METHOD FOR RECYCLING WASTE CEMENTED CARBIDE BY MOLTEN SALT CHEMISTRY

Abstract

The present invention provides a method for recycling waste cemented carbide by molten salt chemistry, comprising the steps of: (1) carrying out vacuum dehydration on a molten salt media; (2) carrying out oxidation-dissolution reaction on waste cemented carbide in the molten salt media; (3) carrying out deoxidation treatment on a molten salt system; (4) carrying out thermal reduction reaction on the molten salt system; and (5) washing filtering and vacuum drying obtained mixture by thermal reduction reaction to carry out separation and collection of the molten salt media and waste cemented carbide nano powder. Compared with existing method for recycling waste cemented carbide, the invention has the advantages of short flow, simple equipment, low energy consumption, and excellent recycled products. Moreover, the invention doesn't produce solid/gas/liquid harmful substances to pollute the environment, and can create enormous economic and social benefits.

Claims

1. A method for recycling waste cemented carbide by molten salt chemistry, characterized in that the method comprises the steps of: (1) dehydrating a molten salt media comprising compound A, compound B and NaCl under vacuum, vacuum degree is 0.10.2 MPa, dehydration temperature is 70300 C., and mole percentage content of the compound A, the compound B and the NaCl in the molten salt media is 530 mol %, 060 mol % and 1050 mol % respectively; (2) adding waste cemented carbide into the molten, salt media, stirring and introducing an oxidizing gas to carry out oxidation-dissolution reaction, and reaction temperature is 3001000 C.; (3) deoxidizing a molten salt reaction system after the oxidation-dissolution reaction by introducing a gas containing chlorine, and deoxidation temperature is 3001000 C.; (4) carrying out thermal reduction reaction on the deoxidized molten salt reaction system by adding reductant, and reaction temperature is 400850 C.; (5) washing, filtering and vacuum drying obtained mixture by thermal reduction reaction, vacuum degree is 0.10.5 MPa, and temperature is 2040 C., and carrying out separation and collection of the molten salt media and waste cemented carbide nanopowder.

2. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the compound A in the step (1) is selected from a group consisting of Na.sub.2O, CaO, K.sub.2O, CoO/CoO.sub.3, WO.sub.3, Na.sub.2WO.sub.4, K.sub.2WO.sub.4 and CaWO.sub.4. and the compound B is selected from a group consisting of CaCl.sub.2, KCl and LiCl.

3. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the reaction temperature of oxidation dissolution in the step (2) is 500800 C.

4. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the waste cemented carbide in the step (2) includes wolfram carbide (WC) based cemented carbide, titanium carbide (TiC) based cemented carbide, titanium carbonitride (TiCN) based cemented carbide, W/Ti/Ta cemented carbide, W/Ti/Ta/Nb cemented carbide and chromium carbide based cemented carbide.

5. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the oxidizing gas in the step (2) is selected from a group consisting of air, oxygen or mixed gas containing oxygen, wherein volume fraction of oxygen in the mixed gas containing oxygen is 20100%, and the rest is nitrogen or argon.

6. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the oxidizing gas is introduced to carry out oxidation dissolution reaction in the step (2) by controlling gas flow to be 550 ml/s or controlling gas partial pressure to be 1.051.50 atmospheric pressure, and when the oxidizing gas is the mixed gas containing oxygen, the oxidation dissolution reaction is carried out by controlling the flow.

7. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the reaction temperature of deoxidation treatment in the step (3) is 300600 C.

8. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the gas containing chlorine in the step (3) is selected from a group consisting of chlorine, hydrogen chloride, chlorine mixture or hydrogen chloride mixture, volume fraction of chlorine in the chlorine mixture is 30100%, and the rest is nitrogen or argon, volume fraction of hydrogen chloride in the hydrogen chloride mixture is 50100%, and the rest is nitrogen or argon.

9. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the gas containing chlorine is introduced to carry out deoxidation treaty treatment in the step (3) by controlling gas flow to be 550 ml/s or controlling gas partial pressure to be 1.051.50 atmospheric pressure, and when the gas containing chlorine is chlorine mixture or hydrogen chloride mixture, the deoxidation treatment is carried out by controlling the flow.

10. The method for recycling waste cemented carbide by molten salt chemistry according to claim 1, characterized in that the reductant in the step (4) is sodium metal or calcium metal.

Description

DESCRIPTION OF THE DRAWINGS

[0031] FIG. 1 shows a structure diagram of a reaction tank of the present invention.

[0032] FIG. 2 is XRD phase analysis graph of wolfram nano metal powder obtained from recycling waste WC cemented carbide of embodiment 1 of the invention.

[0033] FIG. 3 shows FESEM photo of wolfram nano metal powder surface appearance obtained from recycling waste WC cemented carbide of embodiment 1 of the invention.

[0034] FIG. 4 shows XRD phase analysis graph of wolfram nano metal powder obtained from recycling waste WC cemented carbide of embodiment 2 of the invention.

[0035] FIG. 5 shows FESEM photo of wolfram nano metal powder surface appearance obtained from recycling waste WC cemented carbide of embodiment 2 of the invention.

[0036] FIG. 6 shows XRD pattern, of phase analysis graph of wolfram nano metal powder obtained from recycling waste YG16 cemented carbide of embodiment 3 of the invention.

[0037] FIG. 7 shows FESEM photo of wolfram nano metal powder surface appearance obtained from recycling waste YG16 cemented carbide of embodiment 3 of the invention.

[0038] In FIG. 1: 1. sealed container. 2. exhaust vent, 3. reaction tank, 4. feeding pipe, 5. air inlet, 6. storage tank.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0039] The invention is further explained by following embodiments. It should be understood for those skilled in the art that the embodiments are for illustrative purpose and not for limiting the scope of the present invention. Unless otherwise indicated herein, the methods in the embodiments are common in the art.

