JP4632346B2 - Waste treatment method and heavy metal immobilization treatment composition - Google Patents

Description

  The present invention relates to a waste treatment method and a heavy metal immobilizing agent composition that can insolubilize heavy metals contained in waste safely and reliably.

  There are various types of solid substances such as fly ash and incineration ash generated at garbage incinerators, dust, mines discharged from mines, activated sludge generated during wastewater treatment, and contaminated soil such as ruins of chemical factories. It contains metals and may contain a large amount of heavy metals that are harmful to the human body, such as mercury, cadmium, lead, zinc, copper, and chromium. When heavy metals are eluted from solid substances into groundwater, rivers, and seawater, serious environmental pollution is a problem.

  For this reason, it has been proposed to immobilize heavy metals with a heavy metal immobilizing agent before final disposal of solid waste by landfill, etc., because of its excellent ability to collect mercury and cadmium. A dithiocarbamic acid type heavy metal immobilizing agent having a dithiocarbamic acid group or a salt thereof as a functional group is widely used as a heavy metal immobilizing agent. However, the dithiocarbamate-type heavy metal immobilization treatment agent has the advantage of excellent trapping power for mercury, cadmium, etc., but it tends to generate toxic gases such as carbon disulfide when added to fly ash. There was a problem that there was something. Recently, the Ministry of Health, Labor and Welfare has confirmed that carbon disulfide is generated from most of the heavy metal immobilization treatment agents currently used. The company has been instructed to take measures to replace heavy metal immobilizing agents with those that do not easily generate carbon disulfide, and it is desirable to use heavy metal immobilizing agents that generate less carbon disulfide. Yes. From such a viewpoint, a method for stabilizing the heavy metal immobilization treatment agent by adding an amine to the dithiocarbamic acid type heavy metal immobilization treatment agent has been proposed (Patent Document 1).

Japanese Patent No. 3455363

However, although the method described in Patent Document 1 can suppress the generation of carbon disulfide when added to waste such as fly ash, amines generally have high toxicity and sensitization, and heavy metal immobilization treatment is possible. When a chemical agent and a highly volatile low molecular weight amine are used in combination, the amine is likely to scatter, causing an amine odor when disposing of the waste, causing discomfort, causing environmental pollution in the surrounding area, and possibly causing harm to the human body. is there. On the other hand, when a high molecular weight amine is added, there is a possibility that the long-term stability of the heavy metal immobilization treatment agent may be lowered, or the long-term stability of the metal immobilization performance by the heavy metal immobilization treatment agent may be impaired.

  An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a waste treatment method and a heavy metal fixing treatment agent composition capable of safely treating waste.

That is, the present invention
(1) A dithiocarbamate-type heavy metal immobilizing agent having a dithioacid-type functional group introduced by substituting more than 50% of the active hydrogen bonded to nitrogen of the amines, and the nitrogen of the amines From hydroxyl groups and hydroxyl group salts, carboxyl groups and carboxyl group salts, dithioic acid groups and dithioic acid group salts introduced by substituting with 50% or less (except 50%) of the active hydrogens bonded Dithiocarbamic acid with respect to waste at a ratio of 0.01 to 15% by weight of the amine derivative with respect to the total amount of the heavy metal immobilizing agent and the amine derivative, and the amine derivative having the selected N-substituent. A waste treatment method characterized by adding to the waste so that the amount of the type heavy metal immobilization treatment agent is 0.1 to 50% by weight in an anhydrous form, and insolubilizing the heavy metal in the waste,
(2) The waste treatment method according to (1), wherein the waste is fly ash,
(3) A dithiocarbamate-type heavy metal immobilizing agent having a dithioacid-type functional group introduced by substituting more than 50% of the active hydrogen bonded to nitrogen of the amines, and the nitrogen of the amines From hydroxyl groups and hydroxyl group salts, carboxyl groups and carboxyl group salts, dithioic acid groups and dithioic acid group salts introduced by substituting with 50% or less (except 50%) of the active hydrogens bonded Ri Do from the amine derivative having a selected N- substituent, the total amount of the proportion of amine derivative heavy metal immobilizing agent and an amine derivative, characterized in 0.01 to 15 wt% der Rukoto A heavy metal immobilizing agent composition,
Is a summary.

