JPS621406B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing a chelate resin for adsorbing heavy metals. More specifically, a polyamino polydithioic acid or a salt thereof having at least one active hydrogen bonded to nitrogen, an amine compound, an aldehyde, and a phenol are reacted,
Then heated and hardened to obtain mercury, copper, zinc, lead, chromium, vanadium, cadmium, gold,
The present invention relates to a method for producing a novel chelate resin for adsorbing heavy metals that exhibits extremely excellent adsorption ability for heavy metals such as platinum. In recent years, the problem of pollution caused by heavy metals has become an increasingly serious social problem. It started with the mineral poisoning problem in the Watarase River basin caused by copper from the Ashio mine, Minamata disease caused by mercury that occurred in Minamata Bay, Itai-tai disease caused by cadmium that occurred in the Jinzu River basin in Toyama Prefecture, and more recently it has become a major social problem. As the tragic damage caused to humans by heavy metals, such as the chromium pollution incident caused by hexavalent chromium in Tokyo and other lead pollution incidents caused by automobile waste gas, has come to light, the Water Pollution Control Act and air pollution have become more widespread. Legal regulations have become stricter, as seen in the Prevention Act. Against this social background, many heavy metal trapping agents and trapping methods have been proposed and implemented, but among them, the adsorption treatment method using chelate resin has an extremely low limit of removal. This is an optimal method for meeting regulatory values that are expected to become increasingly strict in the future. Conventional chelate resins or heavy metal scavengers with chelate-forming ability include active carbon with dithizone adsorbed, resins with iminodiacetic acid groups or polyamino groups introduced into styrene-divinylbenzene copolymers, and phenolic resins with heavy metal scavengers. Thiourea-type resins or dithiocarbamate-type resins into which coordination groups such as sulfur and nitrogen have been introduced, which have high adsorption properties with sulfur and nitrogen, are known. These have the disadvantages that they have a small adsorption amount of heavy metals, an insufficient adsorption rate, poor durability and chemical resistance, and are expensive. The present inventors focused on the problems of conventional chelate resins as described above, and as a result of intensive research, we found that the adsorption amount is larger and the adsorption speed is faster than that of conventional chelate resins, as described below. We have developed a chelate resin for heavy metal adsorption that has excellent durability and chemical resistance, can adsorb many types of heavy metals, and can be manufactured at low cost. That is, the present invention provides polyaminopolydithioic acid or its salts having at least one active hydrogen bonded to nitrogen, amine compounds, aldehydes, and phenols in the presence of a solvent, preferably in the presence of water or an alcohol. at 20-100℃ for 1-10 hours, preferably 20-60
℃ for 1 to 4 hours, and the resulting precondensation liquid is heated to 70 to 160℃ for 1 to 20 hours, preferably 80 to 120℃.
℃ for 3 to 5 hours, and then pulverized into 10 to 50 meshes, or the precondensation solution may be mixed with benzene, toluene, xylene, carbon tetrachloride, chloroform, trichloroethylene, or perchlorethylene. Alternatively, it is added to a single or mixed solvent such as dichloromethane under stirring, and heated at 40 to 140°C for 1 to 30 hours, preferably 80 to 100 hours.
℃ for 1 to 10 hours, and then 1 to 10 hours.
When the curing and aging reaction is carried out for ~20 hours, a spherical resin of 10 to 60 meshes is obtained, and a chelate resin with extremely excellent heavy metal adsorption ability can be produced. In addition, when adding the precondensation liquid to a solvent, if a surfactant (preferably a nonionic surfactant) or a water-soluble polymer is dissolved in the solvent in advance, the precondensation liquid will be well dispersed and the particle size will It is possible to produce a chelate resin with a small distribution and an almost perfectly spherical shape. Furthermore, it is also possible to obtain a chelate resin with excellent heavy metal adsorption ability by impregnating activated carbon, bone charcoal, silica, cotton, nylon cloth, pulp, paper, etc. with the precondensation liquid and curing the resin. The polyamino polydithio acids or their salts (alkali metal, alkaline earth metal) having at least one active hydrogen bonding to nitrogen used in the present invention include N-(dithiocarboxy)ethylenediamine, N,N'-bis (dithiocarboxy)ethylenediamine, N,N,N'-tri(dithiocarboxy)ethylenediamine, N-(dithiocarboxy)propylenediamine, N,N'-
bis(dithiocarboxy)propylene diamine,
N,N,N'-tri(dithiocarboxy)propylenediamine, N-(dithiocarboxy)hexamethylenediamine, N,N'-bis(dithiocarboxy)hexamethylenediamine, N,N,
