydrocarbon group having 1 to 22 carbon atoms, the carbon number of ^{R 2} is not less than the number of carbon atoms in ^{R 3,} the total number of carbon atoms in ^{R 2} and ^{R 3} is 10 or more).

The present invention is a treatment method for removing a treatment target from water, and is characterized by including the following steps:
A step of adding the treatment agent to the water to be treated and a step of adjusting the water to be treated to be neutral.

According to the present invention, the elements of Group 6 to Group 16 of the periodic table or compounds thereof can be effectively treated.

The present invention will be described in detail below.
(Processing agent)
The treatment agent of the present invention contains a compound represented by the formula (I).

In formula (I), R ¹ represents a linear or branched polyhydroxyalkyl group having 3 or more hydroxyl groups and having 4 to 12 carbon atoms. The polyhydroxyalkyl group is not particularly limited, and examples thereof include tri, tetra, penta, hexa, hepta, and octahydroxyalkyl groups. Specifically, for example, but not particularly limited, 1,2,3 trihydroxybutane-1-yl group, 1,2,4 trihydroxybutane-1-yl group, 1,3,4 trihydroxybutane-1 -Trihydroxybutane-1-yl group such as -yl group, 2,3,4 trihydroxybutane-1-yl group; tetrahydroxybutane-1-yl group; 1,2,3 trihydroxybutane-2-yl group , 1,2,4 trihydroxybutane-2-yl group, 1,3,4 trihydroxybutane-2-yl group, 2,3,4 trihydroxybutane-2-yl group, etc. Il group; tetrahydroxybutane-2-yl group; tri, tetra, or pentahydroxypentane-1-yl group; tri, tetra, penta, or hexahydroxyhexane-1-yl group; tri, tetra, penta, hexa, Alternatively, heptahydroxyheptane-1-yl group; tri, tetra, penta, hexa, hepta, octahydroxyoctane-1-yl group and the like can be mentioned.

The polyhydroxyalkyl group preferably has 3 or more hydroxyl groups, more preferably 4 or more, further preferably 5 or more, and the alkyl group has 5 carbon atoms in terms of efficiently bonding to the element to be treated or a compound thereof. A straight chain or branched compound having ~ 12 is preferable, and one having 6 to 8 carbon atoms is more preferable. Among these, a linear or branched one having 4 or more hydroxyl groups and 4 to 8 carbon atoms is preferable, and a linear or branched one having 5 or more hydroxyl groups and 6 to 8 carbon atoms is more preferable. , A linear or branched one having 5 hydroxyl groups and 6 carbon atoms is more preferable, and a linear one having 5 hydroxyl groups is particularly preferable.

R ² represents a hydrocarbon group having 9 to 22 carbon atoms, and the hydrocarbon group is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. .. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group and the like. The alkyl group includes a straight chain or a branch, and is not particularly limited, and is, for example, nonane-1-yl group, decane-1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl. Il group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptadecane-1-yl group, octadecane-1-yl group, nonadecane-1-yl group, icosane-1-yl group Examples thereof include a group, heneicosane-1-yl group, docosane-1-yl group, α, α-dimethylbenzyl group and the like. The alkenyl group includes a linear group or a branched group, and is not particularly limited, but for example, a nona-1-ene-1-yl group, a nona-8-en-1-yl group, a deca-1-en-1-yl group, and the like. Deca-9-en-1-yl group, undeca-1-en-1-yl group, undeca-10-en-1-yl group, dodeca-1-en-1-yl group, dodeca-11-en-yl group 1-yl group, trideca-1-en-1-yl group, trideca-12-en-1-yl group, tetradeca-1-en-1-yl group, tetradeca-13-en-1-yl group, pentadeca -1-en-1-yl group, pentadeca-14-en-1-yl group, hexadeca-1-en-1-yl group, hexadeca-15-en-1-yl group, heptadeca-1-en-1 -Il group, heptadeca-16-en-1-yl group, octadeca-1-en-1-yl group, octadeca-9-en-1-yl group, octadeca-17-en-1-yl group, nonadeca- Examples thereof include 1-ene-1-yl group, eikosa-1-en-1-yl group, heneicosa-1-en-1-yl group, docosa-1-en-1-yl group and the like. The alkynyl group includes a linear group or a branched group, and is not particularly limited, but for example, a nona-1-in-1-yl group, a nona-8-in-1-yl group, a deca-1-in-1-yl group, and the like. Deca-9-in-1-yl group, undeca-1-in-1-yl group, undeca-10-in-1-yl group, dodeca-1-in-1-yl group, dodeca-11-in- 1-yl group, trideca-1-in-1-yl group, trideca-12-in-1-yl group, tetradeca-1-in-1-yl group, tetradeca-13-in-1-yl group, pentadeca -1-In-1-yl group, pentadeca-14-in-1-yl group, hexadeca-1-in-1-yl group, hexadeca-15-in-1-yl group, heptadeca-1-in-1 -Il group, heptadeca-16-in-1-yl group, octadeca-1-in-1-yl group, octadeca-17-in-1-yl group, nonadeca-1-in-1-yl group, ecosa- Examples thereof include a 1-in-1-yl group, a heneicosa-1-in-1-yl group, and a docosa-1-in-1-yl group.

The alicyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclononyl group and a cyclodecyl group.

The aromatic hydrocarbon group is not particularly limited, and examples thereof include groups containing aromatic ring residues such as phenyl residue, naphthalene residue, and anthracene residue. The aromatic hydrocarbon group is not particularly limited, but for example, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butyl. Phenyl group, 4-tert-butylphenyl group, 4-pentylphenyl group, 4-tert-pentylphenyl group, 2,4-bis (4-tert-pentyl) phenyl group, 1,1,3,3-tetramethyl Butylphenyl group, 2-methyl-5-tert-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-heptylphenyl group, 4-octylphenyl group, 4-nonylphenyl group, 4-decanyl Phenyl group, 4-undecylphenyl group, 4-dodecylphenyl group, 4-tridecylphenyl group, 4-tetradecylphenyl group, 4-pentadecylphenyl group, 4-hexadecylphenyl group, 4-biphenyl group, 1 Examples thereof include −methylnaphthyl group, 1-ethylnaphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group and the like.

Among these, a linear or branched alkyl group having 10 to 18 carbon atoms is preferable, and a linear or branched alkyl group having 10 to 16 carbon atoms is more preferable in terms of efficiently bonding to the element to be treated or a compound thereof. A linear alkyl group having 10 to 14 carbon atoms is more preferable.

R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group and the like. The alkyl group includes a linear group or a branched group, and is not particularly limited, but for example, a methyl group, an ethane-1-yl group, a propane-1-yl group, a 1-methylethane-1-yl group, a butane-1-yl group. , Butane-2-yl group, 2-methylpropan-1-yl group, 2-methylpropan-2-yl group, pentane-1-yl group, pentan-2-yl group, hexane-1-yl group, heptane -1-yl group, octane-1-yl group, 1,1,3,3-tetramethylbutane-1-yl group, nonane-1-yl group, benzyl-1-yl group, undecane-1-yl group , Dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, heptadecane-1-yl group, octadecane-1-yl group, Benzyl group, α, α-dimethylbenzyl group and the like can be mentioned. The alkenyl group includes a linear group or a branched group, and is not particularly limited, but for example, a vinyl group, a propa-1-ene-1-yl group, an allyl group, an isopropenyl group, a pig-1-ene-1-yl group, a pig. -2-En-1-yl group, porcine-3-ene-1-yl group, 2-methylpropa-2-ene-1-yl group, 1-methylpropa-2-ene-1-yl group, penta-1 -En-1-yl group, penta-2-en-1-yl group, penta-3-en-1-yl group, penta-4-en-1-yl group, 3-methylbut-2-ene-1 -Il group, 3-methylbut-3-en-1-yl group, hexa-1-en-1-yl group, hexa-2-en-1-yl group, hexa-3-en-1-yl group, Hexa-4-en-1-yl group, hexa-5-en-1-yl group, 4-methylpenta-3-ene-1-yl group, 4-methylpenta-3-en-1-yl group, hepta- 1-en-1-yl group, hepta-6-en-1-yl group, octa-1-en-1-yl group, octa-7-en-1-yl group, nona-1-en-1-yl group Il group, nona-8-en-1-yl group, deca-1-en-1-yl group, deca-9-en-1-yl group, undeca-1-en-1-yl group, undeca-10 -En-1-yl group, dodeca-1-en-1-yl group, dodeca-11-en-1-yl group, trideca-1-en-1-yl group, trideca-12-en-1-yl group Group, tetradeca-1-en-1-yl group, tetradeca-13-en-1-yl group, pentadeca-1-en-1-yl group, pentadeca-14-en-1-yl group, hexadeca-1- En-1-yl group, hexadeca-15-en-1-yl group, heptadeca-1-en-1-yl group, heptadeca-16-en-1-yl group, octadeca-1-en-1-yl group , Octadeca-9-ene-1-yl group, octadeca-17-ene-1-yl group and the like. The alkynyl group includes a linear group or a branched group, and is not particularly limited. For example, ethynyl, propa-1-in-1-yl group, propa-2-in-1-yl group, buta-1-in-1-yl group. Group, porcine-3-in-1-yl group, 1-methylprop-2-in-1-yl group, penta-1-in-1-yl group, penta-4-in-1-yl group, hexa- 1-in-1-yl group, hexa-5-in-1-yl group, hepta-1-in-1-yl group, hepta-6-in-1-yl group, octa-1-in-1- Il group, octa-7-in-1-yl group, nona-1-in-1-yl group, nona-8-in-1-yl group, deca-1-in-1-yl group, deca-9 -In-1-yl group, undeca-1-in-1-yl group, undeca-10-in-1-yl group, dodeca-1-in-1-yl group, dodeca-11-in-1-yl group Group, trideca-1-in-1-yl group, trideca-12-in-1-yl group, tetradeca-1-in-1-yl group, tetradeca-13-in-1-yl group, pentadeca-1- In-1-yl group, pentadeca-14-in-1-yl group, hexadeca-1-in-1-yl group, hexadeca-15-in-1-yl group, heptadeca-1-in-1-yl group , Heptadeca-16-in-1-yl group, octadeca-1-in-1-yl group, octadeca-17-in-1-yl group and the like.

The alicyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

The aromatic hydrocarbon group is not particularly limited, and examples thereof include groups containing aromatic ring residues such as phenyl residue, naphthalene residue, and anthracene residue. The aromatic hydrocarbon group is not particularly limited, but for example, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, and a 2,5-dimethylphenyl group. Group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-pentylphenyl group, 4-tert-pentylphenyl group, 2,4-bis (4-tert-pentyl) phenyl group, 1 , 1,3,3-tetramethylbutylphenyl group, 2-methyl-5-tert-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-heptylphenyl group, 4-octylphenyl group, 4 − Nonylphenyl group, 4-decanylphenyl group, 4-undecylphenyl group, 4-dodecylphenyl group, 4-tridecylphenyl group, 4-tetradecylphenyl group, 4-pentadecylphenyl group, 4-hexadecyl Phenyl group, 4-heptadecylphenyl group, 4-octadecylphenyl group, 4-biphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group , 4-ethoxyphenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-hydroxyphenyl group, 1-naphthyl group , 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group and the like.

Among these, a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms is preferable in terms of efficiently bonding to the element to be treated or a compound thereof, and a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. Is more preferable, a straight chain having a hydrogen atom or 1 to 4 carbon atoms or a branch is more preferable, and a straight chain having a hydrogen atom or 1 to 2 carbon atoms is particularly preferable.

On the other hand, the total carbon number of R ² and R ³ is preferably 10 to 17, more preferably 10 to 14.

In the formula (I), the hydrocarbon group of ^{R 2} and ^{R 3,} the carbon number of ^{R 2} is not less than the number of carbon atoms in ^{R 3,} as the combination of ^{R 2} and ^{R 3,} but are not limited to, processed element Alternatively, in terms of efficient bonding with the compound, for example, a linear or branched alkyl group having R ³ having 1 to 8 carbon atoms and a linear or branched alkyl group having R ² having 10 to 18 carbon atoms are preferable. The number of carbon atoms is more preferably 10 to 16, and the number of carbon atoms is further preferably 10 to 14. R ³ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and R ² is preferably a linear or branched alkyl group having 10 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and 10 to 10 carbon atoms. 14 is more preferable. Further, an alkyl group having 1 or 2 carbon atoms in R ³ and a linear or branched alkyl group having 10 to 18 carbon atoms in R ² are preferable, more preferably 10 to 16 carbon atoms, and further preferably 10 to 14 carbon atoms. preferable. Among the above, as a preferable combination, R ³ is an alkyl group having 1 or 2 carbon atoms, and R ² is a linear or branched alkyl group having 10 to 18 carbon atoms, more 10 to 16 carbon atoms, and 10 carbon atoms. ~ 14 can be mentioned.

Further, as another preferable combination, R ³ is a hydrogen atom, R ² is a linear or branched alkyl group having 10 to 18 carbon atoms, more 10 to 16 carbon atoms, and further 10 to 14 carbon atoms.

The treatment agent of the present invention targets the elements of Groups 6 to 16 of the periodic table or compounds thereof. Group 6 elements include chromium, molybdenum, tungsten, and seabogium, Group 7 elements include manganese, technetium, renium, and borium, and Group 8 elements include iron, ruthenium, and so on. Examples of Group 9 elements include osmium and hassium, Group 9 elements include cobalt, rhodium, iridium, and mitenerium, and Group 10 elements include nickel, palladium, platinum, and dermstatium, and Group 11 elements. Examples of the elements of Group 12 include copper, silver, gold and roentgenium, Group 12 elements include zinc, cadmium, mercury and copernicium, and Group 13 elements include boron, aluminum, gallium and indium. , Thalium, Nihonium, Group 14 elements include carbon, silicon, germanium, tin, lead, Frelovium, Group 15 elements include nitrogen, phosphorus, arsenic, antimony, bismus, moskovium. Examples of Group 16 elements include oxygen, sulfur, selenium, tellurium, polonium, and ribamorium. Among the above elements, the Group 6 elements are chromium, molybdenum, tungsten, the Group 7 elements are manganese, the Group 8 elements are iron, ruthenium, osmium, and the Group 9 elements are. , Cobalt, rhodium, iridium, nickel, palladium, platinum as Group 10 elements, copper, silver, gold as Group 11 elements, zinc, cadmium, mercury, mercury as Group 12 elements. Group 13 elements include boron, gallium, indium, and tarium, Group 14 elements include germanium, tin, and lead, Group 15 elements include arsenic, antimony, bismuth, and Group 16 elements. , Selene, tellurium, chromium, manganese, iron, cobalt, nickel, copper, silver, zinc, cadmium, boron, tin, lead, arsenic, selenium or a compound thereof can be preferably treated. Examples of these compounds include, but are not limited to, oxides, hydroxides, oxo acids and salts thereof, halides, complex salts and the like. From the viewpoint of the amount of the treatment agent of the present invention to be treated per unit gram, the 6th to 8th groups and the 11th to 14th groups can be preferably treated, and among these, chromium, manganese, iron, copper, silver, Zinc, boron and lead can be treated more favorably.

In the present invention, the treatment refers to a treatment for separating the target element or its compound from the water to be treated, and is not particularly limited. For example, the treatment agent of the present invention adsorbs the target element or its compound and is insoluble. This includes a treatment for separating flocs, a treatment for separating insoluble matter produced by the reaction between the treatment agent of the present invention and the target element or a compound thereof, and the like. In addition, a treatment for separating the target element or its compound from the water to be treated by using a treatment agent containing the compound represented by the formula (I) and water is included. Specifically, for example, an aqueous solution or an aqueous dispersion in which the compound represented by the formula (I) is dissolved or dispersed is added to the water to be treated, and the treatment agent of the present invention comprises a target element or a floc insoluble in the compound. The process of forming and separating the compound is included.

Chromium is a metal that is widely distributed in nature and has various valence forms, but the forms that normally exist in nature are trivalent chromium and hexavalent chromium. Chrome is used as an alloy material such as stainless steel, as a refractory material for industrial kilns, plating, pigments, catalysts, and the like. The treatment agent of the present invention is not particularly limited, but can treat chromium existing as a compound such as chromic acid.

Manganese is an essential element for the human body, but overexposure causes manganese poisoning. In the environment, it may be contained in groundwater. For industrial use, it is mainly used for steelmaking, and ferromanganese, which is an alloy of manganese and iron, is used for deoxidation and desulfurization, and is added for the purpose of adding toughness, abrasion resistance, and corrosion resistance to steel. Will be done. In addition, manganese dioxide is used as the positive electrode of the dry battery. In addition, permanganate is used as an oxidizing agent, a bleaching agent, and a medical disinfectant. The treatment agent of the present invention is not particularly limited, but can treat manganese existing as a compound such as permanganate.

Iron is contained in hemoglobin in erythrocytes and is one of the essential elements for the human body, but overdose causes iron poisoning and iron overload. Iron has been used in people's lives since ancient times because it has abundant reserves and is easy to process. Today, it is used as steel, stainless steel, tool steel, building materials, machines, daily necessities, automobiles, home appliances, etc. In addition to a wide variety of fields, it is also used as a raw material for magnets and pigments. The treatment agent of the present invention is not particularly limited, but can treat iron existing as ions or the like, for example.

Copper has various properties such as electric wires, printed circuit boards, electronic materials, ship screws, faucet valves, water pipes, cooking utensils, and alloys due to its excellent conductivity, corrosion resistance, processability, antibacterial properties, and thermal conductivity. Used in various industries. The treatment agent of the present invention is not particularly limited, but can treat copper existing as ions or the like, for example.

Zinc is used not only as a rust preventive plating on steel materials, but also as a copper product, die casting or an inorganic chemical. Zinc is a trace element that is indispensable to the human body along with iron and manganese. The treatment agent of the present invention is not particularly limited, but can treat zinc existing as an ion or the like, for example.

Boron does not exist in nature by itself, but exists as a boron compound such as borax and boric acid. In the environment, it is contained in river water, groundwater, seawater, and soil, and is present in relatively high concentrations especially in hot spring water. Boric compounds are used as raw materials for glass, enamel, glazes for ceramics, etc., and are also used as boric acid as pharmaceuticals, plating additives, preservatives and insecticides. The treatment agent of the present invention is not particularly limited, but can treat boron existing as a compound such as boric acid. For example, it is preferable that the boron concentration of the treated water can be treated to 10 mg / L or less, which is the wastewater standard.

Arsenic is used in semiconductor materials such as gallium arsenide, glass defoamers, insecticides, inorganic chemicals and the like. In addition, arsenic may be contained in hot spring water or strata such as marine mudstone even in the natural world, and may be eluted in groundwater at a high concentration. The treatment agent of the present invention is not particularly limited, but can treat arsenic existing as a compound such as arsenic acid and arsenous acid.

Selenium is used in a wide range of applications such as electronic materials such as photoconductors, catalysts, metallurgy, and production of glass and ceramics. The treatment agent of the present invention is not particularly limited, but can treat selenium existing as a compound such as selenic acid and selenous acid.

In addition, another form of the treatment agent of the present invention comprises the compound represented by the formula (I) and water. In the case of this form, the concentration of the compound represented by the formula (I) is preferably 1 to 50% by weight in terms of efficiently binding to the element to be treated or a compound thereof. Further, in the case of this form, the pH of the treatment agent is preferably less than 6.5 in terms of efficiently binding to the element to be treated or a compound thereof.

(Treatment method using a treatment agent)
The treatment using the treatment agent of the present invention can be carried out by adding the treatment agent to the water to be treated. The water to be treated refers to water containing the element to be treated or a compound thereof, and includes water before and after the addition of the treatment agent.

The method of addition is not particularly limited, but in industrial use, for example, the treatment agent can be added as a solid, mixed with water as an aqueous dispersion, or dissolved in an acid and added as a liquid. When the compound represented by the formula (I) is mixed with water and used, it can be used in the state of a dispersion, a slurry, a cloudy liquid, or a transparent solution, and is preferably a transparent solution. Is. The pH of the solution is preferably less than pH 7 from the viewpoint of transparency, more preferably less than pH 6.5, and particularly preferably pH 6 or less. Among them, the content of the compound when stored at a low temperature is preferably 50% by mass or less. Further, in terms of handleability during use, the viscosity of the solution is preferably 50 mPa · S or less, and the content of the compound is preferably less than 40% by mass. The amount of the treatment agent added to the water to be treated is preferably small, the amount of the compound (effective component) added is preferably 10,000 mg / L or less, and the content of the compound in the treatment agent is preferably 20% by mass or more. That is, in that the treatment target is effectively treated, and the appearance, low temperature stability, and usability are good, the aqueous solution treatment agent of the present invention has a pH of less than 7, and the content of the compound is 1 to 50% by mass. It is preferably 20 to 40% by mass, more preferably 20 to 35% by mass, and particularly preferably 20 to 30% by mass.

