JPS6014089B2 - Separation and recovery method of valuable metal components - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating and recovering valuable metal components from a metal salt solution.

Recently, the separation and recovery of valuable metals from metal-containing materials such as metal scraps, waste catalysts, and heavy oil residues has become important from the perspective of resource conservation and recycling2, and various studies have been carried out. ing.

The present inventors have been conducting research on methods for separating and recovering valuable metals from various metal-containing materials. It has been discovered that molybdenum of extremely high purity can be obtained by extracting and separating 2Dene.

Examples of the molybdenum-containing material used in the production of the metal chloride solution used in the present invention include Timken (16-25-6), which is used as heat-resistant steel, heat-resistant alloy, and corrosion-resistant alloy.
, Incoloy901, Hayues ALLOY21
, Hastelloy C. HastelloyB,Ni
Alloy scrap such as monjcloo and/or semi-finished products from molybdenum-containing ores or ores.

Conventional methods for recovering molybdenum from these alloy scraps include dissolving them in acid and adsorbing the molybdenum on activated carbon, and also using chemical methods such as alkali dissolution and crystallization separation, depending on the components contained after dissolution. A method has been proposed in which molybdenum is treated and recovered as a precipitate, but the former method inevitably adsorbs other mixed components, making it difficult to recover molybdenum as highly pure molybdenum. However, there are drawbacks such as the need for complicated steps, especially when multiple components are involved.

In the present invention, for example, a mixed solution of metal chlorides obtained by chlorinating a molybdenum-containing material as described above is brought into contact with an organic solvent that dissolves chlorine-containing molybdenum compounds to extract the molybdenum compounds, and then the molybdenum compounds are extracted by back extraction and boat extraction. The idea is to recover molybdenum through processes such as conditioning.

The mixed solution of metal chloride used in the present invention can be prepared by, for example, burning the molybdenum-containing metal scrap 1 described above in an oxygen-containing atmosphere, or by oxygen blowing the melted material.
It is obtained by oxidizing and removing contaminants such as sulfur and carbon contained in these, bringing them into contact with a hydrochloric acid solution, and dissolving them by passing chlorine gas into the solution as necessary. The method of chlorination is not particularly limited, but in order to perform chlorination efficiently, for example, the material to be chlorinated is filled in a tower-type reactor or continuously charged, and hydrochloric acid and, if necessary, chlorine are added. Preferred methods include a method in which the gas is passed in cocurrent or countercurrent and the resulting chloride solution is obtained sequentially or continuously, or a method in which they are brought into contact with each other in a crossing tank. Molybdenum-containing scrap, such as heat-resistant steel, is obtained in the form of turnings, grinding shoulders or blocks, and usually contains aluminum, titanium silicon, etc. Therefore, before chlorinating these scraps, for example, in a turtle furnace, they are mixed with a fluxing agent such as limestone or crab stone and melted, the mixture is removed as oxide slag by oxygen blowing, and then pulverized. In view of improving the efficiency of chlorination, it is a preferable method to subject the alloy to the chlorination process as a powder or shot alloy. Further, such treatment is preferable because it simultaneously removes deposits such as oil and sand that may accompany the scrap. The organic solvent used when extracting and separating molybdenum from a metal chloride solution may be a solvent that dissolves molybdenum compounds containing chlorine, such as trioctyl phosphate, tributyl phosphate, di-
These are 3 organic phosphorus compounds such as 2-ethylhexyl phosphate, triptylphosphine oxide, and trioctylphosphine oxide.

These solvents include kerosene, normal hexane, trichlorethylene, and chlorine.

Hydrocarbons such as loform, carbon tetrachloride or their chlorides,
It is preferable to use it after diluting it with an aromatic hydrocarbon such as xylene, toluene, or benzene. If a diluent is used, the solvent concentration is, for example, from 5 to 9% by weight, preferably from 20 to 6% by weight when using an organic phosphorus compound.

Template table for contacting a mixed solution of metal chlorides with the catalyst mentioned above-1
(Weight omitted) Although the method is not particularly limited, it is preferable to bring these into contact using, for example, a countercurrent multistage contact device.

The solvent that has come into contact with the mixed solution of metal chlorides selectively extracts molybdenum compounds containing chlorine, but if iron is present in the mixed solution, the iron is also extracted as iron chloride.