  According to the method of the present invention, when heavy metals in waste are insolubilized, heavy metals in waste can be safely and reliably produced without causing unpleasant odor, contamination of the work environment, and harm to the human body. Can be insolubilized. In addition, the heavy metal immobilizing agent composition of the present invention has no possibility of generating carbon disulfide, carbonyl sulfide, amine or the like when added to waste such as fly ash. Also, by using an amine derivative having a highly water-soluble functional group such as a carbonyl group salt or a dithioic acid group salt in combination with a heavy metal fixing treatment agent, the water solubility can be increased or the amount added during treatment can be increased. And the long-term stability of the product can be improved.

The dithiocarbamic acid type heavy metal immobilizing agent used in the present invention is, for example, a nitrogen compound of amines among compounds obtained by reacting carbon disulfide with amines and introducing a dithioacid group or a salt thereof into nitrogen of amines. Is a compound in which the substitution rate between the active hydrogen bonded to and the dithioic acid type functional group exceeds 50%. For compounds in which the substitution rate between the active hydrogen of amines and the dithioic acid type functional group exceeds 50%, the amines must be reacted with carbon disulfide exceeding 0.5 times moles of active hydrogen of amines. Can be obtained. Examples of amines include monoalkylamines such as monomethylamine, monoethylamine, monopropylamine, monoisopropylamine, monobutylamine, monoisobutylamine, amylamine, 2-ethylhexylamine, cyclohexylamine, benzylamine; dimethylamine, diethylamine , Dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, ethylmethylamine, methylpropylamine, isopropylmethylamine, butylmethylamine, isobutylmethylamine, ethylpropylamine, ethylisopropylamine, butylethylamine, ethylisobutylamine, isopropyl Propylamine, butylpropylamine, butylisobutylamine, diamylamine, di-2-ethylhexyl Dialkylamines such as amines; ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tripropylenetetramine, tributylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, Tetrabutylene pentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, iminobispropylamine, monomethylaminopropylamine, methyliminobispropylamine, 1,3-propanediamine, 1,4-butanediamine, hexa Methylene diamine, octamethylene diamine, N, N′-dimethylethylenediamine, N, N′-diethylpropylene diamine , N, N′-diethylethylenediamine, N, N′-diethylpropylenediamine and other aliphatic amines; monomethanolamine, monoethanolamine, monopropanolamine, monoisopropanolamine, monobutanolamine, monoisobutanolamine and other monoamines Alcoholamines: Diethanolamines such as dimethanolamine, diethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, diisobutanolamine; methylphenylamine, ethylphenylamine, phenylpropylamine, isopropylphenylamine, butylphenylamine, isobutyl Alkylphenylamines such as phenylamine; morpholine; 2-methylmorpholine, 2-ethylmorpholine, 2-propylmorpholine, 2 Monoalkylmorpholine such as isopropylmorpholine, 2-butylmorpholine, 2-isobutylmorpholine, 3-methylmorpholine, 3-ethylmorpholine, 3-propylmorpholine, 3-isopropylmorpholine, 3-butylmorpholine, 3-isobutylmorpholine; Dialkylmorpholines such as 3-dimethylmorpholine, 2,5-diethylmorpholine and 2-ethyl-5-methylmorpholine; trialkylmorpholines such as 2,3,5-trimethylmorpholine and 2,3-dimethyl-6-ethylmorpholine; Tetraalkylmorpholines such as 2,3,5,6-tetraethylmorpholine, 2-ethyl-3,5,6-trimethylmorpholine; piperazine; 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-isopropyl