JPS5854178B2 - 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 tungsten and cobalt-containing materials such as cemented carbide scrap and/or sludge generated during the processing of said alloy.

For more details, see Tungsten Carbide-Cobalt (
The present invention relates to a method for recovering tungsten and cobalt from tungsten and cobalt-containing substances such as sludge generated during processing such as electrolytic grinding and/or electrolytic grinding of cemented carbide scrap (hereinafter abbreviated as W C-Co).

Since tungsten carbide is extremely hard, it is widely used in various types of carbide tools, and as a result, large amounts of scrap such as non-standard products and used products are generated.

Further, although cemented carbide is processed by various methods, recently electrolytic grinding has come into widespread use, and the amount of sludge produced has also increased accordingly.

Therefore, the recovery of valuable metal components from these scraps and sludge is important from the standpoint of effective resource utilization, and various studies have been carried out heretofore.

The present inventors have studied various conventional methods for recovering tungsten, cobalt, etc. from tungsten and cobalt-containing materials such as cemented carbide scrap and sludge.

As a result, the present inventors were able to produce tungsten chloride and cobalt chloride with extremely good yield and high purity by pre-oxidizing the scrap and/or sludge and then chlorinating it under certain conditions. They discovered that it could be recovered and completed the present invention.

That is, the present invention oxidizes tungsten and cobalt-containing materials such as W C-Co cemented carbide scrap and/or electrolytic grinding sludge of the alloy, and then chlorinates it in the presence of carbonaceous material to produce tungsten chloride and cobalt chloride. It is characterized by collecting things.

The sludge obtained by heating and dehydrating electrolytic grinding sludge of WC-Co cemented carbide is known as WC, COWO4, Na2WO4, etc.

Among these components, high temperatures of about 80,000 ℃ or more are required to chlorinate and recover active ingredients such as tungsten and cobalt.

Furthermore, when chlorination is carried out at such a high temperature, tungsten chloride and cobalt chloride are simultaneously precipitated out of the reaction system as products, so a further step is required to separate them into each other.

The present inventors found that when chlorinating tungsten and cobalt-containing materials in the presence of carbonaceous matter, COWO4,
The reaction of N a 2 WO 4 proceeds significantly even at low temperatures, for example about 500°C, but among the scrap and sludge constituents, WC is not chlorinated at such low temperatures even in the presence of carbonaceous matter. As mentioned above, by oxidizing the scrap and/or sludge in advance, WC in these components can be converted into tungsten oxide in the presence of carbonaceous materials at low temperatures. This made it possible to chlorinate the tungsten chloride and easily separate and recover it as high-purity tungsten chloride and cobalt chloride.

In the present invention, the oxidation temperature of the tungsten- and cobalt-containing material is not limited as long as the WC contained therein easily becomes an oxide, but is preferably 400'C or higher.

Further, in the chlorination reaction, chlorine may be supplied in an amount necessary for the reaction to proceed.

Further, the carbonaceous substance added to the reaction system is not particularly limited, and ordinary coke or the like may be used.

Also, the amount added is 10% to oxidized sludge, etc.
~50wt is preferable.

In addition, the temperature of the chlorination reaction ranges from a temperature at which all components such as sludge are chlorinated, that is, about 350°C, to a temperature at which the vapor pressure of cobalt chloride can be ignored, for example, about 500°C.
After separating and recovering the tungsten chloride, the temperature of the chloride is further raised to a temperature at which cobalt chloride vaporizes, and cobalt 2 chloride is recovered.

Tungsten chloride is obtained as a component containing WO2C12 and WOCl4, but it can be converted to WCl6 by contacting these with chlorine at a temperature of about 700°C or higher in the presence of carbonaceous substances as described above. .

The obtained chloride can be used as a raw material for metallic tungsten, metallic cobalt, or useful compounds containing these.

The present invention can recover highly purified tungsten chloride and cobalt chloride under extremely mild conditions and at a high recovery rate.

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

Example 1 WC-Co non-electrolytic grinding sludge was heated to about 3000C to remove water and the like, resulting in CoWO4; 69%.

Na2WO4; 20%, WCloo%, C:
The one containing 1% of the constituent components was used.

The above sludge was oxidized in air at about 500°C, part 1
0g was placed in a quartz boat, mixed with approximately 2g of coke powder, heated to 500°C in a reactor purged with argon, and heated for 10 minutes.
Chlorine gas was passed through at 0 m1/min for 3 hours.

As a result, 9.89 tungsten chloride was obtained in the receiver which was kept at the same temperature as the room temperature outside the heating section connected to the reactor.

As a result of chemical analysis, WO2C12; 98%, WOCl4;
2, and approximately 100φ of W could be recovered.

Next, the chlorine gas was stopped and the mixture was heated at 750° C. for 4 hours while flowing argon gas for 4 minutes to obtain 2.9 g of cobalt chloride.

Therefore, almost 100% of cobalt could be recovered.

Example 2 Chlorination was carried out in the same manner as in Example 1, except that a reactor filled with coke was connected to the reactor used in Example 1, and the produced tungsten chloride was passed through it together with chlorine gas. Ta.

Incidentally, the coke packed bed was maintained at 900°C.

The resulting product was 13.6 g in WCA 6.

Example 3 WC-Co alloy scrap was heated to 18% in an argon atmosphere.
The mixture was heated at 00 to 2000'C for 1 hour and pulverized to obtain a raw material.

The ingredients were as follows. W: 87.0%, Co
: 5.9%, C: 5.9%.

Next, this was oxidized in air at 90000C to form this 1(
Bi' was mixed with 2 g of coke powder and chlorinated under the same conditions as in Example 1.

As a result, tungsten chloride 11.6.9 was obtained.

As a result of chemical analysis of this product, WO2C12; 98φ.

It contained 2% WOCA.

Then, the temperature was raised in the same manner as in Example 1 to obtain 1.1 g of cobalt chloride.

The recovery rate of W and Co was almost 100%.

Claims (1)

[Claims] 1. Tungsten and cobalt-containing materials such as tungsten carbide-cobalt cemented carbide scrap and/or electrolytic grinding sludge of the alloy are oxidized in advance, and then chlorinated at 350 to 500 degrees Celsius in the presence of carbonaceous material. A method for separating and recovering valuable metal components.