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CN115285995B - Tungsten carbide powder production process - Google Patents

Tungsten carbide powder production process Download PDF

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Publication number
CN115285995B
CN115285995B CN202210837446.4A CN202210837446A CN115285995B CN 115285995 B CN115285995 B CN 115285995B CN 202210837446 A CN202210837446 A CN 202210837446A CN 115285995 B CN115285995 B CN 115285995B
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carbon
gas
tungsten carbide
organic resin
carbide powder
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CN115285995A (en
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黄自力
谢中华
张秋和
王明生
刘斌
钟鑫
黄贵晔
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Ganzhou Huamao Tungsten Materials Co ltd
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Ganzhou Huamao Tungsten Materials Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/914Carbides of single elements
    • C01B32/949Tungsten or molybdenum carbides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a tungsten carbide powder production process, which relates to the technical field of tungsten carbide production, and comprises the following steps: heating the raw materials containing tungsten oxide and organic resin to at least 600 ℃, then heating to the highest temperature of 850 ℃ to perform primary gas-phase carburizing reaction with reducing gas, and finally heating to 1200-1600 ℃ to perform secondary gas-phase carburizing reaction with carbon-containing gas. According to the production process of the tungsten carbide powder, the organic resin is mixed in the raw materials, and when the raw materials are heated, the raw materials begin to be carbonized to provide a gaseous carbon source, and the gaseous carbon source further has a certain reducibility to react with tungsten in an anaerobic environment to form the tungsten carbide powder. And when the organic resin is heated at low temperature, the organic resin consumes residual low-content oxygen to produce carbon monoxide, and the carbon monoxide has reducibility in the subsequent high-temperature reaction, so that the stability of the reducing atmosphere is ensured, and the carbon source is also ensured.