Monoalkylpiperazines such as piperazine, 1-butylpiperazine, 2-methylpiperazine, 2-ethylpiperazine, 2-propylpiperazine, 2-isopropylpiperazine, 2-butylpiperazine, 2-isobutylpiperazine; 2,3-dimethylpiperazine, 2 Dialkyl piperazines such as 1,5-diethylpiperazine, 1,3-diethylpiperazine; Trialkylpiperazines such as 2,3,5-trimethylpiperazine, 1,2,5-trimethylpiperazine, 2,3-dimethyl-5-ethylpiperazine Tetraalkylpiperazines such as 2,3,5,6-tetramethylpiperazine, 1,3,5,6-tetrapropylpiperazine, 3-ethyl-2,5,6-trimethylpiperazine; pyrrolidine; 2-methylpyrrolidine; 2-ethylpyrrolidine, 2-pro Mono, such as pyrpyrrolidine, 2-isopropylpyrrolidine, 2-butylpyrrolidine, 2-isobutylpyrrolidine, 3-methylpyrrolidine, 3-ethylpyrrolidine, 3-propylpyrrolidine, 3-isopropylpyrrolidine, 3-butylpyrrolidine, 3-isobutylpyrrolidine Alkylpyrrolidines; dialkylpyrrolidines such as 2,3-dimethylpyrrolidine, 2,4-diethylpyrrolidine, 2-ethyl-3-methylpyrrolidine; 2,3,4-trimethylpyrrolidine, 2,3-dimethyl-5-ethylpyrrolidine, etc. Trialkylpyrrolidines; tetraalkylpyrrolidines such as 2,3,4,5-tetramethylpyrrolidine and 2-ethyl-3,4,5-trimethylpyrrolidine; piperidine; 2-methylpiperidine, 2-ethylpiperidine, 2-propyl Piperidi 2-isopropylpiperidine, 2-butylpiperidine, 2-isobutylpiperidine, 3-methylpiperidine, 3-ethylpiperidine, 3-propylpiperidine, 3-isopropylpiperidine, 3-butylpiperidine, 3-isobutyltipiperidine, 4-methyl Monoalkylpiperidines such as piperidine, 4-ethylpiperidine, 4-propylpiperidine, 4-isopropylpiperidine, 4-butylpiperidine, 4-isobutylpiperidine; 2,3-dimethylpiperidine, 2,5-diethylpiperidine, 2,4- Dialkylpiperidines such as dipropylpiperidine and 2-methyl-4-propylpiperidine; Trialkylpiperidines such as 2,4,6-trimethylpiperidine and 2,4-ethyl-6-propylpiperidine; 2,3,5,6- Tetrame Tetraalkylpiperidines such as lupiperidine and 2,3,4,6-triethylpiperidine; pentaalkylpiperidines such as 2,3,4,5,6-pentamethylpiperidine and 2,3,4,5,6-pentaethylpiperidine And homopiperazine.
Also thiomorpholine; 2-methylthiomorpholine, 2-ethylthiomorpholine, 2-propylthiomorpholine, 2-isopropylthiomorpholine, 2-butylthiomorpholine, 2-isobutylthiomorpholine, 3-methylthiomorpholine, 3-ethylthiomorpholine, Monoalkylthiomorpholine such as 3-propylthiomorpholine, 3-isopropylthiomorpholine, 3-butylthiomorpholine, 3-isobutylthiomorpholine, 2,3-dimethylthiomorpholine, 2,5-diethylthiomorpholine, 2,6-di Dialkylthiomorpholines such as propylthiomorpholine, 2-ethyl-3-methylthiomorpholine, 2-methyl-6-propylthiomorpholine; 2,3,5-trimethylthiomorpholine, 2,3,6-triethylthiomorpholine, etc. Trialkylthiomorpholine; tetraalkylthiomorpholine such as 2,3,5,6-tetramethylthiomorpholine, 2-ethyl-3,5,6-trimethylthiomorpholine; imidazolidine; 1-methylimidazolidine, 1-ethylimidazolidine, 1-propylimidazolidine, 1-isopropylimidazolidine, 1-butylimidazolidine, 1-isobutylimidazolidine, 2-methylimidazolidine, 2-ethylimidazolidine, 2-propylimidazolidine, 2-isopropylimidazolidine, 2- Butyl imidazolidine, 2-isobutyl imidazolidine, 3-methyl imidazolidine, 3-ethyl imidazolidine, 3-propyl imidazolidine, 3-isopropyl imidazolidine, 3-butyl imidazolidine, 3-isobutyl imidazole Lysine, 4-methylimidazolidine, 4-ethylimidazolidine, 4-propylimidazolidine, 4-isopropylimidazolidine, 4-butylimidazolidine, 4-isobutylimidazolidine, 5-methylimidazolidine, 5-ethylimidazolidine, Monoalkylimidazolidines such as 5-propylimidazolidine, 5-isopropylimidazolidine, 5-butylimidazolidine, 5-isobutylimidazolidine; 2,3-dimethylimidazolidine, 2,5-diethylimidazolidine, 4,5- Dialkylimidazolidines such as dipropylimidazolidine and 1-methyl-4-propylimidazolidine; trialkylimidazolidines such as 2,4,5-trimethylimidazolidine and 3,4-diethyl-5-propylimidazolidine; 