The treatment conditions after the addition are not particularly limited, but can be carried out, for example, by stirring and allowing to stand. The treatment agent after the treatment may be separated and recovered by filtration.

The device, operation, and the like are not particularly limited for stirring, and conventionally known devices and operations can be used. For static standing, solid-liquid separation may be performed by installing a sedimentation separation tank or the like without using a special device.

In the treatment using the treatment agent of the present invention, the pH of the water to be treated is not particularly limited, but is adjusted to, for example, pH 3 to 8 from the viewpoint of forming insoluble flocs between the treatment agent of the present invention and the target element or a compound thereof. It is preferable, pH 5 to 8 is more preferable, 5 to 7 is further preferable, and 6 to 7 is particularly preferable.

In the treatment using the treatment agent of the present invention as an aqueous solution, the pH of the water to be treated is not particularly limited from the viewpoint of forming insoluble flocs between the treatment agent of the present invention and the target element or a compound thereof, but is, for example, pH 7 to 12. It is preferable to adjust.

By using the treatment agent of the present invention as an aqueous solution, the handleability of the treatment agent is greatly improved, and an insoluble floc between the treatment agent of the present invention and the target element or a compound thereof can be formed only by a simple operation of adjusting the pH. Water to be treated can be easily obtained by solid-liquid separation. Further, since the treatment operation is simple, when used in many actual treatment facilities, the treatment agent is quantitatively supplied by a pump, and an aqueous solution is preferable to a solid.

In addition, the treatment method of the present invention can be used in combination with or in combination with a treatment method for other elements. For example, the treatment target is highly removed by performing the treatment method of the present invention after treatment by a conventional method such as a coagulation precipitation method, or by treating with an adsorbent such as a chelate resin after treatment by the treatment method of the present invention. Treated water can be obtained. Further, by using the conventional method such as the coagulation precipitation method, the sulfide method, the heavy metal collecting agent method such as dithiocarbamate, and the treatment method of the present invention in combination, the water to be treated can be obtained from which the treatment target has been removed.

The dithiocarbamate is not particularly limited, and examples thereof include an alkali metal salt, an alkaline earth metal salt, and an ammonium salt of dithiocarbamic acid obtained by reacting an amine compound with carbon disulfide and a base. The amine compound is not particularly limited, but for example, ethylamine, diethylamine, propylamine, dipropylamine, piperazine, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene. Hexamine, heptaethyleneoctamine, morpholin, polyethyleneimine and the like can be mentioned. Among these, diethylamine, piperazine, tetraethylenepentamine and polyethyleneimine are preferable, piperazine, tetraethylenepentamine and polyethyleneimine are more preferable, and tetraethylenepentamine and polyethyleneimine are even more preferable. Tetraethylenepentamine can also be a mixture of branched or cyclic amine compounds. Examples of the alkali metal include lithium, sodium and potassium, and sodium and potassium are preferable. Examples of alkaline earth metals include magnesium and calcium. The reaction molar ratio of the amine compound and carbon disulfide is not particularly limited.

When the treatment agent of the present invention is used in combination with dithiocarbamate, the order of addition to the water to be treated is not particularly limited. For example, even if the treatment agent of the present invention is added after adding dithiocarbamate, the reverse is true. May be added in the order of, or at the same time. The same applies when the treatment agent is an aqueous solution. In terms of effectively treating the object to be treated in the water to be treated, it is preferable to add dithiocarbamate to the water to be treated having a pH of 4 or higher. The compound represented by the formula (I) and the dithiocarbamate can efficiently treat a wide range of treatment targets at the same time by a series of operations without inhibiting the effects of both. The mass ratio of the compound to dithiocarbamate is not particularly limited. As an example, when boron is treated, the mass ratio of the compound / dithiocarbamate is preferably 30 to 0.01, more preferably 30 to 0.1, and even more preferably 30 to 1.

Further, it may be a mixed solution of the compound represented by the formula (I) and dithiocarbamate, and is not particularly limited, but for example, an aqueous solution containing the compound of the formula (1) and dithiocarbamate, an aqueous dispersion or the like is used. be able to.

The processing method of the present invention may include a plurality of steps. The step is not particularly limited, but for example, a step of adding the treatment agent of the present invention to the water to be treated, a step of adjusting the water to be treated to neutral, acidic or alkaline, and a step of adding an additive such as a coagulant. And so on.

When adjusting to acidic or alkaline, the pH adjusting agents listed below can be used. The pH adjuster is not particularly limited, but is, for example, an inorganic acid such as hydrochloric acid, sulfuric acid, hydrochloric acid, nitrate, or phosphoric acid and an aqueous solution thereof, an organic acid such as acetic acid, lactic acid, citric acid, or succinic acid and an aqueous solution thereof, or water. Examples thereof include inorganic bases such as sodium oxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and calcium carbonate, and an aqueous solution thereof.

When adjusting to alkaline, the pH can be adjusted to 7-14 for treatment. Among them, when an inorganic base is used as a pH adjuster, a base containing a Group 2 element is preferable, and a hydroxide or a carbonate of the Group 2 element is more preferable, because the pH range in which the treatment target can be treated is wide. , Calcium hydroxide is more preferred. In this case, the pH is preferably adjusted to 7.5 to 14, more preferably pH 8 to 14, and even more preferably pH 10 to 14. Further, among the above-mentioned inorganic bases, bases containing Group 1 elements are preferable, and sodium hydroxide and sodium carbonate are further preferable, in that the treatment target can be treated at a pH near neutral and the pH adjuster is excellent in usability in an aqueous solution. Preferably, in this case, the pH is preferably adjusted to 7 to 9, more preferably pH 7.5 to 8.5, and even more preferably pH 8 to 8.5.

As a preferred example, the treatment method of the present invention includes a step of adding a treatment agent to the water to be treated and a step of adjusting the water to be treated to neutrality. For example, the water to be treated after adding the treatment agent is adjusted to be neutral.

By making the treatment neutral in at least one step of the treatment in this way, the treatment agent becomes insoluble, and boron and the like can be separated and treated efficiently and easily. From the viewpoint of efficient and easy treatment of boron and the like, it is preferable that the water to be treated after the addition is neutral at least in the final stage of the treatment.

In the present specification, neutral, acidic, and alkaline refer to the conventional wisdom, but neutral means a range of about pH 5 to 8, and acidic means a range of about pH 0 to 4. Alkaline generally means the range of pH 9-14.

In one preferred example, the water to be treated is made acidic or alkaline in at least one step of treatment, after which the acidic or alkaline water to be treated is adjusted to neutral. For example, the water to be treated is made acidic or alkaline, and then a treatment agent is added to the water to be treated to adjust the water to be treated to be neutral. Alternatively, the treatment agent is added to the water to be treated, and then the water to be treated is made acidic or alkaline, and the water to be treated is adjusted to be neutral. As a result, the reaction product of the treatment agent which was acidic or alkaline and water-soluble and boron or the like is adjusted to be neutral and becomes insoluble, so that boron or the like can be treated efficiently and easily. In one example, when the water to be treated before adding the treatment agent is acidic or alkaline, the pH is adjusted to neutral after adding the treatment agent.

When adjusting the acidic or alkaline water to be treated to neutrality, the above pH adjusting agent can be added.

Further, by making it acidic in at least one step of the treatment, the treatment agent is once dissolved and efficiently reacts with the target element or its compound, and then when the pH is raised to neutral, flocs (aggregates and precipitates) are formed. ) Improves sedimentation.

In the step of making the water acidic in at least one step of the treatment, when the water to be treated is acidic before the treatment agent is added, and after the treatment agent is added, the acid is added to the water to be treated such as neutral or alkaline. Including the case of making it acidic.

When raising the pH of the acidified water to be treated, it is preferable to adjust the acidic water to be treated to neutrality thereafter. As a result, the sedimentation property of flocs (aggregates and sediments) is particularly improved. When adjusting to neutrality, for example, a pH adjusting agent can be added. As the pH adjuster, the above can be used. In terms of floc sedimentation, divalent or monovalent acid, monovalent base is preferable, and sulfuric acid, nitric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide and an aqueous solution thereof are more preferable.

In the treatment using the treatment agent of the present invention, other components such as a flocculant may be added to the water containing boron or the like together with the treatment agent of the present invention. By adding the treatment agent and the flocculant, the sedimentation property of the flocs (aggregates and precipitates) is improved.

In one preferred example, a flocculant is added to adjust the water to be treated to neutrality at least in one step of the treatment. When the water to be treated is acidic, an alkaline flocculant is added, and when the water to be treated is alkaline, an acidic flocculant is added. In this case, the reaction product of the treatment agent and boron or the like is adjusted to be neutral so that it becomes insoluble, and boron or the like can be treated efficiently and easily.

