Interembedded autogenous tungsten (molybdenum)-copper alloy powder, and preparation method and use thereof

Abstract

An interembedded autogenous tungsten (molybdenum)-copper alloy powder, and a preparation method and use thereof are provided. By controlling concentration and type of an organic complex, positive ion metal salts and negative ion metal groups form coordination bonds with hydroxyl oxygen and carboxyl carbon of the organic complex so as to form complexes, respectively. A stepwise heat treatment is conducted to controllably prepare a tungsten (molybdenum)-copper alloy powder with a unique interembedded autogenous structure.

What is claimed is: 
     
         1 . A method for preparing an interembedded autogenous tungsten-copper alloy powder, comprising the following steps:
 (1) preparing an aqueous solution of a soluble copper salt, and adding an organic complex into the aqueous solution of the soluble copper salt to obtain a mixed solution A;   (2) preparing an aqueous solution of a soluble tungsten salt, adding the aqueous solution of the soluble tungsten salt into the mixed solution A, stirring continuously while heating, and concentrating a resulting mixture to obtain a gel, and then drying the gel through a drying oven to obtain a precursor;   (3) calcining the precursor in air to obtain a tungsten-copper composite metal oxide powder; and   (4) subjecting the tungsten-copper composite metal oxide powder to thermal reduction in an argon-hydrogen atmosphere to obtain the interembedded autogenous tungsten-copper alloy powder.   
     
     
         2 . The method of  claim 1 , wherein in step (1),
 the soluble copper salt is one or more selected from the group consisting of copper nitrate and copper sulfate;   the aqueous solution of the soluble copper salt has a concentration of 0.01 mol/L to 2.3 mol/L;   the organic complex is one or more selected from the group consisting of lactic acid, glycolic acid, and gelatin; and   under a condition that the organic complex is the lactic acid or the glycolic acid, a molar ratio of the lactic acid or the glycolic acid to the soluble copper salt is in a range of greater than 1:1.   
     
     
         3 . The method of  claim 1 , wherein in step (2),
 the soluble tungsten salt is one or more selected from the group consisting of ammonium metatungstate and sodium tungstate, and the aqueous solution of the soluble tungsten salt has a concentration of 0.01 mol/L to 1.0 mol/L;   a volume ratio of the aqueous solution of the soluble tungsten salt to the aqueous solution of the soluble copper salt is 1:1;   the resulting mixture is concentrated after heating to a temperature of 30° C. to 50° C. to obtain a gel; and   the drying is conducted in the drying oven at a temperature of 80° C. to 120° C. for 2 h to 6 h.   
     
     
         4 . The method of  claim 1 , wherein in step (3),
 calcining the precursor in the air is conducted by the following two stages:   heating the precursor from room temperature to a first-stage calcination temperature, and calcining the precursor at the first-stage calcination temperature for a period of time; and   heating a resulting material from the first-stage calcination temperature to a second-stage calcination temperature, and calcining the resulting material at the second-stage calcination temperature for a period of time.   
     
     
         5 . The method of  claim 1 , wherein in step (3),
 heating the precursor from the room temperature to the first-stage calcination temperature is conducted at a heating rate of 0.5° C./min to 6° C./min, and heating the resulting material from the first-stage calcination temperature to the second-stage calcination temperature is conducted at a heating rate of 5° C./min to 13° C./min;   the first-stage calcination temperature is in a range of 250° C. to 420° C., and calcining the precursor at the first-stage calcination temperature is conducted for 2 h to 7 h; and   the second-stage calcination temperature is in a range of 450° C. to 600° C., and calcining the resulting material at the second-stage calcination temperature is conducted for 1 h to 5 h.   
     
     
         6 . The method of  claim 1 , wherein in step (4),
 the thermal reduction is conducted by the following two stages:   in the argon-hydrogen atmosphere, heating the tungsten-copper composite metal oxide powder from room temperature to a first-stage reduction temperature, and reducing the tungsten-copper composite metal oxide powder at the first-stage reduction temperature for a period of time; and   heating a resulting powder from the first-stage reduction temperature to a second-stage reduction temperature, and reducing the resulting powder at the second-stage reduction temperature for a period of time.   
     
     
         7 . The method of  claim 6 , wherein in step (4), in the argon-hydrogen atmosphere,
 heating the tungsten-copper composite metal oxide powder from the room temperature to the first-stage reduction temperature is conducted at a heating rate of 0.2° C./min to 5° C./min, and heating the resulting powder from the first-stage reduction temperature to the second-stage reduction temperature is conducted at a heating rate of 3° C./min to 6° C./min;   the first-stage reduction temperature is in a range of 300° C. to 450° C., and reducing the tungsten-copper composite metal oxide powder at the first-stage reduction temperature is conducted for 2 h to 5 h;   the second-stage reduction temperature is in a range of 750° C. to 850° C., and reducing the resulting powder at the second-stage reduction temperature is conducted for 1 h to 7 h; and   the argon-hydrogen atmosphere has a hydrogen volume fraction of 5% to 15%.   
     
