JPS64445B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing metals selected from Ni, Co, Cd, In and Mn. Conventionally, these metals (Ni, Co, Cd, In and
One method for recovering Mn) is to obtain pine through a dry process of mixing sulfides, and then electrorefining it to recover more than 99% of the metal, but this method has the drawback of limiting the raw materials. . In addition, raw materials are leached with acid or alkali, and impurities are removed by pH
After removal using a separation method, the target metal ions are purified using electrowinning methods or solvent extraction techniques, and then an electrolyte stock solution is used to guide these ions in the organic solvent to the electrolysis process. Although methods have been used to collect it, the process is complicated, and electrowinning has the drawbacks of consuming an extremely large amount of electrical energy. An example is shown in Table 1 below.

[Table] Also, it has the disadvantage that the construction cost of the electrolytic equipment required to improve purity is high, and it is necessary to mass produce it intensively, which is often a disadvantage considering the distance between the market and the production area. The present invention has already been filed by the inventor in Japanese Patent Application No. 55-119308.
As disclosed in Japanese Patent Application No. 55-119310, the present invention relates to a method for producing metals using H2 _- containing gas at low temperatures and in a relatively short time by recovering the metals via ammonium fluoride salts. This method was developed to overcome the drawbacks of conventional methods. The invention will be explained below with reference to the figures. The first part that explains the gist of one aspect of the present invention
According to the flow sheet shown in the figure, one type of ammonium fluoride salt or ammonium fluoride salt (A) selected from Ni, Co, Cd, In, and Mn is heated in a hydrogen-containing gas stream in a thermal decomposition process (B). A basic flow sheet for obtaining these metals (Ni, Co, Cd, In, and Mn) (M), for example, as shown below, by thermal decomposition in the atmosphere of (G) is shown. (NH ₄ )NiF ₃ +H ₂ Ni+NH ₄ F+2HF (NH ₄ ) ₂ CoF ₄ +H ₂ Co+2NH ₄ F+2HF (NH ₄ ) ₂ CdF ₄ +H ₂ Cd+2NH ₄ F+2HF (NH ₄ ) ₃ InF ₆ +1 1/2H ₂ In+3NH ₄ F+3HF (NH ₄ ) ₂ MnF ₄ +2H ₂ Mn+2NH ₄ F+4HF The ammonium fluoride salt of each metal is not limited to the above reaction formula as there are compounds other than those shown above. NH ₄ F, a by-product gas (K) generated by thermal decomposition,
HF or NH ₃ and NH ₄ HF ₂ produced by their decomposition or recombination are absorbed into water and recycled to produce these metal fluorides. One embodiment of the method of the invention shown in the flow sheet in FIG. 1 is shown in FIG. According to the flow sheet in Figure 2, Ni, Co, Cd,
Raw material containing one selected from In and Mn (J)
In the dissolution step (E), add and dissolve hydrofluoric acid (H) or ammonium hydrofluoride aqueous solution (H), and if necessary, add ammonia (L), and then perform the over-separation step (D). The mother liquor (H) and these metals (M) (Ni,
Co, Cd, In, and Mn) ammonium fluoride salt or ammonium fluoride salt (A) is obtained by precipitation. This is then subjected to the thermal decomposition process in the same manner as shown in Figure 1.
In (B), these metals (M), NH ₄ F (K) and HF are heated in a hydrogen-containing gas flow (G) atmosphere.