The coagulant is not particularly limited, and examples thereof include a polymer coagulant, an inorganic coagulant, and a mineral. The polymer flocculant is not particularly limited, but for example, anionic type such as polyacrylamide type, sodium polyacrylate type, polyacrylic acid type, polymethacrylic acid ester type, polyacrylic acid ester type, polyamine type, polydadomac type. , Cationic type such as dicyandiamide type, nonionic type such as polyacrylamide type, polyethylene glycol and polyvinyl alcohol, and amphoteric type such as polyacrylic acid ester-acrylic acid copolymer type. The inorganic flocculant is not particularly limited, and examples thereof include ferric chloride, polytetsu, sulfuric acid band, polyaluminum chloride, aluminum chloride, calcium chloride, potassium aluminate, sodium sulfate, magnesium hydroxide, and copper hydroxide. Be done. The minerals are not particularly limited, but are, for example, carbonate minerals such as hydrotalcite and magnesite, silicate minerals such as zeolite, montmorillonite, kaolin, bentonite and silica, oxidized minerals such as alumina, and carbonates such as limestone. Examples thereof include minerals, sulfate minerals such as plaster, and phosphate minerals such as hydroxyapatite. One type of flocculant may be used alone, or two or more types may be used in combination. Among these, for example, when the treatment target is boron, an inorganic flocculant can be used from the viewpoint of floc sedimentation, and copper hydroxide can be preferably used. From the viewpoint of treatment of boron, a polymer flocculant can be preferably used, and an anionic, cationic or amphoteric polymer flocculant is more preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The treatment agents (Compounds 1 to 11) of the present invention were synthesized as follows. As Compounds 12 to 17 in Comparative Examples, compounds or products synthesized as follows were used.
[Compound 1]
12.0 g of 1-bromodecane, 10.7 g of N-methyl-D-glucamine and 11.2 g of potassium carbonate were added to 36 g of N, N-dimethylformamide and reacted at 80 ° C. for 15 hours. The reaction solution was filtered, 70 g of water was added to the filtrate, and the precipitated precipitate was filtered off, purified and dried to obtain 12.5 g of Compound 1.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 3H, C H 3 - (CH 2) 9 -N), 1.32 (s, 14H, CH 3 - (C H 2) 7 - (CH 2) 2 -N), 1.53 (quin, 2H, CH _3- (CH ₂ ) ₇ -C H ₂ -CH ₂ -N), 2.34 (s, 3H, CH _3- (CH ₂ ) ₉ -N (C H ₃ ) -CH _2- ), 2.46 (m, 2H, CH _3- (CH ₂ ) _8- C H _2- N), 2.57 (m, 2H, N (CH ₃ ) -C H _2- (CH (OH)) _{4 -CH 2 OH), 3.65 (} m, 2H, N (CH 3) -CH 2 - (CH (OH)) 4 -C H 2 OH), 3.76 (m, 3H, N (CH 3) -CH 2 -CH (OH)-(C H (OH)) ₃ -CH ₂ OH), 3.90 (q, 1H, N (CH ₃ ) -CH ₂ -C H (OH)-(CH (OH)) ₃ -CH ₂ OH)
[Compound 2]
15.2 g of Compound 2 was obtained in the same manner as in Compound 1, except that 12.0 g of 1-bromododecane, 9.5 g of N-methyl-D-glucamine and 10.0 g of potassium carbonate were used.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 3H, C H 3 - (CH 2) 11 -N), 1.31 (s, 18H, CH 3 - (C H 2) 9 - (CH 2) 2 -N), 1.53 (quin, 2H, CH _3- (CH ₂ ) ₉ -C H ₂ -CH ₂ -N), 2.33 (s, 3H, CH _3- (CH ₂ ) ₁₁ -N (C H ₃ ) -CH _2- ), 2.47 (m, 2H, CH _3- (CH ₂ ) ₁₀ -C H _2- N), 2.57 (m, 2H, N (CH ₃ ) -C H _2- (CH (OH)) _{4 -CH 2 OH), 3.65 (} m, 2H, N (CH 3) -CH 2 - (CH (OH)) 4 -C H 2 OH), 3.80 (m, 3H, N (CH 3) -CH 2 -CH (OH)-(C H (OH)) ₃ -CH ₂ OH), 3.90 (q, 1H, N (CH ₃ ) -CH ₂ -C H (OH)-(CH (OH)) ₃ -CH ₂ OH)
[Compound 3]
13.8 g of Compound 3 was obtained in the same manner as in Compound 1, except that 12.0 g of 1-bromotetradecane, 9.3 g of N-methyl-D-glucamine and 8.9 g of potassium carbonate were used.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 3H, C H 3 - (CH 2) 13 -N), 1.31 (s, 22H, CH 3 - (C H 2) 11 - (CH 2) 2 -N), 1.53 (quin, 2H, CH _3- (CH ₂ ) ₁₁ -C H ₂ -CH ₂ -N), 2.34 (s, 3H, CH _3- (CH ₂ ) ₁₃ -N (C H ₃ ) -CH _2- ), 2.47 (m, 2H, CH _3- (CH ₂ ) ₁₂ -C H _2- N), 2.58 (m, 2H, N (CH ₃ ) -C H _2- (CH (OH)) _{4 -CH 2 OH), 3.65 (} m, 2H, N (CH 3) -CH 2 - (CH (OH)) 4 -C H 2 OH), 3.80 (m, 3H, N (CH 3) -CH 2 -CH (OH)-(C H (OH)) ₃ -CH ₂ OH), 3.90 (q, 1H, N (CH ₃ ) -CH ₂ -C H (OH)-(CH (OH)) ₃ -CH ₂ OH)
[Compound 4]
13.3 g of Compound 4 was obtained in the same manner as in Compound 1, except that 12.0 g of 1-bromohexadecane, 8.4 g of N-methyl-D-glucamine and 8.1 g of potassium carbonate were used.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 3H, C H 3 - (CH 2) 15 -N), 1.31 (s, 26H, CH 3 - (C H 2) 13 - (CH 2) 2 -N), 1.53 (quin, 2H, CH _3- (CH ₂ ) ₁₃ -C H ₂ -CH ₂ -N), 2.33 (s, 3H, CH _3- (CH ₂ ) ₁₅ -N (C H ₃ ) -CH _2- ), 2.47 (m, 2H, CH _3- (CH ₂ ) ₁₄ -C H _2- N), 2.57 (m, 2H, N (CH ₃ ) -C H _2- (CH (OH)) _{4 -CH 2 OH), 3.65 (} m, 2H, N (CH 3) -CH 2 - (CH (OH)) 4 -C H 2 OH), 3.77 (m, 3H, N (CH 3) -CH 2 -CH (OH)-(C H (OH)) ₃ -CH ₂ OH), 3.90 (q, 1H, N (CH ₃ ) -CH ₂ -C H (OH)-(CH (OH)) ₃ -CH ₂ OH)
[Compound 5]
11.4 g of Compound 5 was obtained in the same manner as in Compound 1, except that 12.0 g of 1-bromooctadecane, 7.7 g of N-methyl-D-glucamine and 7.5 g of potassium carbonate were used.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 3H, C H 3 - (CH 2) 17 -N), 1.31 (s, 30H, CH 3 - (C H 2) 15 - (CH 2) 2 -N), 1.53 (quin, 2H, CH _3- (CH ₂ ) ₁₅ -C H ₂ -CH ₂ -N), 2.33 (s, 3H, CH _3- (CH ₂ ) ₁₇ -N (C H ₃ ) -CH _2- ), 2.47 (m, 2H, CH _3- (CH ₂ ) ₁₆ -C H _2- N), 2.57 (m, 2H, N (CH ₃ ) -C H _2- (CH (OH)) _{4 -CH 2 OH), 3.65 (} m, 2H, N (CH 3) -CH 2 - (CH (OH)) 4 -C H 2 OH), 3.77 (m, 3H, N (CH 3) -CH 2 -CH (OH)-(C H (OH)) ₃ -CH ₂ OH), 3.90 (q, 1H, N (CH ₃ ) -CH ₂ -C H (OH)-(CH (OH)) ₃ -CH ₂ OH)
[Compound 6]
9.0 g of Compound 6 was obtained in the same manner as in Compound 1, except that 8.0 g of 1-bromodecane, 7.6 g of N-ethyl-D-glucamine and 4.4 g of sodium carbonate were used.
¹ H-NMR (MeOD 400MHz): δ 0.92 (t, 3H, C H _3- (CH ₂ ) ₉ -N), 1.08 (t, 3H, CH _3- (CH ₂ ) ₉ -N (CH ₂ C H) _{3) -CH 2 -), 1.32} (s, 14H, CH 3 - (C H 2) 7 - (CH 2) 2 -N), 1.52 (quin, 2H, CH 3 - (CH 2) 7 -C H ₂ -CH ₂ -N), 2.63 (m, 6H, CH _3- (CH ₂ ) ₈ -C H ₂ -N (C H ₂ CH ₃ ) -C H ₂ -CH (OH)-), 3.65 (m _{, 2H, N (CH 2 CH} 3) -CH 2 - (CH (OH)) 4 -C H 2 OH), 3.77 (m, 4H, N (CH 2 CH 3) -CH 2 - (C H (OH )) _4- CH ₂ OH)
[Compound 7]
10.6 g of Compound 7 was obtained in the same manner as in Compound 1, except that 12.0 g of 1-bromodecane, 4.9 g of D-glucamine and 6.6 g of sodium carbonate were used.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 6H, (C H 3 - (CH 2) 9) 2 -N-CH 2 -), 1.32 (s, 28H, (CH 3 - (C H 2 _{) 7 - (CH 2) 2} ) 2 -N-CH 2 -), 1.52 (quin, 4H, (CH 3 - (CH 2) 7 -C H 2 -CH 2) 2 -N-CH 2 -), 2.62 (m, 6H, (CH _3- (CH ₂ ) _8- C H ₂ ) ₂ -NC H _2- CH (OH)-), 3.64 (m, 2H, (CH _3- (CH ₂ ) ₉ ) ₂ -N-CH _2- (CH (OH)) ₄ -C H ₂ OH), 3.78 (m, 4H, (CH _3- (CH ₂ ) ₉ ) ₂ -N-CH _2- (C H (OH)) _4- CH ₂ OH)
[Compound 8]
2.7 g of Compound 8 was obtained in the same manner as in Compound 1, except that 8.0 g of 1-bromodecane, 6.6 g of D-glucamine and 4.4 g of sodium carbonate were used.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 3H, C H 3 - (CH 2) 9 -NH-CH 2 -), 1.32 (s, 14H, CH 3 - (C H 2) 7 - ( CH ₂ ) ₂ -NH-CH _2- ), 1.55 (quin, 2H, CH _3- (CH ₂ ) ₇ -C H ₂ -CH ₂ -NH-CH _2- ), 2.64 (m, 2H, CH _3-) (CH ₂ ) _8- C H ₂ -NH-CH _2- ), 2.78 (m, 2H, CH _3- (CH ₂ ) ₉ -NH-C H _2- CH (OH)-), 3.64 (m, 2H) _{, NH-CH 2 - (CH} (OH)) 4 -C H 2 OH), 3.78 (m, 3H, NH-CH 2 -CH (OH) - (C H (OH)) 3 -CH 2 OH), 3.90 (m, 1H, NH-CH ₂ -C H (OH)-(CH (OH)) _3- CH ₂ OH)
[Compound 9]
9.0 g of Compound 9 was obtained in the same manner as in Compound 1, except that 9.0 g of 1-bromooctadecane, 5.7 g of N-ethyl-D-glucamine and 3.3 g of sodium carbonate were used.
¹ H-NMR (MeOD 400MHz): δ 0.88 (t, 3H, C H _3- (CH ₂ ) ₁₇ -N), 1.03 (t, 3H, CH _3- (CH ₂ ) ₁₇ -N (CH ₂ C H) _{3) -CH 2 -), 1.26} (s, 30H, CH 3 - (C H 2) 15 - (CH 2) 2 -N), 1.43 (quin, 2H, CH 3 - (CH 2) 15 -C H ₂ -CH ₂ -N), 2.57 (m, 6H, CH _3- (CH ₂ ) ₁₆ -C H ₂ -N (C H ₂ CH ₃ ) -C H ₂ -CH (OH)-), 3.73 (m _{, 2H, N (CH 2 CH} 3) -CH 2 - (CH (OH)) 4 -C H 2 OH), 3.81 (m, 4H, N (CH 2 CH 3) -CH 2 - (C H (OH )) _4- CH ₂ OH)
[Compound 10]
5.5 g of Compound 10 was obtained in the same manner as in Compound 1, except that 7.0 g of 1-bromooctadecane, 6.2 g of N-octyl-D-glucamine, and 2.6 g of sodium carbonate were used.
¹ H-NMR (MeOD 400MHz): δ 0.92 (t, 6H, C H _3- (CH ₂ ) ₁₇ -N ((CH ₂ ) ₇ -C H ₃ ) -CH _2- ), 1.31 (s, 40H, _{CH 3 - (C H 2)} 15 - (CH 2) 2 -N ((CH 2) 2 - (C H 2) 5 -CH 3) -CH 2 -), 1.51 (quin, 4H, CH 3 - ( CH ₂ ) ₁₅ -C H ₂ -CH _2- N (CH ₂ -C H _2- (CH ₂ ) ₅ -CH ₃ ) -CH _2- ), 2.60 (m, 6H, CH _3- (CH ₂ ) ₁₆ -C H ₂ -N (C H _2- (CH ₂ ) ₆ -CH ₃ ) -C H ₂ -CH (OH)-), 3.64 (m, 2H, N ((CH ₂ ) ₇ -CH ₃ )- CH _2- (CH (OH)) _4- C H ₂ OH), 3.77 (m, 4H, N ((CH ₂ ) ₇ -CH ₃ ) -CH _2- (C H (OH)) _4- CH ₂ OH )
[Compound 11]
9.1 g of Compound 11 was obtained in the same manner as in Compound 1, except that 9.0 g of 1-bromooctadecane, 4.9 g of D-glucamine and 3.3 g of sodium carbonate were used.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 3H, C H 3 - (CH 2) 17 -NH-CH 2 -), 1.31 (s, 30H, CH 3 - (C H 2) 15 - ( CH ₂ ) ₂ -NH-CH _2- ), 1.51 (quin, 2H, CH _3- (CH ₂ ) ₁₅ -C H ₂ -CH ₂ -NH-CH _2- ), 2.61 (m, 2H, CH _3-) (CH ₂ ) ₁₆ -C H ₂ -NH-CH _2- ), 2.77 (m, 2H, CH _3- (CH ₂ ) ₁₇ -NH-C H _2- CH (OH)-), 3.64 (m, 2H) _{, NH-CH 2 - (CH} (OH)) 4 -C H 2 OH), 3.78 (m, 4H, NH-CH 2 - (C H (OH)) 4 -CH 2 OH)
[Compound 12]
12.0 g of 1-bromooctane, 12.3 g of N-methyl-D-glucamine and 12.9 g of potassium carbonate were added to 30 g of ethanol and reacted under heating under reflux for 24 hours. The reaction solution was filtered, the solvent of the filtrate was distilled off, washed with toluene and water, and dried to obtain 5.6 g of Compound 12.
¹ H-NMR (MeOD 400MHz): δ 0.92 (t, 3H, C H _3- (CH ₂ ) ₇ -N), 1.32 (s, 10H, CH _3- (C H ₂ ) _5- (CH ₂ ) ₂ -N), 1.53 (quin, 2H, CH _3- (CH ₂ ) ₅ -C H ₂ -CH ₂ -N), 2.33 (s, 3H, CH _3- (CH ₂ ) ₇ -N (C H ₃ ) -CH _2- ), 2.45 (m, 2H, CH _3- (CH ₂ ) ₆ -C H _2- N), 2.57 (m, 2H, N (CH ₃ ) -C H _2- (CH (OH)) _{4 -CH 2 OH), 3.66 (} m, 2H, N (CH 3) -CH 2 - (CH (OH)) 4 -C H 2 OH), 3.79 (m, 3H, N (CH 3) -CH 2 -CH (OH)-(C H (OH)) ₃ -CH ₂ OH), 3.90 (q, 1H, N (CH ₃ ) -CH ₂ -C H (OH)-(CH (OH)) ₃ -CH ₂ OH)
[Compound 13]
11.4 g of Compound 13 was obtained in the same manner as in Compound 1, except that 12.0 g of 1-bromooctadecane, 7.7 g of 3-methylamino-1,2-propanediol, and 7.5 g of potassium carbonate were used.
^{1 H-NMR (MeOD 400MHz)} : δ 0.88 (t, 3H, C H 3 - (CH 2) 17 -N), 1.26 (s, 30H, CH 3 - (C H 2) 15 - (CH 2) 2 -N), 1.46 (quin, 2H, CH _3- (CH ₂ ) ₁₅ -C H ₂ -CH ₂ -N), 2.28 (s, 3H, CH _3- (CH ₂ ) ₁₇ -N (C H ₃ ) -CH _2- ), 2.36 (m, 2H, CH _3- (CH ₂ ) ₁₆ -C H ₂ -N), 2.52 (m, 2H, N (CH ₃ ) -C H ₂ -CH (OH) -CH ₂ OH), 3.50 (m, 1H, N (CH ₃ )-CH ₂ -C H (OH) -CH ₂ OH), 3.76 (m, 2H, N (CH ₃ )-CH ₂ -CH (OH)- C H ₂ OH)
[Compound 14]
20.0 g of n-dodecylacrylate and 16.4 g of N-methyl-D-glucamine were added to 30 g of isopropanol, and the mixture was reacted at 80 ° C. for 3 hours. 100 g of water was added, the mixture was cooled, and the precipitated precipitate was filtered off and dried to obtain 32.8 g of compound 14.
^{1 H-NMR (MeOD 400MHz)} : δ 0.92 (t, 3H, C H 3 - (CH 2) 9 -OC (= O)), 1.34 (s, 18H, CH 3 - (C H 2) 9 - ( CH ₂ ) ₂ -OC (= O)), 1.65 (quin, 2H, CH _3- (CH ₂ ) ₉ -C H ₂ -CH ₂ -OC (= O)), 2.34 (s, 3H, OC (=) O)-(CH ₂ ) ₂ -N (C H ₃ ) -CH _2- ), 2.57 (m, 4H, OC (= O)-(C H ₂ ) ₂ -N (CH ₃ ) -CH _2- ) , 2.81 (m, 2H, (CH ₂ ) ₂ -N (CH ₃ ) -C H ₂ -CH (OH)-), 3.64 (m, 2H, N-CH _2- (CH (OH)) ₄ -C H ₂ OH), 3.78 (m, 4H, N-CH _2- (C H (OH)) _4- CH ₂ OH), 4.10 (t, 2H, CH _3- (CH ₂ ) ₉ -C H _2- OC (= O))
[Compound 15]
Miyoshi Oil & Fat Co., Ltd. Boron adsorption resin Eporus B-1 (styrene resin having a glucamine group as a functional group)
[Compound 16]
Miyoshi Oil & Fat Co., Ltd. Arsenic adsorption resin Eporus AS-4 (styrene resin having a terminal iron type iminodiacetic acid group as a functional group)
[Compound 17]
Miyoshi Oil & Fat Co., Ltd. Selenium adsorption resin Eporus SE-3 (styrene resin having a terminal iron type iminodiacetic acid group as a functional group)