N'-tri(dithiocarboxy)hexamethylenediamine, N-(dithiocarboxy)phenylenediamine, N,N'-bis(dithiocarboxy)
phenylenediamine, N,N,N'-tri(dithiocarboxy)phenylenediamine, N-(dithiocarboxy)xylenediamine, N,N'-bis(dithiocarboxy)xylenediamine, N,
N,N′-tri(dithiocarboxy)xylenediamine, N-(dithiocarboxy)diethylenetriamine, N,N″-bis(dithiocarboxy)
Diethylenetriamine, N,N,N″-tri(dithiocarboxy)diethylenetriamine, N,
N,N″,N″-tetra(dithiocarboxy)diethylenetriamine, N-(dithiocarboxy)triethylenetetramine, N,N-bis(dithiocarboxy)triethylenetetramine, N,N,
N-tri(dithiocarboxy)triethylenetetramine, N,N,N,N-tetra(dithiocarboxy)triethylenetetramine, N,N,
N',N,N-penta(dithiocarboxy)
Triethylenetetramine, N(dithiocarboxy)tetraethylenepentamine, N,N'-bis(dithiocarboxy)tetraethylenepentamine, N,N,N'-tri(dithiocarboxy)
Tetraethylenepentamine, N, N, N',
N'-tetra(dithiocarboxy)tetraethylenepentamine, N,N,N',N',N'-penta(dithiocarboxy)tetraethylenepentamine, N,N,N',N'',N',N '-Hex(dithiocarboxy)tetraethylenepentamine, N-(dithiocarboxy)pentaethylenehexamine, N,N″-bis(dithiocarboxy)pentaethylenehexamine, N,N,N″
-tri(dithiocarboxy)pentaethylenehexamine, N,N,N'',N''-tetra(dithiocarboxy)pentaethylenehexamine, and ethylenediamine, propylene diamine, hexamethylene diamine, phenylene diamine, xylene diamine, 1,3- Bis(aminomethyl)cyclohexane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, melamine, aminoethylpiperazine, pepyrazine, polyethyleneimine,
N-alkylethylenediamine, N-alkylpropylenediamine, N-alkylhexamethylenediamine, N-alkylphenylenediamine, N
- Polyamino obtained by adding carbon disulfide (CS ₂ ) to polyamines such as alkylxylene diamine, N-alkyldiethylenetriamine, N-alkyltriethylenetetramine, N-alkyltetraethylenepentamine, and N-alkylpentaethylenehexamine. There are polythio acids and their salts. These may be used alone or in combination of two or more, and are not limited to these.
However, the above N-alkyl group has 1 to 1 carbon atoms.
24 alkyl group or a hydroxyalkyl group having 2 to 28 carbon atoms. The amine compounds used in the present invention include ethylene diamine, propylene diamine, hexamethylene diamine, phenylene diamine, 1,3-
Bis(aminomethyl)cyclohexane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,
Melamine, urea, aniline, polyethyleneimine, polyvinylamine, aminoethylpiperazine, dimethylaminoethylamine, diethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, diethylaminobutylamine, bis(aminoethyl)aminopropylamine, N,N'-bis (3-aminopropyl)ethylenediamine, 1,14-diamino-
4,8,11-triazatetradodecane, 1,18-
Diamino. 4,8,11,15-tetraazaoctadecane, pentapropylenehexamine, N-alkylamine, N,N-dialkylamine, N-alkylethylenediamine, N-alkylpropylenediamine, N-alkylhexamethylenediamine, N-alkylphene Nylenediamine, N-alkylxylylenediamine, N-alkyldiethylenetriamine, N-alkyltriethylenetetramine, N-alkyltetraethylenepentamine,
Examples include N-alkylpentaethylenehexamine and N-alkylpolyethyleneimine, which may be used alone or in combination of two or more, and are not limited to these. However, the above N-alkyl group is an alkyl group having 1 to 24 carbon atoms or a hydroxyalkyl group having 2 to 28 carbon atoms. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfural, benzaldehyde, and aldehyde derivatives of hexamethylenetetramine, which may be used alone or in combination of two or more, and are limited to these. isn't it. Phenols include phenol, alkyl-substituted phenols such as cresol and xylenol, polyhydric phenols such as resorcinol and catechol, hydroquinone, and pyrogallol, and these may be used alone or in combination of two or more, and are not limited to these. Examples will be described below, but the present invention is not limited to the following examples. Example 1 Sodium ethylene bisdithiocarbamate
Dissolve 25.6 parts and 3 parts of ethylenediamine in 79 parts of pure water, add 48.7 parts of 37% formalin aqueous solution, adjust the pH to 8.5 to 9.0 with a predetermined amount of hydrochloric acid, and then heat at 50°C.
The mixture was allowed to react for 4 hours. After the reaction was completed, the mixture was cooled to 0 to 5°C, and 44.0 parts of a 50% resorcinol aqueous solution was added dropwise while maintaining the same temperature. When the system was heated to 60°C over 1.5 hours after completion of the dropwise addition, the viscosity of the system increased and eventually stirring became impossible, but after further heating at 90 to 100°C for about 6 hours with stirring stopped, a dark brown cured product was obtained. This cured product was taken out, crushed into 20 to 50 meshes, and thoroughly washed with heated distilled water to obtain a crushed chelate resin. Moisture content: 58% Example 2 33.2 parts of soda salt of N,N'-bis(dithiocarboxy)-m-xylene diamine and 1.9 parts of urea were added, 60.0 parts of a 37% formalin aqueous solution was added, and the mixture was PHed with a predetermined amount of hydrochloric acid. = 9.0 and reacted at 50°C for 3 hours. After the reaction was completed, 44 parts of a 50% resorcinol aqueous solution was added dropwise while maintaining the temperature at 0 to 5°C and stirring rapidly.
