JPS6347764B2 - - Google Patents

Description

[Detailed description of the invention]

When producing powder alloys or amorphous alloys,
Powder alloys and amorphous alloys are produced by mixing fine powder metals thoroughly using mechanical methods and then molding or melting them. However, if the metal particles before mixing are not very fine, they cannot be mixed well. do not. Further, it requires a large amount of power to form fine metal particles, and has the disadvantage of being reoxidized during mixing and pulverization. The present invention has been made to overcome the drawbacks of conventional methods. That is, the present invention also extracts and mixes two or more organic solvents containing different metal ions, and then brings the metal ions into contact with an aqueous solution containing HF, NH ₄ HF ₂ , or NH ₄ F to remove the metal ions from the organic phase. exfoliates into the phase and regenerates the organic solvent,
The two or more metal ions transferred to the aqueous phase are separated from the aqueous solution as a mixture of metal fluorides of each metal, a mixture of fluorometallic ammonium salts, or a mixture of these different fluorides, and then thermally decomposed in a hydrogen-containing gas stream. This is a method of mixing different metals to form a metal mixture. If necessary, a powder alloy or an amorphous alloy can be obtained by molding or melting. HF, NH ₄ HF ₂ , produced by thermal decomposition,
The NH ₄ F gas is absorbed into water and reused as a metal ion stripping solution. The invention is conveniently implemented as follows. After mixing the extracted metal concentration and liquid volume at a predetermined ratio so that the desired mixed metal is obtained by extracting and containing two or more types of organic solvents containing different metal ions or different metal complex ions, HF is added to this organic solvent. or _NH4F
Alternatively, by contacting with an aqueous solution containing NH ₄ HF ₂ , metal ions or metal complex ions are exfoliated from the organic phase into the aqueous phase and the organic solvent is regenerated as shown in the following formula: (RM _A + RM _B ) + 5NH ₄ HF ₂ ( _{NH 4} ) ₂ M _A F ₄ ↓＋(NH ₄ ) _{3 M B F 6 ↓} ＋ _5R・H ( _{RNH ・ MA} ↓＋NH ₄ M _B F ₃ ↓＋2H ₂ X＋
NH ₄ F (In the above formula, M _A represents a metal of type A, M _B represents a metal of type B, and R represents an extractant; however, in the above formula, M _A is a divalent metal, and M _B is a divalent metal. (indicates the ratio of trivalent metals to stripping agents). The regenerated organic solvent is recycled to extract different metal ions and metal complex ions in accordance with the desired mixing ratio of different metals. The two or more metal ions transferred to the aqueous phase precipitate as a metal-fluorine-containing compound, which is separated from the aqueous solution in a sufficiently mixed state. When the separated metal-fluorine-containing compound is thermally decomposed in a hydrogen-containing gas stream, a mixture of different metal powders is obtained as shown in the following formula. (NH ₄ ) ₂ H _A F ₄ ↓+(NH ₄ ) ₃ M _B F ₆ +21/2H ₂ 5NH ₄ F↑+5HF↑+ (M _A +M _B ) NH ₄ F, HF, NH ₃ produced by decomposition, The F gas is absorbed into water and recycled for stripping metal ions and metal complex ions. The metal-fluorine-containing compounds described above are merely examples. Therefore, fluorometallic acid ammonium salts are naturally included. The organic solvents convenient for preparing the metal-fluorine-containing compound mixtures of the present invention are generally extractants, diluents, and optionally modifiers (to promote phase separation, organic phases, etc.). (increases solubility in). The extractant alkyl phosphoric acid used in the present invention is then selected from the following group:

【formula】

【formula】

【formula】

【formula】

[expression] or

[Formula] (wherein R generally represents an alkyl group having 4 to 22 carbon atoms) and the alkyl and arylthiophosphoric acids are selected from the group of compounds shown in the following formula: (wherein R generally represents an alkyl group or an aryl group having from 4 to 22 carbon atoms) The carboxylic acids used to prepare the metal-fluorine-containing compounds in the present invention are selected from the following group:

[Formula] and

[Formula] (In the formula, R generally represents an alkyl group having 4 to 22 carbon atoms) An example of the hydroxyoxime to be used is shown below: In the formula, R is H, CH ₃ ,

[expression] or

In [Formula], X is Cl or H. Oximes similar to these can of course be used. The alkylsulfonic acids also used are selected from the following group: (In the formula, R represents an alkyl group, and those having 4 to 24 carbon atoms are generally used). The alkylamines used to prepare the metal-fluorine-containing compounds in the present invention are selected from the following groups: Primary amines are represented by RN or _RNH2 ,
Typical examples are: CH ₃ C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₂ CH
₂ C(CH ₃ ) ₂ NH ₂ Secondary amines are represented by R ₂ N or R ₂ NH;
A typical example is shown below: Tertiary amines are represented by R ₃ N or R ₃ NH,
A typical example is shown below: Quaternary amines are represented by [R ₃ NCH ₃ ] ⁺・Cl ^-
The Cl ^- ion portion may be replaced with an anion such as SO ₄ ^2- , NO ₃ ^- , F ^- or a metal complex ion. Also