The following coagulants were used.

As copper hydroxide, a reagent of Kanto Chemical Co., Inc. was used.

As polyacrylic acid, polyethyleneimine and polyethylene glycol, reagents of Wako Pure Chemical Industries, Ltd. were used.

The acrylamide-sodium acrylate copolymer is Miyofrock AP-800 from Miyoshi Oil & Fat Co., Ltd., the polyvinyl alcohol is PVA-117 from Kuraray Co., Ltd., and the bentonite is Kunibond from Kunimine Kogyo Co., Ltd., polyacrylic acid ester. Diaflock KA804E manufactured by Mitsubishi Chemical Co., Ltd. was used as the acrylic acid copolymer.

The method for synthesizing dithiocarbamate or the preparation ratio of raw materials is not particularly limited, but as an example, the one synthesized as follows was used.

For TEPA-based dithiocarbamate, a sample (40% aqueous solution) obtained by reacting 130 g of tetraethylenepentamine (manufactured by Dow Chemical), 209 g of carbon disulfide, and 220 g of 50 mass% sodium hydroxide in 441 g of ion-exchanged water was used. did.

For piperazine-based dithiocarbamate, a sample (40% aqueous solution) obtained by reacting 110 g of piperazine (manufactured by Tokyo Chemical Industry Co., Ltd.), 194 g of carbon disulfide, and 293 g of 50 mass% potassium hydroxide in 403 g of ion-exchanged water was used. did.

For diethyl-based dithiocarbamate, a sample (55% aqueous solution) obtained by reacting 215 g of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 223 g of carbon disulfide, and 329 g of 50% by mass potassium hydroxide in 233 g of ion-exchanged water was used. did.

For the polyamine-based dithiocarbamate, a modified carbon disulfide / caustic soda (30% aqueous solution) of polyethyleneimine / benzyl chloride condensate was synthesized and used in the same manner as described above.

