KR100700197B1 - Process for Manufacturing Sintered Materials Containing Cobalt Component - Google Patents

Abstract

The present invention relates to a method for producing a cobalt-containing sintered alloy by recycling a catalyst waste scrap containing a cobalt component for desulfurization.

The present invention provides a method for producing a cobalt-containing small binder by recycling a catalyst scrap mass in a solid state mixed with an organic material containing a cobalt component for desulfurization, comprising the steps of: pulverizing the catalyst scrap mass; Thermally treating the pulverized catalyst scrap mass at a temperature between 600 ° C. and 1000 ° C. to produce a cobalt oxide; Obtaining the cobalt-based powder by heat treating the cobalt-based oxide powder at a temperature between 750 ° C. and 1000 ° C. under a reducing component crisis; And 95 wt% to 98 wt% of at least one powder among Sn, Fe, Ni, and Cu, including the cobalt-based powder, and the remaining diamond powder, and applying a pressure of 10 MPa or more and 70 MPa or less to 800 ° C. And hot press sintering for 5 minutes at a temperature between 1000 ° C. Cobalt-containing diamond sintered alloys thus produced are more economical than those obtained by conventional methods.

Cobalt Waste Catalyst, Cobalt Powder, Diamond Tools, Sintered

Description

Process for manufacturing cobalt-containing sintered alloy by recycling catalyst scraps containing cobalt for desulfurization {Process for Manufacturing Sintered Materials Containing Cobalt Component}

Table 1 is a table showing the density, hardness and wear amount of the cobalt-containing cemented carbide prepared according to the present invention and the alloy showing a comparative example.

Table 2 is a table showing the density, hardness and wear amount of the alloy showing the comparative example with the cobalt-containing diamond small alloy prepared according to the present invention.

The present invention relates to a method for producing a cobalt-containing sintered alloy by recycling a catalyst waste scrap containing a cobalt component for desulfurization, and more particularly, to prepare a cobalt-based powder from a catalyst waste scrap and to cobalt-containing diamond sintering It relates to a method for producing an alloy.

The waste scrap used in the oil refining plant to use the catalyst containing the cobalt component in the desulfurization process contains about 5 to 15% by weight of the cobalt component in a large amount of organic matter. Such scrap is being landfilled or disposed of. Therefore, it is very economically useful to prepare cobalt powder as a raw material.

Cobalt-containing sintered alloys are mainly classified into cobalt-containing cemented carbides and cobalt-containing diamond sintered alloys, and are most commonly used. Cobalt-containing carbide sintered alloys used in wear-resistant molds, dies, punches, etc. are mainly composed of hard WC and are grain growth inhibitors depending on the situation. And a sintered alloy in which about 6% by weight to 30% by weight of the Co component serving as a known phase is added. Cobalt-containing cemented carbide used in cutting tools is an alloy that improves cutting performance by adding about 7% to 30% by weight of a part of the WC in the WC-Co system by replacing other carbides such as TiC, TaC, and NbC.

In general, the manufacturing process of the cobalt-containing cemented carbide sintered alloy is pulverized and mixed with a carbide powder and cobalt powder, including the main component WC by ball milling, and then produced through a molding and sintering process. Cobalt powder added thereto is an expensive strategic element and a powder that soared due to severe price fluctuations in the international market. The use of cheaper cobalt is necessary to produce cemented carbides more economically.

The cobalt-containing diamond sintered alloy is a sintered alloy composed of about 2% to 5% by weight of the hard phase diamond, and about 95% to 98% by weight of components such as Co, Cu, Sn, Fe, and Ni. These diamond tools are used for stone cutting, road asphalt cutting and concrete cutting. In such a tool, cobalt is an important raw material and it is necessary to use a low cost cobalt raw material to reduce manufacturing costs.

Accordingly, an object of the present invention is to produce a Co powder by recycling catalyst waste scrap containing a cobalt component for desulfurization, and cobalt-containing sintered alloy containing cobalt-based powder and carbide powder or diamond powder to form and sinter more economically. Or a method for producing a cobalt-containing diamond sintered alloy.