[0040] The invention can adopt conventional devices in this art to carry out molten salt oxidation-reduction synthesis. The device shown in FIG. 1 is used In following embodiments, a reaction tank (3) is placed in a sealed container (1), the sealed container provides gas shielding and electrical heating. A pressure and temperature measuring device, an air inlet (5) and an exhaust vent (2) are arranged on the sealed container. A feeding pipe (4) and a reductant storage tank (6) are inserted into the molten salt media.

Embodiment 1

[0041] The embodiment describes a method for preparing tungsten nanopowder by utilizing molten salt to recycle waste WC cemented carbide, comprising the following steps: dehydrating the molten salt with mole percentage of NaCl-52 mol % CaCl.sub.2-3 mol % CaO under vacuum, vacuum degree is 0.10.2 MPa, and dehydration temperature is 70300 C.; adding waste WC cemented carbide into the molten salt media, introducing air to carry out oxidation dissolution-decarburizing reaction, and the oxidation temperature is 750 C. Gradually decreasing the air flow and increasing the inert gas argon flow along with the oxidation-dissolution reaction After 5 hours of oxidation-dissolution reaction, replacing air with chlorine to form mixed gas of 50% chloride and argon to carry out deoxidation reaction, and gradually decreasing the chloride content with the deoxidation reaction until completing after 6 hours, and replacing chlorine with argon to carry out gas protection, meanwhile, the reductant sodium metal enters into the molten salt system through the feeding pipe, the reaction temperature is 750 C., completing metallothermic reduction and obtaining tungsten metal powder and molten salt media, and carrying out separation and collection of molten salt media and product powder by washing, filtering and vacuum drying. The vacuum degree and drying temperature are 0.5 MPa and 40 C. respectively,

[0042] The purity of prepared tungsten metal powder reaches 98.6 wt. %. The particle size range of spherical agglomerated particles is 30400 nm. The XRD phase analysis graph and FESEM photo of tungsten metal nanopowder are shown in the FIG. 2 and FIG. 3 respectively.

Embodiment 2

[0043] The embodiment describes a method for preparing WC nanopowder by utilizing molten salt to recycle waste WC cemented carbide, comprising the following steps: dehydrating the molten salt with mole percentage of NaCl-52 mol % CaCl.sub.2-3 mol % Na.sub.2O under vacuum, vacuum degree is 0.10.2 MPa, and dehydration temperature is 70300 C.; adding waste WC cemented carbide into the molten salt media, introducing oxygen to carry out oxidation-dissolution reaction, and the oxidation temperature is 700 C. Gradually decreasing the air flow and increasing the inert gas argon flow along with the oxidation-dissolution reaction. After 4 hours of oxidation-dissolution reaction, replacing oxygen with hydrogen chloride to form mixed gas of 50% hydrogen and argon to carry out deoxidation reaction, and gradually decreasing the hydrogen chloride content with the deoxidation reaction until completing after 2 hours, and replacing hydrogen chloride with argon to carry out gas protection, meanwhile, the reductant sodium metal enters into the reaction system through the feeding pipe, the reaction temperature is 700 C., completing metallothermic reduction and obtaining WC powder and molten salt media and obtaining WC powder and molten salt media, and carrying out separation and collection of molten salt media and product powder by washing, filtering and vacuum drying. The vacuum degree and drying temperature are 0.5 MPa and 40 C. respectively.

[0044] The purity of prepared WC nanopowder reaches 99.5 wt. %. The particle size range of spherical agglomerated particles is 20350 nm. The XRD phase analysis graph and FESEM photo of WC nanopowder are shown in the FIG. 4 and FIG. 5 respectively.

Embodiment 3

[0045] The embodiment describes a method for preparing WC-Co nanopowder by utilizing molten salt to recycle waste YG16 WC-Co cemented carbide, comprising the following steps: dehydrating the molten salt with mole percentage of NaCl-52 mol % CaCl.sub.2-5 mol % CaO under vacuum, vacuum degree is 0.10.2 MPa, and dehydration temperature is 70300 C.; adding waste YG16 WC-Co cemented carbide into the molten salt media, introducing oxygen to carry out oxidation-dissolution reaction, and the oxidation temperature is 750 C. Gradually decreasing the air flow and increasing the inert gas argon flow along with the oxidation-dissolution reaction. After 6 hours of oxidation-dissolution reaction, replacing oxygen with hydrogen chloride to form mixed gas of 50% hydrogen and argon to carry out deoxidation reaction, and gradually decreasing the hydrogen chloride content with the deoxidation reaction until completing after 3 hours, and replacing hydrogen chloride with argon to carry out gas protection, meanwhile, the reductant sodium metal enters into the reaction system through the feeding pipe, the reaction temperature is 750 C., completing metallothermic reduction and obtaining WC-Co composite nanopowder and molten salt media, and carrying out separation and collection of molten salt media and product powder by washing, filtering and vacuum drying. The vacuum degree and drying temperature are 0.5 MPa and 40 C. respectively.

[0046] The purity of prepared WC-Co composite nanopowder reaches 99.3 wt. %. The particle size range of spherical agglomerated particles is 100400 nm. The XRD phase analysis graph and FESEM photo of WC-Co composite nanopowder are shown in the FIG. 6 and FIG. 7 respectively.

[0047] The above disclosure merely shows several specific embodiments of the present invention, and the present invention is not limited thereto. Any variations and modifications made by those skilled in the art within the spirit a the invention shall fall into the protection scope of the present invention.

[0048] This work is financially supported by the National Natural Science Foundation of China (Nos. 51401004).