Get (K). FIG. 3 is a flow sheet including an embodiment in which ammonium fluoride or ammonium acetate A of metal (M) is obtained by solvent extraction, and is a flow sheet of a method showing the gist of another aspect of the present invention. is shown in Figure 3. According to the flow sheet in Figure 3, Ni, Co,
In the stripping step (B), the organic solvent (S) from which Cd, In, and Mn ions or their complex ions have been extracted is brought into contact with the stripping aqueous solution (H) containing F ions to form an organic phase as shown in the following formula. These metal ions or metal complex ions are then stripped to the aqueous phase of the stripping solution and the organic solvent (S) is regenerated. R ₂ Ni＋2NH ₄ HF ₂ (NH ₄ ) ₂ NiF ₄ ＋2RH R ₂ CoCl ₂ ＋2NH ₄ HF ₂ (NH ₄ ) ₂ CoF ₄ ＋2R・HCl R ₂ Cd＋2NH ₄ HF ₂ (NH ₄ ) ₂ CdF ₄ ＋2RH R ₃ In＋3NH ₄ HF ₂ (NH ₄ ) ₃ InF ₆ +3RH R ₂ Mn+2NH ₄ HF ₂ (NH ₄ ) ₂ MnF ₄ +2RH Regenerated organic solvent (RH) is recycled for metal ion (Ni, Co, Cd, In and Mn) extraction be done. Since the metal ions or complex ions transferred to the aqueous phase become fluorine compounds (A'), they can be over-separated from the aqueous solution (Step D). The organic solvent (S) is an extractant selected from the group consisting of alkyl phosphoric acids, dialkyldithiophosphoric acids, diaryldithiophosphoric acids, carboxylic acids, hydroxyoximes, and neutral phosphoric esters. Diluted with hydrocarbon. Next, the metal ions transferred from the organic phase to the aqueous phase,
Metal fluoride ammonium salt (A') is produced.
After separating the aqueous solution from the metal ammonium fluoride salt (A') and the metal ammonium fluoride salt (A') in the separation process (D), a hydrogen-containing gas stream (G) is generated in the thermal decomposition process (B).
By heating in the atmosphere, metal (M) is obtained as shown below, and NH ₄ F, NH ₄ HF ₂ , HF,
Obtain NH ₃ by-product gas (K). The by-product gas (K) is absorbed with an aqueous solution and regenerated as a stripping solution (H). (NH ₄ ) ₂ NiF ₄ +H ₂ Ni+2NH ₄ F+2HF (NH ₄ ) ₂ CoF ₄ +H ₂ Co+2NH ₄ F+2HF (NH ₄ ) ₂ CdF ₄ +H ₂ Cd+2NH ₄ F+2HF (NH ₄ ) ₃ InF ₆ +1 1/2H ₂ In+3NH ₄ F+3HF (NH ₄ ) ₂ MnF ₄ +H ₂ Mn+2NH ₄ F+2HF Furthermore, in order to recover metals from fluorine complexes, it is essential to use a hydrogen atmosphere, and if these ammonium fluoride salts are heated in the air, As shown, metal oxides and no metals are obtained. (NH ₄ ) ₂ NiF ₄ +1/2O ₂ NiO+2NH ₄ F+2F CoF ₂ +1/2O ₂ CoO+2F However, whether obtaining metals or metal oxides, using ammonium fluoride salt makes it easier than conventional methods. It has the advantage that metals or metal oxides can be recovered at low temperature, and the gases produced by decomposition can be absorbed to obtain these metal ammonium fluoride salts or other metal fluoride complexes again. It has the advantage that it can be used for Accordingly, another aspect of the present invention is to extract one or more selected from the group consisting of alkyl phosphoric acids, dialkyldithiophosphoric acids, diaryldithiophosphoric acids, carboxylic acids, hydroxyoximes, and neutral phosphoric esters. These metals (Ni, Ni,
The method is characterized in that metals are obtained by producing ammonium fluoride salts of Co, Cd, In, and Mn. The alkyl phosphoric acids used as extractants in the present invention are selected from the following group:

【formula】

【formula】

【formula】

[expression] or

[Formula] (However, in each of the above formulas, R represents an alkyl group, and those having 4 to 22 carbon atoms are used). D2EHPA (D2EHPA) described in the examples below.
2-ethylhexyl phosphoric acid) belongs to group (a), and _the alkyl group is _C8H17 . Also, OPPA (octyl pyrophosphoric acid) belongs to group (c), and the alkyl group is
It is of C ₈ H ₁₇ . The dialkyldithiophosphoric acid or diaryldithiophosphoric acid used as extractant in the present invention is selected from the following group:

[Formula] (wherein R represents an alkyl group or an aryl group,
Generally, those having 4 to 22 carbon atoms are used. D2EHPDTA (di-2-ethylhexyl-dithiophosphoric acid) described in the examples has an alkyl group
It refers to C ₈ H ₁₇ . The carboxylic acids used as extractants in the present invention are selected from the following group:

【formula】

[Formula] (In the formula, R represents an alkyl group, and generally has 4 carbon atoms.
~22 are used). V-10 [Versateik-10 is a trade name of Ciel Chemical Co., Ltd.] described in the examples belongs to the group (a),
The number of carbon atoms in the alkyl group is in the range of 9 to 11. An example of a hydroxyoxime for use in the present invention is shown below:

[Formula] (In the formula, R is H, CH ₃ ,

[expression] or

[Formula] X is Cl, H) Hydroxyoximes similar to these can be used,
This is described in the Examples below. The product name SME-529 manufactured by Ciel Chemical Co., Ltd. is a product in which R is CH ₃ X is H. Moreover, the neutral phosphoric acid ester referred to in the present invention is selected from the following group:

【formula】 【formula】

[Formula] and

[Formula] (In the above formula, R represents an alkyl group, and the number of carbon atoms is 4 to 22
TBP (tributyl phosphate) described in the examples belongs to group (a), and R is C ₄ H ₉ . The diluent used in the present invention is a petroleum hydrocarbon,
Both aromatic and aliphatic types are used. Of course, mixtures of these can also be used. Mixtures of miscellaneous hydrocarbons such as kerosene can also be used. Extractants are selected from each group and used two or more or singly. The type and number of mixed extractants are also determined depending on the properties of the target aqueous solution and the coexistence of impurities. Although its concentration is determined in the same manner, it is generally adjusted to 2% to 90% (by volume) before use. The F ion-containing aqueous solution (stripping solution) used in the present invention includes HF, NH ₄ HF ₂ NH ₄ F, KHF ₂ and
A liquid containing one or more types selected from the group of _NaHF2 . The present invention will be specifically described below with reference to Examples. Examples Metal stripping experiment in organic solvent phase The organic solvents shown in the table below were stripped with stripping solution (H) to obtain the fluoride or ammonium fluoride salt shown in the column of product (A').

[Table] Thermal decomposition experiment of ammonium fluoride salt in _H2 gas flow The obtained ammonium fluoride salt of each metal was decomposed by heating in a hydrogen gas flow under the following conditions to obtain each metal: Thermal decomposition Conditions: Temperature increase rate: 7℃/ _H2 supply rate: 100ml/min Trial weight: 100mg Figure 4 shows the weight loss curves of ammonium fluoride salts of Ni, Co, and Cd in the above thermal decomposition experiment.
Figure 5 shows the weight loss curves for Mn and Mn. As is clear from Figures 4 and 5, NH ₄ F begins to desorb from around 180°C, and from 220°C to 280°C (A in the figure).
It is estimated that F is converted to a fluoride at point B (point), and then the separation of F (conversion to a lower fluoride) and reduction to a metallic state proceed simultaneously, and the formation of F at point B (Mn, Ni,
It is confirmed that Co is reduced to metal at temperatures below about 600°C, and In and Cd below 700°C. After completion of heating, the product was confirmed by X-ray analysis.

[Brief explanation of the drawing]

FIG. 1 is a flow sheet of the basic method of the present invention, FIG. 2 is a flow sheet of an embodiment of the method shown in FIG. The figure shows a flow sheet of a method according to another aspect of the present invention, and FIGS. 4 and 5 show heating loss curves for Co, Ni, and Mn, and heating curves for Cd and In, respectively. In the figure: A... Ammonium fluoride salt, B... Thermal decomposition process, G... Hydrogen-containing gas flow, K... By-product gas, M... Metal, J... Metal-containing raw material, E... Melting process, H...Dissolution liquid (stripping liquid), S...Organic solvent, D...Separation step.

[Claims]

1. Mixing short fibers or whiskers of reinforcing fibers with resin powder, heating the mixture to carbonize the resin powder, and binding the short fibers or whiskers together with the carbide to form an aggregate;
A method for producing a composite material, which comprises: then impregnating the aggregate with molten metal and solidifying it.

Claims (1)

A method of producing metals from ammonium salts.