The method for producing a cobalt-containing diamond sintered alloy according to the present invention for achieving the above object is to recycle a cobalt-containing catalyst scrap lump in a solid state mixed with 5 to 15% by weight of a cobalt component for desulfurization and the remaining organic matter. CLAIMS 1. A method of making a small bond comprising the steps of: grinding a catalyst scrap mass; Thermally treating the pulverized catalyst scrap mass at a temperature between 600 ° C. and 1000 ° C. to produce a cobalt oxide; Obtaining the cobalt-based powder by heat treating the cobalt-based oxide powder at a temperature between 750 ° C. and 1000 ° C. under a reducing component crisis; And 95 wt% to 98 wt% of at least one powder among Sn, Fe, Ni, and Cu, including the cobalt-based powder, and the remaining diamond powder, and applying a pressure of 10 MPa or more and 70 MPa or less to 800 ° C. Hot press sintering for 5 minutes at a temperature between 1000 ℃; characterized in that comprises a.

The cobalt-based powder is characterized in that 34.5% by weight is included.

In the step of crushing the catalyst scrap mass, the catalyst scrap mass is characterized in that the diameter is crushed to 70mm or less.

The cobalt oxide powder is heat-treated for 2 hours.
The hot pressure sintering step is characterized in that the progress using the discharge plasma.

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EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, it is preferable to grind as little as possible the solid catalyst scrap mass in which the cobalt component for desulfurization and the remainder of the organic substance are mixed to make contact with the charging raw material and the air. If the diameter or the thickness is about 70 mm or more, the calcination time is too long and it is uneconomical.

Since the pulverized catalyst scrap lump contains about 85% by weight of organic matter, it is necessary to heat-treat it in an atmospheric atmosphere to remove the organic matter and obtain cobalt oxide. The calcination heat treatment is preferably a heat treatment at a temperature of 600 ℃ to 1000 ℃. If the calcination heat treatment temperature is lower than 600 ℃, it takes too long to remove the organic material is uneconomical, if the calcined at a temperature of 1000 ℃ or more cobalt-based oxide particles are grown too much to obtain a powder of several microns.

The heat treatment for producing the cobalt-based powder by reducing the cobalt-based oxide powder prepared above is preferably in a reducing atmosphere at a temperature of 750 ℃ to 1000 ℃. If the reduction temperature is 750 ° C. or less, the reduction treatment time is long or the reduction is not performed properly, and the cobalt particles grow at 1000 ° C. or more to obtain particles having a size of several microns.

Then, 6 wt% to 30 wt% of the cobalt-based powder and WC as a main component to determine the weight of 60 wt% to 94 wt% of one or more powders of carbide powder such as Cr ₃ C ₂ , VC, TiC, TaC, NbC After mixing by ball milling and molding the powder into a desired mold, it is possible to produce a WC-Co-based cemented carbide is vacuum sintered at a temperature of 1320 ℃ to 1470 ℃. Here, if the sintering temperature is less than 1320 ℃ Co-C-based matrix is a solid phase, it is difficult to densify by liquid phase sintering and WC particles do not grow too much or the specimen shape is not maintained uniform at a temperature of 1470 ℃ or more is not good.

On the other hand, in the method of producing a diamond material having a cobalt binder, 95 wt% to 98 wt% of one or more powders such as Sn, Fe, Ni, Cu, including diamond powders, and the like must be included by calcination and reduction of the waste catalyst. 2 to 5 wt% of unavoidable impurities may be mixed and charged into a die, and then sintered at a temperature between 800 ° C and 1000 ° C by applying a pressure of 10 MPa or more and 70 MPa or less to prepare a diamond tool material having a cobalt binder. .

Here, if the pressure is too low at 10 MPa, it is difficult to eliminate pores during sintering, and if it is 70 MPa or more, the graphite die material is easily broken, so it is preferable to apply a pressure of 10 MPa or more and 70 MPa or less. In addition, when the sintering temperature is 800 ° C. or less, densification is difficult, and since the diamond phase deteriorates at 1000 ° C. or more, it is preferable to sinter at a temperature between 800 ° C. and 1000 ° C.

Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to FIG.

Comparative Example 1

Cobalt catalyst scrap lumps containing organic matter were ground to a thickness of about 40 mm or less. The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment for 2 hours at 400 ° C. in an air atmosphere. The calcined cobalt oxide was charged into a hydrogen atmosphere and kept at 800 ° C. for 2 hours. 12% by weight of cobalt powder, 87% by weight of WC powder, 1% by weight of chromium carbide and vanadium carbide powder were mixed by ball milling for 24 hours, and then filled with a die having a diameter of 15 mm, 3.5 g of powder, and 1500 kg / cm. After molding at a pressure of ² , charged into a vacuum sintering furnace and sintered at 1400 ° C. for 30 minutes in a vacuum atmosphere. The sintered density and Rockwell hardness (HRA, 60kg load) were measured, and the height of the worn cemented carbide specimens was measured by rotating alumina at 400 rpm for 1 hour under the load of 30N.