     
         8 . A method for preparing an interembedded autogenous molybdenum-copper alloy powder, wherein the method is conducted according to the method of any one of  claim 1 , except that:
 in step (2), the aqueous solution of the soluble tungsten salt is replaced by an aqueous solution of a soluble molybdenum salt, the soluble molybdenum salt is one or more selected from the group consisting of sodium molybdate and ammonium molybdate, the aqueous solution of the soluble molybdenum salt has a concentration of 0.01 mol/L to 1.0 mol/L, and a volume ratio of the aqueous solution of the soluble molybdenum salt to the aqueous solution of the soluble copper salt is 1:1;   in step (3), a molybdenum-copper composite metal oxide powder is obtained; and   in step (4), the molybdenum-copper composite metal oxide powder is subjected to the thermal reduction in the argon-hydrogen atmosphere to obtain the interembedded autogenous molybdenum-copper alloy powder.   
     
     
         9 . The method of  claim 8 , wherein in step (1),
 the soluble copper salt is one or more selected from the group consisting of copper nitrate and copper sulfate;   the aqueous solution of the soluble copper salt has a concentration of 0.01 mol/L to 2.3 mol/L;   the organic complex is one or more selected from the group consisting of lactic acid, glycolic acid, and gelatin; and   under a condition that the organic complex is the lactic acid or the glycolic acid, a molar ratio of the lactic acid or the glycolic acid to the soluble copper salt is in a range of greater than 1:1.   
     
     
         10 . The method of  claim 8 , wherein in step (2),
 the resulting mixture is concentrated after heating to a temperature of 30° C. to 50° C. to obtain a gel; and   the drying is conducted in the drying oven at a temperature of 80° C. to 120° C. for 2 h to 6 h.   
     
     
         11 . The method of  claim 8 , wherein in step (3),
 calcining the precursor in the air is conducted by the following two stages:   heating the precursor from room temperature to a first-stage calcination temperature, and calcining the precursor at the first-stage calcination temperature for a period of time; and   heating a resulting material from the first-stage calcination temperature to a second-stage calcination temperature, and calcining the resulting material at the second-stage calcination temperature for a period of time.   
     
     
         12 . The method of  claim 8 , wherein in step (3),
 heating the precursor from the room temperature to the first-stage calcination temperature is conducted at a heating rate of 0.5° C./min to 6° C./min, and heating the resulting material from the first-stage calcination temperature to the second-stage calcination temperature is conducted at a heating rate of 5° C./min to 13° C./min;   the first-stage calcination temperature is in a range of 250° C. to 420° C., and calcining the precursor at the first-stage calcination temperature is conducted for 2 h to 7 h; and   the second-stage calcination temperature is in a range of 450° C. to 600° C., and calcining the resulting material at the second-stage calcination temperature is conducted for 1 h to 5 h.   
     
     
         13 . The method of  claim 8 , wherein in step (4),
 the thermal reduction is conducted by the following two stages:   in the argon-hydrogen atmosphere, heating the molybdenum-copper composite metal oxide powder from room temperature to a first-stage reduction temperature, and reducing the molybdenum-copper composite metal oxide powder at the first-stage reduction temperature for a period of time; and   heating a resulting powder from the first-stage reduction temperature to a second-stage reduction temperature, and reducing the resulting powder at the second-stage reduction temperature for a period of time.   
     
     
         14 . The method of  claim 13 , wherein in step (4), in the argon-hydrogen atmosphere,
 heating the molybdenum-copper composite metal oxide powder from the room temperature to the first-stage reduction temperature is conducted at a heating rate of 0.2° C./min to 5° C./min, and heating the resulting powder from the first-stage reduction temperature to the second-stage reduction temperature is conducted at a heating rate of 3° C./min to 6° C./min;   the first-stage reduction temperature is in a range of 300° C. to 450° C., and reducing the molybdenum-copper composite metal oxide powder at the first-stage reduction temperature is conducted for 2 h to 5 h;   the second-stage reduction temperature is in a range of 750° C. to 850° C., and reducing the resulting powder at the second-stage reduction temperature is conducted for 1 h to 7 h; and   the argon-hydrogen atmosphere has a hydrogen volume fraction of 5% to 15%.   
     
     
         15 . An interembedded autogenous tungsten-copper alloy powder prepared by the method of  claim 1 . 
     
     
         16 . An interembedded autogenous molybdenum-copper alloy powder prepared by the method of  claim 8 . 
     
     
         17 . A method of ethanol-assisted energy-saving hydrogen production, comprising using the interembedded autogenous tungsten-copper alloy powder of  claim 15 . 
     
     
         18 . A method of ethanol-assisted energy-saving hydrogen production, comprising using the interembedded autogenous molybdenum-copper alloy powder of  claim 16 .