3, 4, Tetraalkylimidazolidines such as 5-tetramethylimidazolidine, 1,2,4,5-tetramethylimidazolidine; pyrazolidines; 1-methylpyrazolidine, 1-ethylpyrazolidine, 1-propylpyrazolidine, 1 -Isopropylpyrazolidine, 1-butylpyrazolidine, 1-isobutylpyrazolidine, 2-methylpyrazolidine, 2-ethylpyrazolidine, 2-propylpyrazolidine, 2-isopropylpyrazolidine, 2- Butylpyrazolidine, 2-isobutylpyrazolidine, 3-methylpyrazolidine, 3-ethylpyrazolidine, 3-propylpyrazolidine, 3-isopropylpyrazolidine, 3-butylpyrazolidine, 3-isobutyl Pyrazolidine, 4-methylpyrazolidine, 4-ethylpyrazolidine, 4-propylpyrazolidine, 4 Isopropylpyrazolidine, 4-butylpyrazolidine, 4-isobutylpyrazolidine, 5-methylpyrazolidine, 5-ethylpyrazolidine, 5-propylpyrazolidine, 5-isopropylpyrazolidine, 5-butyl Monoalkylpyrazolidine such as pyrazolidine, 5-isobutylpyrazolidine; 3,4-dimethylpyrazolidine, 3,5-diethylpyrazolidine, 2,5-dipropylpyrazolidine, 3-methyl- Dialkylpyrazolidines such as 5-propylpyrazolidine; trialkylpyrazolidines such as 3,4,5-trimethylpyrazolidine and 2,4-diethyl-5-propylpyrazolidine; Tetraalkylpyrazolidine such as 5-tetramethylpyrazolidine and 1,4-diethyl-3,5-dipropylpyrazolidine; pyrrole; Lupyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2-isopropylpyrrole, 2-butylpyrrole, 2-isobutylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-isopropylpyrrole, 3-butyl Monoalkylpyrrole such as pyrrole and 3-isobutylpyrrole; 2,3-dimethylpyrrole, 2,5-diethylpyrrole, 2,4-dipropylpyrrole, 2-ethyl-4-methylpyrrole, 2-methyl-3-propyl Dialkyl pyrrole such as pyrrole; Trialkyl pyrrole such as 2,3,4-trimethylpyrrole, 2,3,5-triethylpyrrole; 2,3,4,5-tetramethylpyrrole, 2-ethyl-3,4,5 -Tetraalkylpyrrole such as trimethylpyrrole; imidazole; 2-methyl Ruimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-butylimidazole, 2-isobutylimidazole, 4-methylimidazole, 4-ethylimidazole, 4-propylimidazole, 4-isopropylimidazole, 4- Monoalkylimidazole such as butylimidazole, 4-isobutylimidazole, 5-methylimidazole, 5-ethylimidazole, 5-propylimidazole, 5-isopropylimidazole, 5-butylimidazole, 5-isobutylimidazole, 2,4-dimethylimidazole, Dialkyl such as 2,5-diethylimidazole, 2,4-dipropylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-5-propylimidazole Midazole; trialkylimidazole such as 2,4,5-trimethylimidazole, 2,4,5-triethylimidazole; pyrazole; 3-methylpyrazole, 3-ethylpyrazole, 3-propylpyrazole, 3-isopropylpyrazole, 3-butyl Pyrazole, 3-isobutylpyrazole, 4-methylpyrazole, 4-ethylpyrazole, 4-propylpyrazole, 4-isopropylpyrazole, 4-butylpyrazole, 4-isobutylpyrazole, 5-methylpyrazole, 5-ethylpyrazole, 5-propyl Monoalkylpyrazoles such as pyrazole, 5-isopropylpyrazole, 5-butylpyrazole, 5-isobutylpyrazole, 3,4-dimethylpyrazole, 3,5-diethylpyrazole, 3,4-dipropylpyrazole Dialkylpyrazoles such as 3-ethyl-5-methylpyrazole; trialkylpyrazoles such as 3,4,5-trimethylpyrazole and 3,4,5-triethylpyrazole; phenylenediamine, o-, m-, p-xylylene diene Aromatic amines such as amine, 3,5-diaminochlorobenzene and aniline; cycloalkane polyamines such as 1,3-bis (aminomethyl) cyclohexane; polyethyleneimine, polypropyleneimine, poly-3-methylpropylimine, poly-2 -Cyclic imine polymers such as ethylpropylimine; polymers of unsaturated amines such as polyvinylamine and polyallylamine. It is also possible to copolymerize unsaturated amines such as vinylamine and allylamine with unsaturated amines such as dimethylacrylamide, styrene, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrene sulfonic acid, and their salts. Copolymers with other monomers having a saturated bond, polyethyleneimine / benzyl chloride condensates and the like can also be mentioned. These can also use 2 or more types of mixtures.