This is because the relative density of the sintered specimens was low as 92%, and organic matter remained after calcination of the spent catalyst, so that excess carbon and the like remained during sintering to form pores during sintering.

Comparative Example 2

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 500 ° C. for 2 hours in an air atmosphere. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 1.

This is because the relative density of the sintered specimens was low as 93%, and organic matter remained after calcination of the spent catalyst, so that excess carbon and the like remained during sintering and pores were formed during sintering.

Example 1

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 800 ° C. for 2 hours in an air atmosphere. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 1.

The relative density of the sintered specimens was high as 99.4%, the hardness was higher than the specimens of Comparative Examples 1 and 2, and the abrasion resistance was smaller than that of the Comparative Examples 1 and 2, resulting in excellent wear resistance.

Example 2

 The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 900 ° C. for 2 hours in an air atmosphere. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 1.

The relative density of the sintered specimen was 99.5%, the hardness was higher than that of Comparative Examples 1 and 2, and the abrasion resistance was smaller than that of Comparative Examples 1 and 2.

Comparative Example 3

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 900 ° C. for 2 hours in an air atmosphere. The calcined cobalt oxide was charged into a hydrogen atmosphere and maintained at 700 ° C. for 2 hours. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 1.

This is because the relative density of the sintered specimens was low as 94%, and organic matter remained after calcination of the spent catalyst, so that excess carbon and the like remained during sintering to form pores during sintering.

Comparative Example 4

The conditions different from Comparative Example 3 are the same and only the reduction temperature is changed to 1100 ° C.

The relative density of the sintered specimens was low as 94% and the powder was large after reduction, so the coalescence of the powder was severe during reduction, and the relative density was low because pores remained between the aggregates after molding and sintering.

Example 3

The conditions different from Comparative Example 3 were the same, and only the reduction temperature was changed to 800 ° C.

 The relative density of the sintered specimens was as high as 99.6%.

Comparative Example 5

The conditions different from Example 3 are the same, and only the sintering temperature is changed to 1300 ° C. The relative density of the sintered specimens was as low as 92%.

Comparative Example 6

The condition different from Example 3 is the same and only the sintering temperature is changed to 1530 degreeC. It was difficult to maintain the formulation phase after sintered specimens.

Example 4

Conditions different from those of Comparative Example 5 were the same, and only the sintering temperature was changed to 1350 ° C.

The relative density of the sintered specimens was as high as 99.0%.

Example 5

Conditions different from those of Comparative Example 5 were the same, and only the sintering temperature was changed to 1450 ° C.

The relative density of the sintered specimens was as high as 99.6%.

Examples 1, 2, 3, 4, and 5 conditions were higher in sinter density and hardness than in Comparative Examples 1, 2, 3, 4, 5, and 6, and the wear amount was small, and thus the wear resistance was excellent.

Hereinafter, another preferred embodiment of the present invention will be described in detail with reference to FIG. 2.

Comparative Example 7

Cobalt catalyst scrap lumps containing organic matter were ground to a thickness of about 40 mm or less. The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment for 2 hours at 400 ° C. in an air atmosphere. The calcined cobalt oxide was charged into a hydrogen atmosphere and maintained at 800 ° C. for 2 hours. 34.5% by weight of cobalt powder, 2% by weight of diamond powder, 25% by weight of Fe powder, 10% by weight of Ni powder, 20% by weight of Cu powder and 3.5% by weight of Sn powder were mixed and the powder was filled into a die having a diameter of 15 mm. After that, discharge plasma hot press sintering was performed at 900 ° C. for 5 minutes at a pressure of 500 kg / cm ² . The sintered density and hardness (HRB, 100 kg load) were measured and the height of the worn diamond-cobalt specimens was measured by rotating alumina at 400 rpm for 1 hour under a load of 30 N.

This is because the relative density of the sintered specimen was low as 87%, and organic matter remained after calcination of the spent catalyst, so that excess carbon and the like remained during sintering to form pores during sintering.

Comparative Example 8

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment for 2 hours at 500 ° C. in an air atmosphere. Subsequent powder reduction, powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 7.

 This is because the relative density of the sintered specimens was low as 88%, and organic matter remained after calcination of the spent catalyst, so that excess carbon and the like remained during sintering to form pores during sintering.

Example 6

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 800 ° C. for 2 hours in an air atmosphere. The calcined cobalt oxide was charged into a hydrogen atmosphere and maintained at 800 ° C. for 2 hours. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 7.