The following reagents were used to prepare the test solution to be treated, and an aqueous sulfuric acid solution or an aqueous sodium hydroxide solution was used to adjust the pH at the time of preparing the test solution.
Chromium (III) chloride / hexahydrate (Kanto Chemical Co., Inc.)
Potassium permanganate (Kanto Chemical)
Iron (II) Sulfate / Hexahydrate (Kanto Chemical Co., Inc.)
Cobalt (II) Chloride / Hexahydrate (Wako Pure Chemical Industries, Ltd.)
Nickel chloride (II) hexahydrate (Kanto Chemical Co., Inc.)
Copper (II) chloride / dihydrate (domestic chemistry)
Silver sulfate (domestic chemistry)
Zinc chloride (II) (domestic chemistry)
Cadmium chloride (II) (Wako Pure Chemical Industries, Ltd.)
Boric acid (Kanto Chemical)
Tin (II) chloride dihydrate (Kanto Chemical Co., Inc.)
Lead (II) Chloride (Kanto Chemical Co., Ltd.)
Arsenous acid (domestic chemistry)
Selenous acid (Wako Pure Chemical Industries, Ltd.)

[Stability of treatment agent (hydrolysis)]
10 mg of compound 2 or compound 14 was added to 10 mL of a 5% aqueous sulfuric acid solution or 10 mL of a 5% aqueous sodium hydroxide solution, and after stirring for 16 hours, water was distilled off and FT-IR measurement of the dried product was performed.

As a result, no change was observed in FT-IR in compound 2 before and after the test with sulfuric acid or sodium hydroxide, but in compound 14, the ester peak of 1730 cm- ¹ was observed before the test. Was observed to disappear, and it was confirmed that the compound had been decomposed. This result suggests that a compound that undergoes hydrolysis, such as compound 14, cannot stably treat acidic or basic boron-containing water. Therefore, it was suggested that the non-hydrolyzable product of the present invention can be used in various environments and is excellent in treatment.

[Various element treatment tests]
A test solution (water to be treated) for each element prepared in advance at pH = 7, 100 mg / L using the above reagents was prepared. 0.5 g of Compound 2 as a treatment agent was added to 500 mL of this test solution, and the mixture was stirred. After stirring for 1.5 hours, sodium hydroxide was added to make it neutral (pH = 7). The test solution was filtered (No. 5A filter paper), the flocs were filtered off, and the concentration of each element in the filtrate (treated water) was measured by an ICP emission spectrometer (Shimadzu Corporation, ICPE-9820). Similarly, a blank test is performed under the condition that no treatment agent is added, the concentration of each element in the filtrate is measured, and the treatment agent unit gram is calculated from the difference between each element concentration in the blank test and each element concentration in the test in which the treatment agent is added. The amount of treatment per treatment (unit: mg / g) was calculated. The results are shown in Table 1.

From Table 1, it was confirmed that the treating agent of the present invention can treat a wide range of elements from Group 6 chromium to Group 16 selenium in the periodic table. In particular, 10.7 mg / g for Group 6 chromium of Example 1, 21.9 mg / g for Group 11 copper of Example 6, and 39.5 mg of Group 11 silver of Example 7. / G, 30.0 mg / g for Group 12 zinc of Example 8, 35.1 mg / g for Group 13 boron of Example 10, and 65.3 mg / g for Group 14 lead of Example 12. It showed a high processing amount of g. Further, in Example 2, when potassium permanganate was used as the group 7 manganese, a very high treatment amount of 99.7 mg / g was shown. Further, in the group 8 iron of Example 3, when the pH was adjusted to 7 in the blank test, the iron was insolubilized. Therefore, when the pH was adjusted to 6, the treatment amount was as high as 49.4 mg / g.

[Boron treatment test]
A test solution prepared in advance at pH = 7 and a boron concentration of 100 mg / L was prepared. 0.5 g of a treatment agent was added to 500 mL of this test solution, and the mixture was stirred. After stirring for 1.5 hours, the mixture is filtered, and the boron concentration in the filtrate (treated water) is measured with an ICP luminescence analyzer. From the residual boron concentration, the amount of boron treated per gram of treatment agent (unit: unit: mg-B / g) was calculated. The results are shown in Table 2.

From Table 2, the treatment agents of the present invention (Compounds 1 to 11) have the same glucamine group as the treatment agent of the present invention as a functional group, and are compared with Comparative Example 4 which is an existing resin for adsorbing boron which is a styrene-based polymer. In comparison, it can be seen that the value of the boron treatment amount is high and the boron treatment ability is excellent. In addition, Comparative Example 3 having the same glucamine group as the treatment agent of the present invention as a functional group showed boron treatment ability, but as can be seen from the result of the above [stability of treatment agent (hydrolysis)], water was added. It may be degraded, suggesting that the treatment agent of the present invention is superior.

Comparing Example 19 and Comparative Example 2 in which R ² and R ³ are common, it is found that Example 19 has a better boron processing capacity, and that the effect is insufficient when the number of hydroxyl groups of R ¹ is 2. Understand.

Focusing on the total number of carbon atoms of R ² and R ^3, R ² and the total number of carbon atoms in R ³ are dissolved all treatment agent added in Comparative Example 1 is 9, but could not be processed boron, and R ² In Examples 15 to 25 in which the total carbon number of R ³ is 10 or more, boron treatment is possible, and Examples 15 to 18 and Example 20 in which the total carbon number of R ² and R ³ is 10 to 17 are possible. In Example 15, Example 16, Example 16, Example 20 and Example 22 in which the amount of boron treated is 20 g-B / g or more and the total number of carbon atoms of R ² and R ³ is 10 to 13. It was confirmed that the amount of boron treated was 23 g-B / g or more, which was particularly excellent.

Total carbon number of 10 to 17 of ^{R 2} and ^{R 3} This is superior to the process of boron, the total carbon number of 10 to 14 of ^{R 2} and ^{R 3} suggest that better.

Further, comparing Examples 15 to 19 and Comparative Example 1 in which R ¹ and R ³ are common, boron could not be treated in Comparative Example 1 in which the carbon number of R ² was 8, but the carbon number of R ² was 10. in a to 18 is example 15 to 19, shows that it is possible the processing of boron, example number of carbon atoms in ^{R 2} is 10 to 16 15 to 18 boronated weight 20 g-B / g or more, implementation the number of carbon atoms in R ² is 10 to 14 cases 15-17 it was confirmed that boron processing amount is particularly excellent and 21g-B / g or more. When comparing the carbon numbers of R ² with 10 and 18, each of Example 15 and Example 19 in which the carbon number of R ³ is 1, and Examples 22 and 25 in which R ³ is a hydrogen atom are all R. It was confirmed that the compound having 10 carbon atoms of ² had an excellent amount of boron treated.

From this, the alkyl group having R ³ having 1 carbon atom and the linear or branched alkyl group having R ² having 10 to 18 carbon atoms are excellent in the treatment of boron, have more excellent 10 to 16 carbon atoms, and have 10 carbon atoms. It is suggested that ~ 14 is excellent.

When R ^{1, R 2} compares the common Examples 15, 20 and 21, towards the smaller examples 15 and 20 carbon number of ^{R 3} is, excellent processing amount of boron, are hydrogen atoms further ^{R 3} It was confirmed that Example 22 also had an excellent boron processing capacity.

[Arsenic treatment test]
A test solution prepared in advance at pH = 7 and an arsenic concentration of 50 mg / L was prepared. 0.5 g of a treatment agent was added to 500 mL of this test solution, and the mixture was stirred. After stirring for 1.5 hours, the mixture is filtered, and the arsenic concentration in the filtrate (treated water) is measured by an ICP emission spectrometer. From the residual arsenic concentration, the amount of arsenic treated per gram of the treatment agent (unit: unit: mg-As / g) was calculated. The results are shown in Table 3.

From Table 3, Example 26 has an arsenic treatment amount as compared with Comparative Examples 5 and 7 having the same glucamine group as the treatment agent of the present invention as a functional group and Comparative Example 6 which is an existing resin for adsorbing arsenic. It was confirmed that the value was high and the treatment agent of the present invention was excellent.

[Selenium treatment test]
A test solution prepared in advance at pH = 7 and a selenium concentration of 100 mg / L was prepared. 0.5 g of a treatment agent was added to 500 mL of this test solution, and the mixture was stirred. After stirring for 1.5 hours, the mixture is filtered, the concentration of selenium in the filtrate (treated water) is measured by an ICP emission spectrometer, and the amount of selenium treated per gram of the treatment agent is measured from the residual selenium concentration (unit: mg-Se / g) was calculated. The results are shown in Table 4.

From Table 4, Example 27 has a selenium treatment amount as compared with Comparative Examples 8 and 10 having the same glucamine group as the treatment agent of the present invention as a functional group and Comparative Example 9 which is an existing resin for adsorbing selenium. It was confirmed that the value was high and the treatment agent of the present invention was excellent.

[Effect of pH]
A test solution prepared in advance to a boron concentration of 100 mg / L was prepared. After adjusting the pH to a predetermined pH using an aqueous sulfuric acid solution or an aqueous sodium hydroxide solution with respect to 500 mL of this test solution, 0.5 g of a treatment agent was added and stirred while maintaining the pH. After stirring for 1.5 hours, the mixture is filtered, and the boron concentration in the filtrate (treated water) is measured with an ICP luminescence analyzer. From the residual boron concentration, the amount of boron treated per gram of treatment agent (unit: unit: mg-B / g) was calculated. The results are shown in Table 5.

From Table 5, in Reference Example 1, compound 2 was dissolved at pH 2 or less or pH 9 or higher, and the amount of boron treated was 0, but at pH 3 to 8, treatment with boron was observed, and pH 5 to 8, especially pH 6 to In No. 7, it was confirmed that the boron treatment was excellent. On the other hand, in Comparative Example 11, compound 14 was dissolved at pH 5 or lower or pH 9 or higher, the amount of boron treated was 0, and a part of the compound was dissolved at pH 8 as well, indicating a decrease in boron treatment. It was confirmed that Reference Example 1 has a wider insoluble pH range and a higher value of the amount of boron treated at the same pH than Comparative Example 11, and the treatment agent of the present invention is excellent.

[Aqueous acid boron aqueous solution treatment test]
A test solution prepared in advance at pH = 2 and a boron concentration of 100 mg / L was prepared. 0.5 g of the treatment agent was added to 500 mL of this test solution and stirred. After stirring for 1.5 hours, the mixture was adjusted to neutral (pH = 7) with an aqueous sodium hydroxide solution. After the treatment, the mixture is filtered, the boron concentration in the filtrate (treated water) is measured with an ICP luminescence analyzer, and the amount of boron treated per gram of the treatment agent is measured from the residual boron concentration (unit: mg-B /). g) was calculated. The results are shown in Table 6.