  The dithiocarbamic acid type heavy metal immobilizing agent may have a dithioacid type functional group of an acid type (terminal is hydrogen) or a salt type (terminal is metal, amine, etc.). Further, one having two or more dithioic acid type functional groups introduced in one molecule may be used. In the case of a compound having two or more dithioic acid type functional groups, it may have only an acid type functional group, may have only a salt type functional group, or may have both good. Examples of the salt-type functional group include barium salt, sodium salt, potassium salt, calcium salt, magnesium salt, amine salt and the like, but sodium salt and potassium salt are usually preferable. Such a compound can be obtained by reacting an amine with carbon disulfide, and the reaction between the amine and carbon disulfide is performed in the presence of an alkali such as the corresponding metal hydroxide or after the reaction. By treating with an alkali, a compound having a salt-type functional group can be obtained. The dithiocarbamic acid type heavy metal immobilization treatment agent can be used in combination of two or more compounds.

Amine derivative used in the present invention, among the compounds with A amine such nitrogen introduced by replacing the bound active hydrogen was N- substituent, an active hydrogen and N- substituent attached to the nitrogen of the amine And a substitution rate of less than 50%. The amines used in amine derivatives, xylene diamine, ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethyleneheptamine, heptaethyleneoctamine, 1,3-propanediamine, 1, 4-butanediamine, hexamethylenediamine, octamethylenediamine, polyethyleneimine, polypropyleneimine, poly-3-methylpropylimine, poly-2-ethylpropylimine, porvinylamine, polyallylamine, polyethyleneimine / benzyl chloride condensate preferable. The N- substituent, for example, salts of dithiophosphoric acid or dithio acid, a salt of a carboxyl group or a carboxyl group, Ru include salts of water acid group or a hydroxyl group.

The process of reacting an amine and carbon disulfide, N- amine derivative having a dithio group as a substituent can be obtained, a method of reacting an amine with a haloalkyl carboxylic acid or amine and acrylic acid it can be a method of reacting an acrylic acid ester, by a method such as reacting an amine with methacrylic acid or methacrylic acid ester, to obtain the amine derivative having a carboxyl group as N- substituent. Also, by reacting amines with aldehydes such as formaldehyde, reacting amines with ketones, reacting amines with ethylene oxide, propylene oxide, aliphatic alkylene oxide, aromatic alkylene oxide, etc. , it is possible to obtain an amine derivative having a hydroxyl group as N- substituent. These reactions can be carried out in the presence of an alkali or treated with an alkali after completion of the reaction to form an N-substituent salt.

Dithiocarbamate type heavy metal immobilization treatment agent used in the present invention, amines derivatives can be obtained by a method such as described above. As amine derivatives, when using a compound having the same dithio group or a salt thereof with the functional groups of the heavy metal immobilization treatment agent as N- substituent, in the reaction product of an amine and carbon disulfide, amines A compound having a dithiocarbamic acid type functional group substituted with more than 50% of active hydrogen (a compound corresponding to a dithiocarbamic acid type heavy metal immobilizing agent), and 50% or less (excluding 50%) of active hydrogen of amines; when a compound having a dithiocarbamate group as substituted N- substituent and (amine derivative) is present in admixture, this can be used as it is as heavy metal immobilization treatment agent composition of the present invention.