[Formula] can also be used. The neutral phosphoric esters also used in the present invention to prepare the metal-fluorine-containing compounds are selected from the following group:

【formula】 【formula】

【formula】

[Formula] In the formula, R represents an alkyl group having 4 to 18 carbon atoms. The diluent used in the present invention is a petroleum hydrocarbon,
These are aromatic hydrocarbons, aliphatic hydrocarbons, or a mixture thereof. Miscellaneous hydrocarbon mixtures such as kerosene are also commonly used. The modifier used is generally a higher alcohol having an alkyl group of 4 to 24 carbon atoms, and depending on the extracted substance, an organic substance is added that allows the extractant and diluent to dissolve well. The addition ratio is generally 0% to 30% (by volume). The concentration of the extractant depends on the properties of the liquid to be treated, the concentration of metals,
It is also determined by the concentration and type of impurities. Generally, the concentration of extractant is between 2% and 95% (by volume). The method for producing a mixture of different metals according to the present invention will be described in detail below with reference to the accompanying drawings, but the method for producing the metal-fluorine-containing compound according to the present invention is not limited thereto. As shown in the flow sheet in Figure 1, two or more metal fluorides, fluorometallic ammonium salts (A) and
After thoroughly mixing (B) in the mixing step (C), the thermal decomposition step
When (G) is thermally decomposed in an atmosphere of hydrogen-containing airflow (J), a mixture of metal powders A and B is produced as shown in the following formula.
(H) is obtained. (NH ₄ ) ₂ M _A F ₄ +NH ₄ M _B F ₃ +2H ₂ 3NH ₄ F↑+4HF↑+(M _A +M _B ) A mixture of metal powders of M _A and M _B can be molded or melted. An amorphous alloy can be obtained by rapid quenching. NH ₄ F, HF, F, and NH ₃ gases (K) generated by decomposition are absorbed (L) by water. The flowsheet shown in Figure 2 consists of two or more organic solvents (A) and organic solvent (B) that extract and contain different metal ions.
After thoroughly mixing in the mixing step (C), the peeling step
(D) Two or more metal ions (A) and (B) which had been extracted into an organic solvent by contacting with HF or an aqueous solution containing NH ₄ HF ₂ or NH ₄ F (E).
is exfoliated into the aqueous phase as shown in the following formula: RM _A +2NH ₄ HF ₂ (NH ₄ ) ₂ M _A F ₄ +2RH RM _B +3NH ₄ HF ₂ (NH ₄ ) ₃ M _B F ₆ +3RH Transferred to the aqueous phase The metal ions are precipitated as a solid mixture of metal and fluorine-containing compound as shown in the above formula. After separating this from the aqueous solution (F), it is decomposed in a hydrogen-containing gas stream (J) in a thermal decomposition step (G) to produce (A).
A mixture (H) of different metals of (B) is obtained. The flowsheet shown in Figure 3 introduces aqueous solutions (N) and (M) containing different metal ions to the extraction steps (A') and (B'), and brings them into contact with the same type of organic solvent to extract the metal ions. Extract (A) and (B) into the organic phase. Next, the mixture is led to a mixing step (C), in which both organic solvents are mixed. The subsequent steps for obtaining a mixture of different metals are exactly the same as those for the flow sheet shown in FIG. The present invention will be explained below with reference to Examples. Example 1 Fe ³⁺ ions were extracted using an organic solvent of 30% D ₂ EHPA + 10% U-10 + 60% isoparaffin, and further Ni ²⁺ ions and Cr ³⁺ ions were extracted, and the amount of these metals was 74:8: After mixing organic solvents at a ratio of 18%, 250g/NH ₄ HF ₂ at pH 7.0.
was brought into contact with the liquid. The contact ratio (volume ratio) was organic phase/aqueous phase=4/1. FIG. 4 shows the results of thermal decomposition of the obtained metal ammonium fluoride in a hydrogen stream. Further, FIG. 5 shows for reference the weight change state of thermal decomposition of (NH ₄ ) ₂ NiF ₄ and (NH ₄ ) ₃ CrF ₆ alone. Example 2 An organic solvent of 30% D ₂ EHPA + 70% isoparaffin was brought into contact with an aqueous solution of PH3 containing Cu ions, and 8.6 g of Cu ions in the aqueous solution were transferred to the organic phase.
extracted at a concentration of Next, adjust the pH to 4 using the same organic solvent.
of the aqueous solution by contacting it with an aqueous solution containing Mo.
Mo was extracted at a concentration of 12.9 g/ml. After mixing these two organic solvents at a volume ratio of 100:10.8,
Contact was made with an aqueous solution containing 250 g/NH ₄ HF ₂ . The contact ratio was organic phase/aqueous phase=5/1. The ammonium fluorides of Mo and Cu that were generated in the aqueous phase were separated from the aqueous solution. Next, it was thermally decomposed in a hydrogen-containing gas flow. The obtained metal is
When the crystals were measured using a line diffraction method, it was confirmed that they were mixed metal powders. The weight change in the thermal decomposition situation is shown in the sixth figure.
The state of thermal decomposition of each metal in a hydrogen stream is shown in FIG. 7. Next, the relationship between the extraction rate of metal ions extracted into the organic solvent and the pH of the metal ion-containing aqueous solution in the present invention is shown in FIGS. 8 to 11. Figure 8 shows the case where an alkyl phosphoric acid is used as the extractant, Figure 9 shows the case where a carboxylic acid is used as the extractant, Figure 10 shows the case where an alkylamine is used as the extractant, and Figure 11 shows the case where a neutral phosphoric acid ester is used as the extractant. , Fig. 10, Fig. 11
In the figure, instead of PH, the Cl concentration in the metal-containing aqueous solution,
HCl concentration was used. Extraction distribution ratio (represented by symbol D) =
It refers to the metal concentration value in the organic phase/metal concentration value in the aqueous phase. Peel test results are shown below:

[Table] The extractant used in the above stripping test was D ₂ EHPA (di-2-ethylhexyl phosphoric acid), selected from the group of alkyl phosphoric acids.

[Formula] R=C ₈ H ₁₇ . SME-529 is a trade name of Ciel Chemical Co., Ltd. and was selected from the group of hydroxyoximes.

[Formula] R=CH ₃ . D ₂ EHPDTA (di-2-ethylhexyldithiophosphoric acid) is

[Formula] R=C ₈ H ₁₇ . V-10 (versatizes-10) is a trade name of Ciel Chemical Co., Ltd. and is selected from the group of carboxylic acids.

[Formula] R = within the range of _C9 to _C11 . TOA (trioctylamine) is selected from the group of tertiary amines,

It is expressed by the formula and R=C ₈ H ₁₇ . TBP (tributyl phosphate) is selected from the group of neutral phosphate esters.

[Formula] R = C ₄ H ₉ . The diluent used was n-paraffin or isoparaffin. It was confirmed that there was no difference in stripping performance between the two hydrocarbons. In the present invention, after mixing this in the state of extracted metal ions or metal complex ions with an organic solvent, this organic solvent is brought into contact with an aqueous solution containing HF, NH ₄ HF ₂ or NH ₄ F, and the metal-fluorine After obtaining a mixture of containing compounds, this is thermally decomposed in a hydrogen-containing air stream to produce a mixed metal powder, which is then used for the purpose of forming or melting it to obtain an amorphous alloy. However, it should also be applied to the production of mixtures of dissimilar metals obtained by thermal decomposition in a hydrogen-containing gas stream after mixing fluorine-metal-containing compounds obtained by other methods. I would like you to understand that.

[Brief explanation of the drawing]

FIG. 1 is a flow sheet of the method of the present invention starting from a fluorine-containing compound of a different metal; FIG. 2 is a flow sheet of the method of the present invention starting from a different metal extracted into an organic solvent; Figure 3 shows a flow sheet of the method of the present invention starting from an aqueous solution containing different metals, and Figure 4 shows the weight change rate and temperature of a metal ammonium fluoride mixture of Ni and Cr when heated in a hydrogen stream. Figure 5 is a graph showing the relationship between Ni and Cr, similar to Figure 4 for metal ammonium fluoride, and Figure 6
The figure is a graph showing the relationship between the weight change rate and temperature of a metal ammonium fluoride mixture of Cu and Mo when heated in a hydrogen stream, and Figure 7 is a graph showing the relationship between the temperature and the weight change rate of a metal ammonium fluoride mixture of Cu and Mo. Figure 8 is a graph showing the relationship between the extraction rate of various metal ions by alkyl phosphoric acid and pH, Figure 9 is a graph similar to .
The figure shows the extraction rate of various metal ions and pH by carboxylic acid.
Figure 10 is a graph showing the relationship between the extraction rate of various metal ions by alkylamine and Cl concentration, and Figure 11 is a graph showing the relationship between the extraction rate of various metals by neutral phosphate ester and HCl concentration. It is a graph showing a relationship.

Claims (1)

[Claims] 1 After pre-mixing two or more organic solvents containing different metal ions, HF or NH ₄ HF ₂
Alternatively, the metal ions are transferred to the aqueous phase by contacting with an aqueous solution containing NH ₄ F, the organic solvent is simultaneously regenerated, and the two or more metal ions transferred to the aqueous phase are taken as metal fluorides or fluorometallic ammonium salts. 1. A method for mixing dissimilar metals, the method comprising: decomposing the metal fluoride or fluorometallic ammonium salt in an H ₂ -containing gas stream to obtain a metal mixture.