阅读说明：本技术 一种利用含钨废料生产粗颗粒碳化钨粉的方法 (Method for producing coarse-particle tungsten carbide powder by using tungsten-containing waste ) 是由 冯国升 冯相聚 于 2017-06-12 设计创作，主要内容包括：本发明属于冶金技术领域,公开了一种利用含钨废料生产粗颗粒碳化钨粉的方法,含钨废料经过除杂提纯及氧化焙烧后,再将物料按一定重量比混合,然后放入反应炉中反应,经过SHS还原法生产成碳化钨粉,出炉后除杂,取样分析合格后,干燥处理,然后筛分,按照客户要求进行包装入库。本发明有效的利用含钨废料,实现了含钨废料的深加工,资源回收率高,经济效益显著；且生产出的碳化钨的纯度高,有害杂质元素低,化学成分优良,外观好。(The invention belongs to the technical field of metallurgy, and discloses a method for producing coarse-grained tungsten carbide powder by using tungsten-containing waste. The method effectively utilizes the tungsten-containing waste, realizes the deep processing of the tungsten-containing waste, and has high resource recovery rate and remarkable economic benefit; and the produced tungsten carbide has high purity, low content of harmful impurity elements, excellent chemical components and good appearance.)

1. A method for producing coarse-grained tungsten carbide powder by using tungsten-containing waste is characterized by comprising the following steps: the method comprises the following steps:

(1) preparing: firstly, removing impurities and purifying tungsten-containing waste materials by using an acidic solution, then placing the waste materials into a roasting furnace for drying and roasting, controlling the temperature to be about 500 ℃, roasting for 8 hours, and then cooling to normal temperature to obtain tungsten oxide with the tungsten content of 60-65%;

the content of metal tungsten in the tungsten-containing waste is more than or equal to 30 percent;

(2) calculating the required ingredient amount according to the tungsten content in the material, and calculating according to the following weight ratio:

tungsten oxide: 50-65%;

aluminum powder: 18-28%;

sodium nitrate: 2-5%;

calcium fluoride: 1-2.7%;

calcium carbide: 1-10%;

carbon black: 0-8%;

the purity of the aluminum powder is more than or equal to 99 percent;

(3) putting the materials into a mixer, and mixing for 21-30 minutes to ensure that the materials are uniformly mixed;

(4) putting the mixed materials into a prepared reaction furnace for multiple times, firstly enabling the volume of the mixed materials to account for one third of the volume of the reaction furnace, igniting, controlling the furnace temperature to be 3400-3600 ℃, gradually adding the mixed materials during the reaction, stopping feeding when the volume of the reacted materials accounts for three quarters of the volume of the reaction furnace, keeping the temperature and standing for 10 minutes, treating the reaction furnace by introducing high-purity argon gas into the reaction furnace for protection or vacuumizing, controlling the separation and burning loss of carbon, and discharging the reaction furnace when the reaction furnace is cooled to normal temperature, wherein a heat insulation layer is arranged around the reaction furnace, and a directional water cooling device is arranged below the bottom of the reaction furnace, so that the tungsten water in the reaction furnace can be directionally crystallized;

(5) after the materials are taken out of the furnace, the materials are put into an acid solution for cleaning, and impurities are removed;

(6) sampling, analyzing, drying after being qualified, then screening, and packaging and warehousing according to the requirements of customers;

the purity of the tungsten carbide powder is 99.5% or 99.8%.

2. The method for producing the coarse-grained tungsten carbide powder by using the tungsten-containing waste material according to claim 1, wherein the method comprises the following steps:

the aluminum powder in the step (2) is characterized in that: the particle size is 60-110 meshes.

3. The method for producing the coarse-grained tungsten carbide powder by using the tungsten-containing waste material according to claim 1, wherein the method comprises the following steps:

the calcium fluoride in the step (2) is characterized in that: CaF₂Not less than 99 percent and the granularity is 60-90 meshes.

4. The method for producing the coarse-grained tungsten carbide powder by using the tungsten-containing waste material according to claim 1, wherein the method comprises the following steps:

the sodium nitrate in the step (2) is sodium nitrate with industrial purity, the granularity is 100-200 meshes, and the carbon black in the step (2) is carbon black with industrial purity, and the granularity is 100-200 meshes.