Therefore, an aqueous solution containing a molybdenum compound obtained by back-extracting a solvent containing these with water or preferably dilute hydrochloric acid is simultaneously extracted and back-extracted iron is separated by performing an alkali treatment. For back extraction, the same equipment as used for solvent extraction can be used, and the back extracted solvent can be circulated and used. The alkali used in this step is an alkali or alkali metal hydroxide, carbonate, ammonium hydroxide, etc., but alkali or alkali metal hydroxides are preferred from the viewpoint of the permanence of the product.

The above-mentioned iron content is separated by the above-mentioned alkali treatment, but in order to minimize the loss of molybdenum during iron separation, an alkali metal hydroxide such as sodium hydroxide is used, and the temperature is preferably 90 to 20,000. is 100
When treated with alkali for 1 to 6 hours at ~150qC, normal pressure or pressurized state, iron can be separated and removed as hydrated iron oxide.
In the aqueous solution from which iron has been removed, molybdenum can be separated and recovered as molybdic acid by subjecting the aqueous solution to unevenness adjustment (PHO.1 to 2, preferably 0.8 to 1.2).

The obtained molybdic acid can be obtained as metal molybdenum by reduction treatment and ammonium molybdate by ammonia treatment.

The present invention can recover high-purity molybdenum from molybdenum-containing materials.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 Alloy scrap having the composition shown in Table 1 was heated in a well set electric arc furnace (30KVA, 500A) while blowing oxygen (1
The molten metal was melted at a rate of 0.00 m (oxygen)/min and 1 (oxygen)/10 k9 (scrap), and the molten metal was pulverized to obtain an alloy powder having the composition shown in Table 1.

Next, 25k9 of hydrochloric acid was added to the 29k9 alloy powder, and 20.8kg of chlorine was passed through the mixture for 13 hours to dissolve it.

*The composition of the filtrate obtained by filtering off the residual liquid was as shown in Table 2.
Table 2 (Evening/Etsu) Next, using a three-stage countercurrent extractor, the above liquid was extracted at a rate of 80 minutes per minute, and the trioctyl phosphate (TOP)-kerosene (43% TOP) solution was added at a rate of 64 minutes per minute. were brought into contact with each other at a speed of

Then, a TOP-kerosene solution containing extracted molybdenum was added at a rate of 80 min. The extracts were brought into contact with each other at a rate of 12.8 min/min using the same extraction tower as above, and the extracted components were transferred to the aqueous phase to obtain an aqueous solution having the composition shown in Table 3.

Table 3) Next, add 3 to this aqueous solution to 7 molar concentration sodium hydroxide solution and 1.2 to 9000, respectively.
11,000, 13,000 (husband M1, 2, 3) = 5
The product was heated for a period of time and filtered.

The compositions of impurities in the product and filtrate are shown in Table 4. Table-4 (↓ indicates less than that.

(The same applies hereinafter) (Mo and Fe are values as dry matter.
) The obtained filtrate was concentrated by evaporation, adjusted to pHI with concentrated hydrochloric acid, and molybdenum was precipitated and separated as molybdic acid. The compositions of the concentrate and the filtrate from which molybdic acid was removed were as shown in Table 5. Table 5 Kuyu/Z) In addition, the impurities in the molybdic acid obtained by crystallization were all 0.001% or less of Fe, Co, Nj, and Cr.

M. 80% of the molybdic acid obtained in step 1 was dissolved in 28% ammonia water, adjusted to pH 9, and aged for 3 hours.
The residue A was separated by filtration and concentrated under reduced pressure to obtain 70.6 g of ammonium paramolybdate.

The analytical values of this product are shown in Table 6. Table-6 (Weight Tsutomu)

Claims (1)

[Claims] 1. A metal chloride solution obtained by melting alloy scrap containing molybdenum and/or ore containing molybdenum or a semi-finished product from the ore, oxygen blowing, and then chlorinating the granulated material. , contact with an organic solvent containing an organic phosphorus compound, and contact the organic solvent containing a molybdenum compound with water or hydrochloric acid to transfer the molybdenum compound in the organic solvent to the aqueous phase, and treat the resulting aqueous solution with an alkali to remove molybdenum. A method for separating and recovering valuable metal components, characterized by separating and recovering them. 2. The method according to claim 1, wherein the granulated water is chlorinated by treating it with hydrochloric acid while contacting it with chlorine gas.