The dithiocarbamic acid type heavy metal immobilizing agent having a dithiocarbamic acid type functional group substituted with more than 50% of active hydrogens of amines used in the present invention is excellent in heavy metal collecting ability, but added alone to waste. It is easy to generate carbon disulfide. On the other hand, (excluding 50%) 50% or less of the active hydrogen amine with an amine derivative having a substituted N- substituent, or no heavy metal immobilization ability, N- substituent heavy metal immobilization ability Even if it is a dithiocarbamic acid group (or a salt thereof) having a heavy metal, the heavy metal capturing ability is low, but the heavy metal immobilizing agent composition of the present invention used in combination with the dithiocarbamic acid type heavy metal immobilizing agent is used for the heavy metal immobilizing treatment. The generation of carbon disulfide when the agent is added to the waste can be effectively suppressed, and excellent heavy metal immobilization ability is expressed. When the dithiocarbamic acid type heavy metal immobilizing agent in the heavy metal immobilizing agent composition is a compound having a dithiocarbamic acid type functional group introduced by substituting the active hydrogen of amines with less than 50%, the heavy metal immobilizing ability It becomes inferior to. On the other hand, amine derivative constituting the heavy metal immobilization treatment agent composition, when N- substituent groups introduced by replacing the active hydrogen of amines is a compound of more than 50%, reduction of generation of carbon disulfide The effect becomes low and the intended purpose cannot be achieved.

In the process of the present invention, the dithiocarbamate type heavy metal immobilization treatment agent, the amine derivative, may also be added separately added simultaneously to the waste, but the dithiocarbamate type heavy metal immobilization treatment agent in waste when added, it is preferred that amine derivative is present in the waste. Therefore, either the amine derivative is added before the heavy metal immobilization treatment agent is preferably added simultaneously with the heavy metal immobilization treatment agent. Also when such addition of pre-dithiocarbamate type heavy metal immobilization treatment agent and a heavy metal immobilization treatment composition obtained by mixing an amine derivative to waste, to perform efficient processing on treatment effect and workability Can do. As a method for adding a heavy metal immobilization treatment agent and an amine derivative (or heavy metal immobilization treatment agent composition prepared by mixing the two) to the waste, the method of spraying and the like, for example, as an aqueous solution thereof or suspension. Proportion of amine derivative, against the total amount of heavy metal immobilization treatment agent with an amine derivative, when it exceeds 1 5 wt%, although carbon disulfide occurs some inhibitory effect, heavy metal immobilization performance degrades eyes, 0. 01-15% by weight is used. The amount of dithiocarbamate type heavy metal immobilization treatment agent for waste from 0.1 to 50% by weight anhydride.

  The method of the present invention is suitable for the treatment of waste containing heavy metals, such as solid waste such as slag, soil, fly ash, waste water, exhaust gas, etc., but is particularly suitable as a treatment method for fly ash. Examples of heavy metals to be treated by the method of the present invention include lead, cadmium, hexavalent chromium, arsenic, selenium, mercury, nickel, molybdenum, antimony, copper, zinc, manganese and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. The dithiocarbamic acid type heavy metal immobilizing agent and amine derivatives used in the following examples and comparative examples are as follows.

Heavy metal immobilization treatment agent (1) Heavy metal immobilization treatment agent A: N, N-diethylamine-potassium N-carbodithioate (active hydrogen bonded to nitrogen of diethylamine and substitution rate of dithioacid group type functional group 100%).
(2) Heavy metal immobilizing agent B: tetraethylenepentamine-N, N ′, N ″, N ″ ″-sodium tetracarbodithioate (active hydrogen and dithioate group bonded to nitrogen of tetraethylenepentamine) Type functional group substitution rate 57%).
(3) Heavy metal immobilization treatment agent C: potassium piperazine-N, N′-biscarbodithioate (active hydrogen bonded to nitrogen of piperazine and substitution rate of dithioacid group type functional group 100%).
(4) Heavy metal immobilization treatment agent D: Compound obtained by introducing sodium dithioate into nitrogen of polyethyleneimine / benzyl chloride condensate (active hydrogen bonded to nitrogen of polyethyleneimine and substitution rate of dithioic acid type functional group 60%) Tetraethylenepentamine-N, N ′, N ″, N ″ ″-sodium tetracarbodithioate (active hydrogen bonded to nitrogen of tetraethylenepentamine and substitution rate of dithioacid group type functional group 57%) 1: 8 (weight ratio) mixture.
(5) Heavy metal immobilizing agent E: a compound in which potassium dithioate is introduced into nitrogen of polyethyleneimine / benzyl chloride condensate (active hydrogen bonded to nitrogen of polyethyleneimine and substitution rate of dithioacid type functional group 60%); 1:10 (weight ratio) mixture of potassium piperazine-N, N′-biscarbodithioate (active hydrogen bonded to nitrogen of piperazine and substitution rate of dithioacid group type functional group 100%).