5. The method for producing the coarse-grained tungsten carbide powder by using the tungsten-containing waste material according to claim 1, wherein the method comprises the following steps:

the acidic solution in the step (1) is one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.

6. The method for producing the coarse-grained tungsten carbide powder by using the tungsten-containing waste material according to claim 1, wherein the method comprises the following steps: the acidic solution in the step (5) is one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.

Technical Field

The invention belongs to the technical field of metallurgy, and particularly relates to a method for producing coarse-particle tungsten carbide powder by using tungsten-containing waste.

Background

Tungsten is used as an element capable of generating carbide, the tungsten carbide is added into steel to improve the toughness of the steel, and the tungsten carbide has fine particles and high hardness, so that the hardness and the wear resistance of the steel are greatly improved. Tungsten increases the tempering stability, red hardness and heat strength of steel, increases the self-diffusion activation energy of iron, obviously improves the recrystallization temperature of the steel, thereby also improving the creep deformation capability of the steel at high temperature,

at present, the recovery and processing treatment of the tungsten-containing waste in China are gradually scaled to form an industry, mainly the tungsten-containing waste is treated into sodium tungstate by a wet process, the method has the characteristics of high treatment capacity, low requirement on the tungsten content of the tungsten-containing waste and the like, and is widely applied, but the method has serious environmental pollution and relatively complex process.

The Chinese patent application No. 2016104601868 (application date is 2016.06.22) discloses a method for preparing coarse-grain tungsten carbide from ferrotungsten, which comprises the steps of using ferrotungsten, iron and carbon as raw materials, dissolving the raw materials in molten iron at high temperature to form tungsten carbide with the tungsten and the carbon, cooling and crystallizing, crushing, and acid-soluble leaching to obtain single-crystal tungsten carbide particles with the particle size of several microns to several hundred microns.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention adopts the technical scheme that tungsten-containing waste is subjected to impurity removal, oxidation roasting and SHS reduction to produce tungsten carbide powder.

In order to achieve the above object, the present invention provides a method for producing coarse tungsten carbide powder from tungsten-containing waste, comprising the steps of:

(1) preparing: firstly, removing impurities and purifying tungsten-containing waste materials by using an acidic solution, then placing the waste materials into a roasting furnace for drying and roasting, controlling the temperature to be about 500 ℃, roasting for 8 hours, and then cooling to normal temperature to obtain tungsten oxide with the tungsten content of 60-65%;

the content of metal tungsten in the tungsten-containing waste is more than or equal to 30 percent;

(2) calculating the required ingredient amount according to the tungsten content in the material, and calculating according to the following weight ratio:

tungsten oxide: 50-65%;

aluminum powder: 10-25%;

sodium nitrate: 2-5%;

calcium fluoride: 1-2.5%;

calcium carbide: 1-10%;

carbon black: 0-8%;

the purity of the aluminum powder is more than or equal to 99 percent;

(3) putting the materials into a mixer, and mixing for 21-30 minutes to ensure that the materials are uniformly mixed;

(4) putting the mixed materials into a prepared reaction furnace for multiple times, firstly enabling the volume of the mixed materials to account for one third of the volume of the reaction furnace, igniting, controlling the furnace temperature to be 3400-3600 ℃, gradually adding the mixed materials during the reaction, stopping feeding when the volume of the reacted materials accounts for three quarters of the volume of the reaction furnace, keeping the temperature and standing for 10 minutes, treating the reaction furnace by introducing high-purity argon into the reaction furnace for protection or vacuumizing, controlling the separation and burning loss of carbon, and discharging the reaction furnace after cooling to normal temperature;

(5) after the materials are taken out of the furnace, the materials are put into an acid solution for cleaning, and impurities are removed;

(6) sampling, analyzing, drying after being qualified, then screening, and packaging and warehousing according to the requirements of customers;

the purity of the tungsten carbide powder is 99.5% or 99.8%.

Preferably, the aluminum powder is characterized in that: granularity: 60-110 mesh.

Preferably, the calcium fluoride is characterized by: CaF₂Not less than 99 percent and the granularity is 60-90 meshes.

Preferably, the sodium nitrate is sodium nitrate with industrial purity, and the granularity is 100-200 meshes.

The carbon black is industrially pure carbon black with the granularity of 100-200 meshes.

Preferably, the acidic solution in step (1) is one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.

Preferably, the acidic solution in step (5) is one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.