After the addition was completed, the mixture was heated at 90° C. for 5 hours to obtain a black cured product. This cured product was taken out, crushed into 20 to 50 meshes, and thoroughly washed with heated distilled water to obtain a crushed chelate resin. The moisture content was 52%. Example 3 Sodium ethylene bisdithiocarbamate
Add 31.2 parts of diethylaminoethylamine, 6.2 parts of diethylaminoethylamine, and 83 parts of 37% formalin aqueous solution, and stir at 50°C.
The reaction was allowed to proceed for 1.5 hours. Further, 53.6 parts of a 50% resorcinol aqueous solution was added and reacted in the same manner as in Example 1, followed by pulverization and post-treatment to obtain a black brown crushed chelate resin of 20 to 50 meshes. The moisture content was 63%. Example 4 1.2 parts of ethylenediamine, N, N, N, N
- 56.0 parts of a 20% aqueous solution of sodium salt of tetra(dithiocarboxy)triethylenetetramine, 1.8 parts of dimethylaminoethylamine, and 32.2 parts of a 37% aqueous formalin solution were charged, reacted at 50°C for 2 hours, and then 9.8 parts of phenol was added. The viscous substance obtained by reacting at 50℃ for 1.5 hours was applied on a glass plate.
The cured product obtained by reacting for 4 hours at 90 to 130° C. under reduced pressure in a vacuum dryer was crushed and post-treated in the same manner as in Example 1 to obtain a crushed brown chelate resin of 20 to 50 meshes. Example 5 33.5 parts of sodium hexamethylene bisdithiocarbamate, 1.2 parts of polyethyleneimine, and 37
Example 1
Reaction hardening, crushing and post-treatment in the same manner as 20 to 50
A dark red crushed chelate resin of mesh was obtained. Example 6 42.5 parts of sodium salt of N,N,Z'-tri(dithiocarboxy)diethylenetriamine, 1.8 parts of diethylamine, and 47.0 parts of acetaldehyde were charged, reacted at 20°C for 5 hours, and 26.3 parts of cresol was added. Curing and post-treatment were carried out in the same manner as in 1 to obtain a black brown crushed chelate resin of 20 to 50 meshes. Example 7 Meta-xylene diamine-bis(sodium dithiocarboxylate) 41.4 parts, laurylamine 5.6 parts,
and 65.0 parts of a 37% formalin aqueous solution were added, the pH was adjusted to 9.0 with a predetermined amount of hydrochloric acid, and the mixture was reacted at 50°C for 40 minutes. Next, the mixture was cooled to 30° C., 55.2 parts of a 50% aqueous resorcinol solution was added, and after 1.5 hours, the mixture was dropped into 1000 parts of toluene with rapid stirring to disperse into small spheres. The mixture was further heated and reacted for 4 hours under refluxing toluene, and after curing and aging, the solvent was separated to obtain a dark brown spherical resin having a particle size of 10 to 80 mesh. The obtained spherical resin was classified into 20 to 50 meshes, toluene adhering to the resin was removed under reduced pressure, and thoroughly washed with pure water. Example 8 Table 1 shows the results of adsorption and removal tests for various heavy metal ions on the 20 to 50 mesh chelating polymers obtained in Examples 1 to 7. The adsorption and removal test was carried out by the batch method, that is, 100 ml of heavy metal ion aqueous solutions of various concentrations were placed in a 200 ml Erlenmeyer flask, 1 g of the chelate resin obtained in Examples 1 to 7 was added, and the mixture was stirred for 90 minutes at room temperature with a stirrer. After stirring, the chelating polymer was filtered, and the residual heavy metal ion concentration (ppm) of the filtrate was measured by atomic absorption spectrometry. In addition, heavy metal ion aqueous solutions of various concentrations are
For Cu ²⁺ , Cd ²⁺ , Pb ²⁺ CuSO ₄・5H ₂ O,
Commercially available first-class reagents such as Cd(NO ₃ ) ₂ 4H ₂ O and PbSO ₄ were prepared to a specified concentration, and for Hg ²⁺ , metallic mercury (99.9999%) was dissolved in concentrated nitric acid and adjusted to a specified concentration. did.

[Table] As described above, the present invention has a larger adsorption amount and faster adsorption rate than conventional chelate resins, can adsorb many types of heavy metals, is inexpensive, and is suitable for single use. This has the effect of making it possible to produce a chelate resin for adsorbing heavy metals.

Claims (1)

[Claims] 1. A heavy metal obtained by precondensing a polyaminopolydithioic acid having at least one active hydrogen bonding to nitrogen or its salts, amine compounds, aldehydes, and phenols, followed by heating and curing. A method for producing a chelate resin for adsorption.