From Table 6, it was found that Example 28 was superior in the amount of boron treated as compared with Comparative Examples 12 and 13, and the treatment agent of the present invention was added to acidic boron-containing water, stirred, and neutralized. By adjusting, the treatment agent of the present invention once dissolved in acid reacts efficiently with boron, and by adjusting it to neutrality, flocs are formed, and boron can be treated easily and efficiently.

[Alkaline boron aqueous solution treatment test]
A test solution prepared in advance at pH = 13 and a boron concentration of 100 mg / L was prepared. 0.5 g of the treatment agent was added to 500 mL of this test solution and stirred. After stirring for 1.5 hours, the mixture was adjusted to neutral (pH = 7) with an aqueous sulfuric acid solution. After the treatment, the mixture is filtered, the boron concentration in the filtrate (treated water) is measured with an ICP luminescence analyzer, and the amount of boron treated per gram of the treatment agent is measured from the residual boron concentration (unit: mg-B /). g) was calculated. The results are shown in Table 7.

From Table 7, it was found that Example 29 was superior in the amount of boron treated as compared with Comparative Examples 14 and 15, and the treatment agent of the present invention was added to alkaline boron-containing water, stirred, and neutralized. By adjusting, boron reacts efficiently with the treatment agent of the present invention once dissolved in alkali, and by adjusting it to neutrality, flocs are formed, and boron can be treated easily and efficiently.

[Boron aqueous solution treatment test]
A test solution prepared in advance at pH = 7 and a boron concentration of 100 mg / L was prepared. To 500 mL of this test solution, 1.0 g of Compound 2 was added as a treatment agent, an acid or alkaline pH adjuster was added, and the mixture was stirred to obtain a predetermined pH (pH adjustment (1)). After stirring for 1.5 hours, a pH adjuster (alkali or acid) was added to make it neutral (pH = 7) (pH adjustment (2)). After the treatment, the mixture is filtered, the boron concentration in the filtrate (treated water) is measured with an ICP luminescence analyzer, and the amount of boron treated per gram of the treatment agent is measured from the residual boron concentration (unit: mg-B /). g) was calculated. In addition, the sedimentation property of the flocs at the end of the test was visually confirmed, and those having better sedimentation property were evaluated as ⊚ and those having the same degree of sedimentation property were evaluated as ◯ as compared with Example 30 in which no acid or alkali was added. The results are shown in Table 8.

From Table 8, as shown in Examples 31 to 34, by adding an acid to dissolve the treatment agent once, and then adding an alkali to adjust the pH to neutral, the floc sedimentation property is improved as compared with Example 30. It was confirmed that the pH was about the same or higher, and it was confirmed that the floc sedimentation property was improved especially when sulfuric acid was used as the pH adjuster. Further, by adding an alkali to dissolve the treatment agent once as in Examples 35 to 37 and then adding an acid to adjust the pH to neutral, the floc sedimentation property becomes equal to or higher than that of Example 30. It was confirmed that, in particular, when sulfuric acid was used as the pH adjuster, the floc sedimentation property was improved. In this way, the treatment agent of the present invention, which has been adjusted to be acidic or alkaline and once dissolved, reacts efficiently with boron, and by adjusting it to neutral again, flocs can be formed and boron can be treated easily and efficiently. , It is suggested that the sedimentation property of flocs is improved.

[Boron aqueous solution treatment test (coagulant)]
A test solution prepared in advance at pH = 7 and a boron concentration of 100 mg / L was prepared. To 500 mL of this test solution, 1.0 g of Compound 2 as a treatment agent was added and stirred. After 1.5 hours, each flocculant was added. After the treatment, the mixture is filtered, the boron concentration in the filtrate (treated water) is measured with an ICP luminescence analyzer, and the amount of boron treated per gram of the treatment agent is measured from the residual boron concentration (unit: mg-B /). g) was calculated. In addition, the sedimentation property of the flocs at the end of the test was visually confirmed, and those having better sedimentation property were evaluated as ⊚ and those having the same degree of sedimentation property were evaluated as ◯ as compared with Example 30 in which no flocculant was added. The results are shown in Table 9.

From Table 9, it was confirmed that in Example 38 to which the inorganic flocculant was added, the sedimentation property was equal to or higher than that in Example 30. In Examples 39 to 43 to which the polymer flocculant was added, a boron treatment amount equal to or higher than that in Example 30 was confirmed, and in particular, Examples 39 and 40 which are anionic polymer flocculants and cationic polymers were confirmed. In Example 41, which is a flocculant, an excellent amount of boron treated was confirmed. Further, in Example 44 to which the mineral was added, the amount of boron treated in Example 30 or more was confirmed, and the treatment effect by adding the flocculant was confirmed.

In addition, the following tests were conducted as a treatment in which an inorganic flocculant and a polymer flocculant were combined. To 500 mL of the above test solution, 1.0 g of compound 2 was added as a treatment agent, and after stirring for 1.5 hours, 50 mg / L of polyaluminum chloride as an inorganic flocculant and polyacrylic acid ester as an amphoteric polymer flocculant-. It was confirmed that the precipitation property of flocs was improved by adding 10 mg / L of the acrylic acid copolymer. Further, 1.0 g of compound 2 as a treatment agent was added to 500 mL of the above test solution, and after stirring for 1.5 hours, pH = 2 (acidic) was set using an acidic pH adjuster, and then poly as an inorganic flocculant. About the treatment of adding 50 mg / L of aluminum chloride, adjusting the pH to 7 (neutral) using an alkaline pH adjuster, and adding 10 mg / L of a polyacrylic acid ester-acrylic acid copolymer as a polymer flocculant. It was confirmed that the floc settling property was good.

[Form of treatment agent]
When the solubility of the solid compound 2 as a treatment agent was confirmed with an aqueous hydrochloric acid solution, it began to dissolve at a concentration of 50% by weight or less at a pH of less than 6.5, and completely dissolved at pH 6. An aqueous solution (pH = 6) of compound 2 having a dissolved concentration of 50% by weight or less shown in Table 10 was prepared, and the appearance, low temperature stability at −5 ° C., and viscosity are shown in Table 10.

Regarding the appearance, some dispersion was observed in the 60% by mass aqueous solution of Example 45, and a uniform transparent liquid was obtained in the 50% by mass aqueous solution of Example 46 to the 10% by mass aqueous solution of Example 50, and 50% by mass or less. It was confirmed that the liquid became transparent at the concentration. Regarding the low temperature stability at -5 ° C, it was confirmed that the concentration was stable without any change even after 3 weeks. The viscosity of the aqueous solution was 200 mPa · s or more in the 50 mass% aqueous solution of Example 46, 119 mPa · s in the 40 mass% aqueous solution of Example 47, and 10 mPa · s or less in Examples 48 to 50, and wastewater. Considering the usability and handleability in the treatment, less than 40% by mass is desirable. When the amount of addition (usage amount) required as an aqueous solution for treating the test solution prepared in advance at pH = 7 and the boron concentration of 25 mg / L to the boron concentration of 1 mg / L or less was determined, the amount used was the aqueous solution of compound 2. It depends on the concentration (% by weight), and the lower the concentration of the compound 2 in the treatment agent, the larger the amount used. Therefore, considering the practicality as an aqueous solution, the concentration is preferably more than 10% by weight.

Further, the solid compound 2 is dissolved in dilute sulfuric acid, the aqueous solution of the compound 2 having a concentration of 20% by weight (pH = 6) and the solid compound 2 are dissolved in hydrochloric acid, and the aqueous solution of the compound 2 having a concentration of 20% by weight (pH = 6) is dissolved. pH = 1) was prepared, the same test was performed, the low temperature stability was good, the required addition amount was not different, the acid used for the preparation was not particularly limited, and the pH at the time of preparation was the dissolved pH. It was confirmed that the following is not particularly limited.

Based on the above results, the following studies were conducted using a 30% by mass aqueous solution that can effectively treat the object to be treated, has stability at low temperatures, has low viscosity during use, and is easy to handle.

[Effect of pH]
As a treatment agent, solid compound 2 was dissolved in an aqueous hydrochloric acid solution to prepare a 30% by mass aqueous solution of compound 2 (pH = 6). To 500 mL of the test solution prepared in advance to a boron concentration of 25 mg / L, 1500 mg / L of a 30% by mass aqueous solution of Compound 2 was added as Compound 2 and stirred. After stirring for 10 minutes, the pH was adjusted to a predetermined pH with an aqueous sulfuric acid solution, an aqueous sodium hydroxide solution, or a calcium hydroxide slurry. After the treatment, the mixture is filtered, the boron concentration in the filtrate (treated water) is measured with an ICP luminescence analyzer, and the amount of boron treated per gram of the treatment agent is measured from the residual boron concentration (unit: mg-B /). g) was calculated. The results are shown in Table 11.

From Table 11, in Reference Example 2, compound 2 was dissolved at pH 6 or less or pH 10 or more, and the amount of boron treated became 0, but treatment of boron was observed at pH 7-9. The treatment pH range of boron in a system using sodium hydroxide, which is a Group 1 element, is excellent in the order of pH 6 to less than pH 10, pH 7.5 to 8.5, and pH 8.0 to 8.5. I confirmed that. In Reference Example 3, treatment with boron was observed at pH 7 or higher. Treatment of boron in a system using calcium hydroxide, which is a Group 2 element It was confirmed that the pH range was over pH 6 and the pH was 7.5 or higher, and the boron treatment was excellent. It was confirmed that pH adjustment with calcium can be processed in a wider pH range.

[Boron aqueous solution treatment test (form of treatment agent)]
As a treatment agent, solid compound 2 was dissolved in hydrochloric acid to prepare a 30% by mass aqueous solution (pH = 6) of compound 2. A predetermined amount of solid compound 2 or a 30% by mass aqueous solution of compound 2 was added to 500 mL of the test solution prepared in advance to a boron concentration of 25 mg / L so that the amount of compound 2 added was as shown in Table 12, and the mixture was stirred. After stirring for 10 minutes, it was adjusted to neutral (pH = 8) with an aqueous sodium hydroxide solution. After the treatment, it was filtered and the boron concentration in the filtrate (treated water) was measured by an ICP emission spectrometer. The boron concentration in the treated water is shown in Table 12. The addition amount in the table indicates the addition amount of compound 2.

