JPS59162989A - Collection of metal ion - Google Patents

Abstract

PURPOSE:To collect various kinds of metal ions over a wide range in a short time, by adding an anionic surfactant to an aqueous solution containing metal ions to form hydrophobic reaction products, and collecting said reaction products with the special colloidal complex body of organic substance with clay. CONSTITUTION:An anionic surfactant (Type-carboxyl such as the sodium salt of a higher fatty acid or the like) is added to an aqueous solution containing divalent or more multivalent metal ions such as Ca, Al and copper, to form hydrophobic reaction products. Then, the colloidal complex body of organic substance with clay obtd. by reacting an aliphatic amine (e.g. lauryl or dioctyl amine) with clay such as montmorillonite is added to collect said hydrophobic reaction products. Hereon, it is preferable to react the aliphatic amine in an amount of about 20-100m equivalent in terms of exchange capacity by 100g of clay.

Description

[Detailed description of the invention] The present invention relates to a method for collecting metal ions.

Conventionally, adsorption using ion exchange resin is known as a method for collecting metal ions contained in aqueous solutions.
Depending on the type of metal ion, the adsorption rate is extremely slow and the collection efficiency is poor.

The purpose of the present invention is to eliminate the above-mentioned disadvantages and provide a method for collecting a wide variety of metal ions, especially divalent or higher, in a short time, by adding an anionic surfactant to an aqueous solution containing metal ions Collecting the hydrophobic reaction product of the metal ion and the anionic surfactant obtained by using a colloidal clay organic biomass obtained by reacting aliphatic amines with clay such as montmorillonite. It is characterized by

Next, examples of the present invention will be described in detail.

The metal ions in the aqueous solution to be collected are those containing divalent or higher valence metal ions, such as calcium, aluminum layer copper, and zinc chrome.

The anionic surfactant added to the aqueous solution containing the above metal ions is a carboxylic acid type such as higher fatty acid sodium, a sulfone such as sodium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, etc. ! , alkyl ether phosphate ester salts, alkyl phosphate ester salts, and other phosphate ester type anionic surfactants are added to an aqueous solution containing divalent or higher metal ions. Stirring causes hydrophobic reaction products to be produced by metathesis or exchange reactions between the metal ions and the anionic surfactant, such as its soda salt. A colloidal clay-organic composite described in detail below is added to the aqueous solution containing the hydrophobic reaction product thus obtained. In this way, the above-mentioned hydrophobic reaction product is collected by the colloidal clay-organic composite, and metal ions of divalent or higher valence in the aqueous solution are removed. The collected material is then separated by filtration or the like to form an aqueous solution that does not contain harmful heavy metal ions or radioactive metal ions.

When an anionic surfactant has already been used as a detergent, such as laundry wastewater, and metal ions of divalent or higher valence in the aqueous solution combine with it to produce, for example, metal soap, the above-mentioned colloidal surfactant may be used. It is advantageous to simply add the clay-organic complex.

When mainly selectively collecting only 5r(II) in an aqueous solution containing multiple types of metal ions, such as 5r(II) and Y(to), phosphoric acid is used as an anionic surfactant. The purpose is achieved by using surfactants of the ester type.

Furthermore, the colloidal clay-organic composite has excellent heat resistance, and the present invention is convenient as a method for collecting radioactive metal ions, etc. contained in hot wastewater of nuclear power plants.

The trapping effect of the hydrophobic substance by the colloidal clay-organic composite is thought to be due to the large number of alkyl groups of the hydrophobic aliphatic amines protruding into the water to form an iceberg. .

The colloidal clay organic composite is composed of bentonite and other montmorillonite clays, and
The constituent aliphatic amines include, for example, primary amines such as laurylamine, secondary amines such as dioctylamine and didodecylamine, tertiary amines such as trihexylamine, trioctylamine, and dodecyldimethylamine. All aliphatic amines such as quaternary ammonium salts such as dodecyltrimethylammonium chloride, and those in which at least one carbon chain of the alkyl group has 4 to 20 carbon atoms are preferably used. In addition, these aliphatic amines have an exchange capacity of 20 to 100 meq per 100 g of the clay.
It is preferable to react.

In addition, an example of the method for producing the colloidal clay-organic composite is as follows: 'First, bentonite is dispersed in water, and an aliphatic group having an alkyl group having at least one carbon chain having 4 to 20 carbon atoms is dispersed in water. Amine hydrochloride is added and stirred to react with the bentonite to obtain a colloidal clay organic complex.