Has the advantages that:

1) the invention adopts metal reducing agent with low impurity content and high-content tungsten oxide after removing impurities, so that the produced tungsten carbide has high purity, low harmful impurity elements, excellent chemical components and good appearance. The metal recovery rate of the method is 1-2% higher than that of the same domestic method, the product cost is low, and the economic benefit advantage is obvious.

2) The invention puts the mixed materials into the reaction furnace for a plurality of times, can fully utilize the space of the reaction furnace, prevents the materials from being blown out of the reaction furnace by the reaction hot air flow to cause material waste, and is convenient for controlling the furnace temperature.

3) Because the raw materials used in the process are from the waste materials polished in the production of tungsten-containing products, the tungsten oxide obtained by impurity removal, calcination and other treatments has high tungsten content and the content of other impurity elements is far lower than that of products produced by ores.

4) The process equipment of the invention has less investment, changeable scale, direct application in industrial production, simple operation, good working environment, no labor intensity, low labor cost, energy conservation, environmental protection, low energy consumption, less water resource consumption, no generation of harmful waste water and CO₂And the waste gas contains recyclable tungsten, and can be completely recycled by adopting a cyclone dust removal and water spraying method, so that the dual requirements of resource recycling and environmental protection are met.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example one

(1) Preparation: firstly, removing impurities and purifying tungsten-containing waste materials by using a hydrochloric acid solution, then placing the waste materials into a roasting furnace for drying and roasting, controlling the temperature at 500 ℃, roasting for 8 hours, and then cooling to normal temperature to obtain tungsten oxide with the tungsten content of 60%.

(2) Calculating the required ingredient amount according to the tungsten content in the material, and calculating according to the following weight ratio (unit: kg):

tungsten oxide: 765

Aluminum powder: 299

Sodium nitrate: 25

Calcium fluoride: 30

Calcium carbide: 40

Carbon black: 20

(3) The materials are put into a mixer and mixed for 25 minutes, and the materials are uniformly mixed.

(4) Putting the mixed materials into a prepared reaction furnace for multiple times, firstly enabling the volume of the mixed materials to account for one third of the volume of the reaction furnace, igniting, controlling the furnace temperature to be 3400 ℃, gradually adding the mixed materials during the reaction, stopping feeding when the volume of the mixed materials accounts for three quarters of the volume of the reaction furnace, keeping the temperature and standing for 10 minutes, introducing high-purity argon into the reaction furnace for protection, controlling the separation and burning loss of carbon, and discharging the mixture when the mixture is cooled to normal temperature.

(5) And putting the materials into a hydrochloric acid solution for cleaning after the materials are taken out of the furnace, and removing impurities.

(6) Sampling and analyzing, drying after being qualified, then screening, and packaging and warehousing according to the requirements of customers.

Example two

(1) Preparation: firstly, removing impurities and purifying tungsten-containing waste materials by using a sulfuric acid solution, then placing the waste materials into a roasting furnace for drying and roasting, controlling the temperature at 500 ℃, roasting for 8 hours, and then cooling to normal temperature to obtain tungsten oxide with the tungsten content of 65%.

(2) Calculating the required ingredient amount according to the tungsten content in the material, and calculating according to the following weight ratio (unit: kg):

tungsten oxide: 765

Aluminum powder: 299

Sodium nitrate: 25

Calcium fluoride: 30

Calcium carbide: 20

Carbon black: 60

(3) The materials are put into a mixer and mixed for 30 minutes, and the materials are uniformly mixed.

(4) And putting the mixed materials into a prepared reaction furnace for multiple times, firstly enabling the volume of the mixed materials to account for one third of the volume of the reaction furnace, igniting, controlling the furnace temperature to be 3400 ℃, gradually adding the mixed materials during the reaction, stopping feeding when the volume of the mixed materials accounts for three quarters of the volume of the reaction furnace, preserving heat, standing for 10 minutes, vacuumizing the reaction furnace, controlling the separation and burning loss of carbon, and discharging the mixture when the mixture is cooled to normal temperature.

(5) And putting the materials into a sulfuric acid solution for cleaning after the materials are taken out of the furnace, and removing impurities.

(6) Sampling and analyzing, drying after being qualified, then screening, and packaging and warehousing according to the requirements of customers.

Chemical compositions of tungsten carbide products obtained in the first and second examples:

although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.