As Comparative Example 16, the boron concentration in the filtrate which was operated in the same manner except that the treatment agent was not added to the test solution having a boron concentration of 25 mg / L is shown.

From Table 12, the boron concentration of the treated water fell below the wastewater standard of 10 mg / L due to the addition of the treatment agent. Comparing Example 50 and Example 51, the boron concentration in the filtrate decreased as the amount of Compound 2 added increased, confirming the effect of the treatment agent. Further, also in Examples 52 and 53 in which the treatment was carried out with a 30% mass solution of Compound 2, the boron concentration in the filtrate decreased as the amount of Compound 2 added increased, and the effect of the treatment agent was confirmed. It was confirmed that boron can be treated regardless of the form of the treatment agent. Comparing Example 50 and Example 52, and Example 51 and Example 53, although the amount of compound 2 added is the same, Examples 52 and 53, which are aqueous solutions, are in the filtrate. The boron concentration is low, and both solid and aqueous solutions can be treated, but it was confirmed that the aqueous solution has a higher treatment effect. It was suggested that the aqueous solution was uniformly dissolved in the system and the reaction with boron was facilitated. Using an aqueous solution treatment agent with excellent handleability as described above, the treatment can be performed simply by forming flocs with the object to be treated and separating them by a simple and efficient method of adjusting the pH to neutral.

[Boron and nickel mixed aqueous solution treatment test]
Assuming plating wastewater, a test solution prepared in advance with a boron concentration of 100 mg / L and a nickel concentration of 650 mg / L was prepared. 0.5 g or 1.0 g of Compound 2 as a treatment agent was added to 500 mL of this test solution, and the mixture was stirred. After stirring for 1.5 hours, the mixture was adjusted to neutral (pH = 7) with an aqueous sodium hydroxide solution. After the treatment, the mixture was filtered, and the boron concentration and the nickel concentration in the filtrate (treated water) were measured by an ICP emission spectrometer. Table 13 shows the concentrations of each element in the treated water.

From Table 13, it was confirmed that the boron concentration and the nickel concentration in the filtrate were lowered by the addition of the treatment agent. Comparing Example 54 and Example 55, the boron concentration and the nickel concentration in the filtrate decreased as the amount of the treatment agent added increased, and the effect of the treatment agent was confirmed. Comparing boron and nickel, the decrease in boron concentration was remarkable, and it was confirmed that boron could be treated selectively.

[Boron, nickel, zinc mixed aqueous solution treatment test 1]
Test solutions prepared in advance at pH = 7, boron concentration 25 mg / L, nickel concentration 10 mg / L, and zinc concentration 10 mg / L were prepared. To 500 mL of this test solution, TEPA-based, piperazine-based, diethyl-based, and polyamine-based aqueous solutions as dithiocarbamate were added so as to have the amount of dithiocarbamate (effective component) shown in Table 14, and the mixture was stirred for 5 minutes and then treated. A solid 30% by mass aqueous solution (pH = 6) of compound 2 or compound 2 was added as an agent so that the amount of compound 2 added was as shown in Table 14, and the mixture was stirred for 10 minutes. After stirring, the pH was adjusted to neutral (pH = 7 or 8) with an aqueous sodium hydroxide solution. Then, 2 mg / L of a polyacrylic acid ester-acrylic acid copolymer was added, the mixture was slowly stirred for 2 minutes, and allowed to stand for 5 minutes. After standing, it was filtered, and the boron concentration, nickel concentration and zinc concentration in the filtrate (treated water) were measured by an ICP emission spectrometer. Table 14 shows the concentrations of each element in the treated water.

As Comparative Example 18, each of the treated waters operated in the same manner except that dithiocarbamate and a treatment agent were not added to the test solutions having pH = 7, boron concentration 25 mg / L, nickel concentration 10 mg / L and zinc concentration 10 mg / L. The concentration of each element is shown as Comparative Examples 19 and 20, except that only dithiocarbamate is added, and the concentration of each element in the treated water is similarly manipulated.

From Table 14, it was confirmed that in Examples 56 to 58, boron, nickel and zinc could be treated regardless of the type of dithiocarbamate by using dithiocarbamate and the solid compound 2. In Examples 59 to 68, it was confirmed that boron, nickel and zinc can be treated regardless of the type of dithiocarbamate by using the dithiocarbamate and the aqueous solution compound 2, and in particular, boron can be treated, and nickel and zinc can also be treated. I was able to process it. It was also confirmed that the treatment effect was enhanced by increasing the amount of each addition. Comparing Example 59, Example 63, Example 65, and Example 67 with different types of dithiocarbamate, the concentrations of each element in the treated water are polyamine-based ≒ TEPA-based <piperazine-based <dithiocarbate-based in ascending order. The same tendency was observed in Example 60, Example 64, Example 66, and Example 68 in which the amount of dithiocarbamate added was different, and polyamine-based and TEPA-based dithiocarbamate had excellent treatment effects. It was. On the other hand, in Comparative Example 18 in which the dithiocarbamate and the treatment agent were not added, the treatment with boron, nickel and zinc was insufficient, and in Comparative Examples 19 and 20 in which only the dithiocarbamate was added, the heavy metals nickel and zinc were treated. Although the treatment was possible, the treatment with boron was insufficient. Further, when Example 56 and Example 62 are compared, although the amount of the treatment agent added is the same, the aqueous solution of Example 62 has a lower boron concentration in the filtrate, and both the solid and the aqueous solution have a lower boron concentration. Although treatment is possible, it was confirmed that the aqueous solution has higher processing capacity. From the above, it was confirmed that boron, nickel and zinc can be treated efficiently at the same time by using the treatment agent of the present invention in combination with dithiocarbamate.

[Boron, nickel, zinc mixed aqueous solution treatment test 2]
Test solutions prepared in advance at pH = 7, boron concentration 25 mg / L, nickel concentration 10 mg / L, and zinc concentration 10 mg / L were prepared. A solid compound 2 or a 30% by mass aqueous solution of compound 2 (pH = 6) was added to 500 mL of this test solution so that the amount of compound 2 added was as shown in Table 15, and the mixture was stirred for 10 minutes. , A TEPA aqueous solution was added as dithiocarbamate so as to have the amount of dithiocarbamate (effective content) shown in Table 15, and the mixture was stirred for 5 minutes. After stirring, the pH was adjusted to neutral (pH = 7 or 8) with an aqueous sodium hydroxide solution. Then, 2 mg / L of a polyacrylic acid ester-acrylic acid copolymer was added, the mixture was slowly stirred for 2 minutes, and allowed to stand for 5 minutes. After standing, it was filtered, and the boron concentration, nickel concentration and zinc concentration in the filtrate (treated water) were measured by an ICP emission spectrometer. Table 15 shows the concentrations of each element in the treated water.

From Table 15, comparing Example 69 and Example 70 using dithiocarbamate and the solid compound 2, Example 69, which can treat boron, nickel and zinc, and has a treatment pH of 7, is better. , Confirmed that the processing effect is high. It was confirmed that in Example 71 and Example 72 using the compound 2 of the dithiocarbamate and the aqueous solution, both boron, nickel and zinc could be treated, and the treatment effect was enhanced by increasing the addition amount of the treatment agent.

From Tables 14 and 15, Examples 56 and 69, Example 60 and Example 71, and Example 62 and Example 72, in which the addition amounts of the treatment agent and dithiocarbamic acid of the present invention are the same but the order of addition is different, are shown. In comparison, all the elements could be treated in the same manner, and there was no difference in the order of addition between the treatment agent of the present invention and dithiocarbamate, and the treatment agent of the present invention and dithiocarbamate were used in combination. It was confirmed that multiple processing targets can be processed efficiently.

Claims (15)

A treatment agent for treating at least one selected from Group 6 to Group 16 elements of the periodic table or a compound thereof.
A treatment agent containing a compound represented by the following formula (I):

(In the formula, R ¹ represents a linear or branched polyhydroxyalkyl group having 4 to 12 carbon atoms having 3 or more hydroxyl groups, R ² represents a hydrocarbon group having 1 to 22 carbon atoms, and R ³ is hydrogen. atom or a hydrocarbon group having 1 to 22 carbon atoms, the carbon number of ^{R 2} is not less than the number of carbon atoms in ^{R 3,} the total number of carbon atoms in ^{R 2} and ^{R 3} is 10 or more). The first aspect of claim 1, wherein the treatment target is at least one selected from elements of chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, boron, tin, arsenic, selenium, silver and lead or compounds thereof. Treatment agent. The treatment agent according to claim 1, wherein the treatment target is at least one selected from the elements of groups 6 to 8 and groups 11 to 14 or compounds thereof. The treatment agent according to claim 3, wherein the treatment target is at least one selected from elements of chromium, manganese, iron, copper, zinc, boron, silver and lead or compounds thereof. The treatment agent according to any one of claims 1 to 4, which comprises water. The treatment agent according to claim 5, wherein the concentration of the compound represented by the formula (I) is 1 to 50% by weight. The treatment agent according to claim 5 or 6, wherein the pH is less than 6.5. A treatment method for removing a treatment target from water, which includes the following steps:
A step of adding the treatment agent according to any one of claims 1 to 7 to the water to be treated, and a step of adjusting the water to be treated to be neutral. The treatment method according to claim 8, wherein the water to be treated after adding the treatment agent is adjusted to be neutral. The treatment method according to claim 8 or 9, wherein the water to be treated is made acidic or alkaline, and then a treatment agent is added to the water to be treated to adjust the water to be treated to neutrality. The treatment method according to claim 8 or 9, wherein the treatment agent is added to the water to be treated, and then the water to be treated is made acidic or alkaline and the water to be treated is adjusted to be neutral. The treatment method according to any one of claims 8 to 11, further comprising at least one step of adding a flocculant in the treatment step. The treatment method according to claim 12, wherein the flocculant is at least one selected from a polymer flocculant, an inorganic flocculant and a mineral. The treatment method according to any one of claims 8 to 13, further comprising a step of adding dithiocarbamate to the water to be treated. The treatment method according to claim 14, wherein the dithiocarbamate is obtained by reacting an amine compound selected from diethylamine, piperazine, tetraethylenepentamine, and polyethyleneimine with carbon disulfide and a base.