Amine derivative (1) amine derivative A: and tetraethylenepentamine tetraethylene obtained by reacting 1 molar formaldehyde to pentamine -N- methanol (active hydrogen attached to the nitrogen of tetraethylene pentamine Hydroxyl type functional group substitution rate 14%)
(2) Amine derivative B: Tetraethylenepentamine-N, -propanoic acid sodium salt obtained by reacting 1 mol of methyl acrylate with tetraethylenepentamine and then saponifying and decomposing with sodium hydroxide (Substitution rate of 14% of active hydrogen bonded to nitrogen of tetraethylenepentamine and carboxyl functional group)
( 3 ) Amine derivative C : tetraethylenepentamine-sodium N-carbodithioate obtained by reacting 1 mol of carbon disulfide with sodium hydroxide with respect to tetraethylenepentamine (to the nitrogen of tetraethylenepentamine) 14% substitution rate of bonded active hydrogen and dithioic acid type functional groups)

Examples 1 to 3
Per fly ash 100g caused by garbage incineration, heavy metal immobilization treatment composition 0.8 g (anhydride dithiocarbamate type heavy metal immobilization treatment agent and the amine derivative in a mixing ratio shown in the table shown in Table 1 ) And water were added to a total amount of 20 g and kneaded for 10 minutes. Table 1 shows the results of measuring the amount of metal elution from the treated fly ash based on the Environmental Agency Notification No. 13 test method. Table 1 also shows the results of measuring the amount of carbon disulfide generated by the following measurement method.

Method for measuring carbon disulfide generation amount After charging 20.0 g of alkaline fly ash into a sealed 500 ml four-necked flask and substituting with nitrogen, 0.4 g (as anhydride) of the heavy metal immobilizing agent and the total amount of water is 30 It adjusted to 0.0g, and it melt | dissolved uniformly, and added to the fly ash. After the addition, the mixture was stirred at 60 ° C. for 15 minutes, and the amount of carbon disulfide generated was measured with a carbon disulfide detector tube (manufactured by Gastec Co., Ltd.).

Comparative Examples 1-6
The fly ash was treated in the same manner as in Examples 1 to 3 except that 100 g of the heavy metal immobilizing agent shown in Table 1 was added per 100 g of fly ash. The amount of metal elution from the treated fly ash was measured in the same manner as in Examples 1 to 3 . The measurement results of the amount of carbon disulfide generated are also shown in Table 2.

Claims (3)

Dithiocarbamic acid type heavy metal immobilizing agent having dithioic acid type functional group introduced by replacing more than 50% of active hydrogens bonded to nitrogen of amines, and activity of amines bonded to nitrogen Selected from hydroxyl groups and hydroxyl group salts, carboxyl groups and carboxyl group salts, dithioic acid groups and dithioic acid group salts introduced by replacing with 50% or less of hydrogen (excluding 50%) of active hydrogen Dithiocarbamic acid type heavy metal immobilization with respect to the waste with an amine derivative having an N-substituent in an amount of 0.01 to 15% by weight of the amine derivative with respect to the total amount of the heavy metal immobilization treatment agent and the amine derivative A waste treatment method comprising adding an amount of a chemical treatment agent to waste so as to be 0.1 to 50% by weight of an anhydride to insolubilize heavy metals in the waste. The waste treatment method according to claim 1, wherein the waste is fly ash. Dithiocarbamic acid type heavy metal immobilizing agent having dithioic acid type functional group introduced by replacing more than 50% of active hydrogens bonded to nitrogen of amines, and activity of amines bonded to nitrogen Selected from hydroxyl groups and hydroxyl group salts, carboxyl groups and carboxyl group salts, dithioic acid groups and dithioic acid group salts introduced by replacing with 50% or less of hydrogen (excluding 50%) of active hydrogen Ri Do from the amine derivative having a N- substituent, the total amount of the proportion of amine derivative heavy metal immobilizing agent and an amine derivative, a heavy metal, wherein 0.01 to 15 wt% der Rukoto Immobilizing treatment composition.