 The relative density of the sintered specimens was high as 96%, and the hardness value was higher than that of Comparative Example 7, 8 masses, and the wear height was also lower than that of Comparative Example 7, 8 masses. .

Example 7

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 900 ° C. for 2 hours in an air atmosphere. The calcined cobalt oxide was charged into a hydrogen atmosphere and maintained at 900 ° C. for 2 hours. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 7. The relative density of the sintered specimens was high as 96%, and the hardness value was higher than that of Comparative Example 7, 8, and the wear height was also lower than that of Comparative Example 7, 8.

Comparative Example 9

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 900 ° C. for 2 hours in an air atmosphere. The calcined cobalt oxide was charged into a hydrogen atmosphere and maintained at 700 ° C. for 2 hours. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 7.

Comparative Example 10

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 900 ° C. for 2 hours in an air atmosphere. The calcined cobalt oxide was charged into a hydrogen atmosphere and maintained at 1100 ° C. for 2 hours. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 7.

Example 8

The cobalt catalyst scrap containing the pulverized organic material was subjected to calcination heat treatment at 900 ° C. for 2 hours in an air atmosphere. The calcined cobalt oxide was charged into a hydrogen atmosphere and maintained at 800 ° C. for 2 hours. Subsequent powder mixing, molding and sintering conditions, and test evaluation conditions were the same as in Comparative Example 7.

Comparative Example 11

The conditions different from those of Example 8 were the same, except that the powder molding pressure was 5 MPa.

Comparative Example 12

The conditions different from those of Example 8 were the same, except that the powder molding pressure was 90 MPa.

Comparative Example 13

The conditions different from Example 8 were the same, but the sintering temperature was 700 degreeC.

Comparative Example 14

The conditions different from Example 8 were the same, but the sintering temperature was 1100 degreeC.

Example 9

The conditions different from those of Example 8 were the same, except that the sintering temperature was 850 ° C.

The relative density of the sintered specimens was high as 97%, the hardness value was also high compared to Comparative Examples 13 and 14, and the wear height was also low compared to Comparative Examples 13 and 14, indicating excellent wear resistance.

Example 10

The conditions different from those of Example 8 were the same, except that the sintering temperature was 950 ° C.

The relative density of the sintered specimen was 97.5%, and the hardness value was also high compared to Comparative Examples 13 and 14, and the wear height was also low compared to Comparative Examples 13 and 14, indicating excellent wear resistance.

Examples 6,7, 8, 9, and 10 conditions were higher in sinter density and hardness than in Comparative Examples 7, 8, 9, 10, 11, 12, 13, and 14, and the wear amount was small and the wear resistance was good.

Although described above based on the preferred embodiment of the present invention, various modifications and improvements can be made within the scope of the technical idea of the present invention, and those skilled in the art that such modifications and improvements also belong to the present invention You will notice.

As described above, the present invention provides a cobalt oxide powder by pulverizing a solid catalyst scrap agglomerate containing the cobalt component for desulfurization and heat treatment in an atmospheric atmosphere and heat treatment in a reducing atmosphere to obtain a cobalt powder and a cobalt powder and carbide It is effective to provide a method of manufacturing cobalt-containing cemented carbide sintered alloy or cobalt-containing diamond small alloy by economically forming and sintering by mixing powder or diamond powder.

Claims (6)

delete In the method for producing a cobalt-containing small binder by recycling a solid catalyst scrap lump mixed with 5 to 15% by weight of the cobalt component for desulfurization and the remaining organic matter, Grinding the catalyst scrap mass; Thermally treating the pulverized catalyst scrap mass at a temperature between 600 ° C. and 1000 ° C. to produce a cobalt oxide; Obtaining the cobalt-based powder by heat treating the cobalt-based oxide powder at a temperature between 750 ° C. and 1000 ° C. under a reducing component crisis; And 95 wt% to 98 wt% of at least one powder among Sn, Fe, Ni, and Cu, including the cobalt-based powder, and the remaining diamond powder, and applying a pressure of 10 MPa or more and 70 MPa or less to 800 ° C. A method of producing a cobalt-containing small alloy comprising a step of hot press sintering for 5 minutes at a temperature between 1000 ° C. 3. The method of claim 2, wherein the cobalt-based powder comprises 34.5 wt%. The method of claim 2, wherein in the step of grinding the catalyst scrap mass, The catalyst scrap mass is cobalt-containing small-alloy manufacturing method characterized in that the diameter is crushed to less than 70mm. The method of claim 2, wherein the cobalt-based oxide powder is heat-treated for 2 hours. 3. The method of claim 2, wherein the hot press sintering step is performed using a discharge plasma.

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