The colloidal clay organic complex adsorbing the hydrophobic reaction product is separated from water by sedimentation, filtration, centrifugation, etc., and the hydrophobic substance is eluted with a solvent such as alcohol. The colloidal clay-organic composite can be recycled and used by removing the hydrophobic substances.

Next, the present invention will be explained in detail.

Example 1 10M of Fe04.6H20 was prepared and 110M of sodium laurylbenzenesulfonate was added thereto, but no change was observed. Also 10M Fe0
4.6H20 was prepared and a colloidal clay organic complex consisting of laurylamine and bentonite equivalent to 51n9 was added thereto, but no change was observed. Add 10 M of sodium laurylbenzenesulfonate to 5 my of the colloidal clay organic complex, and add 10 M of sodium laurylbenzenesulfonate to the clay organic complex.
When the mixture was stirred lightly, Fe0ID was adsorbed to the colloidal clay-organic composite and precipitated. This is F
This shows that e(2) and sodium laurylbenzenesulfonate formed an ion pair, and their hydrophobic association was adsorbed on the colloidal clay-organic composite. Also at this time FeG
The ID collection rate was over 90%.

Example 2 Co(If) in a 4×10 M 0o04 solution was adjusted to pH 11 using various molar amounts of sodium laurate and a clay-organic complex similar to that of Example 1 was used to prepare 10 μm of the colloidal clay-organic. Collected with a complex. As a result, the maximum collection rate was obtained when the molar ratio of sodium laurate and 0oO12 was 2:1. This is sodium laurate and 0o0
Corresponds to the stoichiometric molar ratio in the metathesis reaction with 1z. In this way, an economical amount of anionic surfactant to be added can be determined.

Example 3 C0(II) in a solution of 4X10 M OoO40
was collected on the same colloidal clay-organic complex as in Example 1 using sodium laurate at various pH values and equivalent to 1101n. As a result, as shown in Figure 1, the collection rate improves as the alkalinity increases, and the pH
No. 11 showed a collection rate of 98%. In this way, the collection rate can be improved by adjusting the pH.

Example 4 3 μOi/mL of “5r(II)-”YQII) (
This is 5r(n) and 1.0X10 M, YOII)
Example 1: Take 2 ml of T3
200 mg of the same colloidal clay-organic composite was added and stirred for 5 to 10 minutes to be adsorbed onto the colloidal clay-organic composite. The concentrations of o s r (B) and moth I were measured. As a result, “Sr (loss 100
%, "Y([20% of 10 was collected. Figure 2 shows what remains in the water". 5r(n), the ion concentration of YQ[I) is [
s r (n)], -Y (t)] and ζ;
The ion concentration of hl is [5r (II 几 [Y@)]. Thus, [″5r(If)] o / [”5r(II):
] and [″Y 011))./[oOy([[I)]t, pH 7!: Q:)” shows the relationship 1. fc, pH
This shows that the ratio differs depending on the As is clear from this, it can be seen that two or more metal ions can be selectively collected by appropriately setting the pH value.Example 5: 200-fold detergent (Abratore White, manufactured by Mitsui Kinzoku Co., Ltd.) 10 to 10 μO1/mt of 8"5r(II) was added to a solution of 100 pplN of N1LOt, and this was used as a simulated wastewater. To this, the same colloidal clay organic complex as in Example 1 was added to The mixture was stirred for 5 to 10 minutes, and the adsorption of "5r(If)" to the colloidal clay-organic composite was examined. As a result, the decontamination rate of "5r(If)" by the colloidal clay-organic composite was 83% to 91%. Also, the time to reach equilibrium was about 30 minutes, compared to the case of activated carbon under similar conditions. Equilibrium adsorption was reached in a very short time of about 20 hours, compared to about 5 hours for ion exchange resins.

As explained above, according to the present invention, a colloid obtained by reacting a hydrophobic reaction product of a divalent or higher valent metal ion and an anionic surfactant with an aliphatic amine and clay such as montmorillonite It has the effect of quickly collecting a wide range of metal ions because it is collected using a clay-like organic complex.

[Brief explanation of the drawing]

Figure 1 is a characteristic diagram showing the relationship between the collection rate of metal ions and pH, and Figure 2 is a graph showing the concentration of metal ions adsorbed on the colloidal clay organic complex and the metal ions remaining in the water. FIG. 2 is a characteristic diagram showing the relationship between the ratio of concentration and pH.

Claims (1)

[Claims] A hydrophobic reaction product of the metal ions and the anionic surfactant obtained by adding an anionic surfactant to an aqueous solution containing metal ions is reacted with an aliphatic amine and a clay such as montmorillonite. A method for collecting metal ions, which is characterized by collecting metal ions using a colloidal clay-organic composite obtained by