Description

Tungsten carbide powder production process
Technical Field
The invention relates to the technical field of tungsten carbide production, in particular to a tungsten carbide powder production process.
Background
Tungsten carbide powder (WC) is a main raw material for producing hard alloy, is black hexagonal crystal, has metallic luster, has hardness similar to diamond, and is a good conductor of electricity and heat. A large number of applications are in high-speed cutting tools, kiln construction materials, jet engine parts, cermet materials, resistive heating elements, etc.
The traditional process is to produce tungsten carbide from black tungsten concentrate or white tungsten concentrate, and usually, many procedures such as ammonium paratungstate production, tungsten powder preparation, carbonization and the like must be carried out, so that the production cost is high, the process is long, and the traditional reduction sintering temperature is up to 1800 ℃.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a tungsten carbide powder production process.
The technical scheme of the invention is as follows: a tungsten carbide powder production process comprises the following steps:
heating the raw materials containing tungsten oxide and organic resin to at least 600 ℃, then heating to the highest temperature of 850 ℃ to perform primary gas-phase carburizing reaction with reducing gas, and finally heating to 1200-1600 ℃ to perform secondary gas-phase carburizing reaction with carbon-containing gas.
As a preferable mode of the invention, the raw material is added with grain inhibitor accounting for 1-5wt% of the raw material.
As a preferred embodiment of the present invention, the grain inhibitor is a raw material containing at least B element.
As a preferred embodiment of the present invention, the organic resin is one or more of acrylic resin, phenolic resin, rosin resin and polyamide resin.
As a preferred embodiment of the present invention, the organic resin accounts for 1 to 6wt% of the raw material.
As a preferred embodiment of the present invention, the reducing gas includes hydrogen.
As a preferred embodiment of the present invention, the carbon-containing gas includes hydrogen, carbon monoxide and methane.
As a preferred embodiment of the present invention, the total volume of carbon monoxide and methane is 1-3% of the volume of the carbon-containing gas.
The beneficial effects of the invention are as follows:
(1) According to the production process of the tungsten carbide powder, the organic resin is mixed in the raw materials, and when the raw materials are heated, the raw materials begin to be carbonized to provide a gaseous carbon source, and the gaseous carbon source further has a certain reducibility to react with tungsten in an anaerobic environment to form the tungsten carbide powder. And when the organic resin is heated at low temperature, the organic resin consumes residual low-content oxygen to produce carbon monoxide, and the carbon monoxide has reducibility in the subsequent high-temperature reaction, so that the stability of the reducing atmosphere is ensured, and the carbon source is also ensured.
(2) According to the production process of the tungsten carbide powder, the B element in the grain inhibitor can enable the raw material to form a liquid state at low temperature, so that the heating time is shortened, the growth of grains at high temperature is reduced, and therefore the grains are thinned.
(3) According to the production process of the tungsten carbide powder, disclosed by the invention, the two-time gas-phase carburization is adopted, so that the residue of free carbon is reduced, and the performance of the tungsten carbide powder is improved. The carbon source of the primary gas-phase carburization reaction is organic resin, the carbon source of the secondary gas-phase carburization reaction is carbon-containing gas, the primary reduction carburization reaction of the traditional reaction is divided into two steps, the carbonization reaction rate is reduced, bursting in the grain formation process is reduced, and meanwhile, the reaction is more thorough.
Detailed Description
The following examples are given for the purpose of illustration only and are not to be construed as limiting the scope of the invention, which is susceptible to several non-essential modifications and adaptations by those skilled in the art based on the teachings of the present invention.
Example 1
A tungsten carbide powder production process comprises the following steps:
heating the raw material containing tungsten oxide and organic resin to 600deg.C under flowing nitrogen gas with flow rate of 30cm 3 And/s, then heating to 850 ℃ to perform a gas-phase carburizing reaction with a reducing gas with a flow rate of 300cm 3 Reaction time is 4h, and finally, the temperature is raised to 1200 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, and the flow rate of the carbon-containing gas is 230cm 3 Reaction time was 2h.
The raw material is added with grain inhibitor accounting for 1 weight percent of the raw material.
The grain inhibitor is boron carbide.
The organic resin is acrylic resin.
The organic resin accounts for 1wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide or methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1:1.
Example 2
A tungsten carbide powder production process comprises the following steps:
heating the raw material containing tungsten oxide and organic resin to 650 ℃ under flowing nitrogen atmosphere, wherein the flow rate of nitrogen is 35cm 3 And/s, then heating to 850 ℃ to perform a gas-phase carburizing reaction with a reducing gas with a flow rate of 400cm 3 Reaction time is 3h, and finally the reaction time is raised to 1300 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, the flow rate of the carbon-containing gas is 250cm 3 Reaction time was 2h.
The raw material is added with grain inhibitor accounting for 3wt% of the raw material.
The grain inhibitor is boron carbide.
The organic resin is one or more of acrylic resin, phenolic resin, rosin resin and polyamide resin
The organic resin accounts for 3wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide or methane. The total volume of carbon monoxide and methane is 2% of the volume of the carbon-containing gas.
Example 3
A tungsten carbide powder production process comprises the following steps:
heating the raw material containing tungsten oxide and organic resin to 700 ℃ under flowing nitrogen atmosphere, wherein the flow rate of nitrogen is 30cm 3 And/s, then heating to 850 ℃ to perform primary gas-phase carburization reaction with reducing gas with the flow rate of the reducing gas being 350cm 3 Reaction time is 2h, and finally, the temperature is increased to 1500 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, and the flow rate of the carbon-containing gas is 280cm 3 Reaction time was 1h.
The raw material is added with grain inhibitor accounting for 4 weight percent of the raw material.
The grain inhibitor is boron carbide.
The organic resin is rosin resin.
The organic resin accounts for 5wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide or methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1:1.
Example 4
A tungsten carbide powder production process comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 650deg.C under flowing nitrogen atmosphere, wherein the flow rate of nitrogen is 33cm 3 And/s, then heating to 850 ℃ to perform primary gas-phase carburization reaction with reducing gas with the flow rate of the reducing gas being 350cm 3 Reaction time is 3h, and finally, the temperature is increased to 1600 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, and the flow rate of the carbon-containing gas is 230cm 3 Reaction time was 2h.
The raw material is added with grain inhibitor accounting for 2wt% of the raw material.
The grain inhibitor is specifically boron carbide.
The organic resin is a mixture of acrylic resin, phenolic resin and rosin resin with the mass of 1:1:1.
The organic resin accounts for 3wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide or methane. The total volume of the carbon monoxide and the methane accounts for 3 percent of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1:1.
Example 5
A tungsten carbide powder production process comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 670 deg.C under flowing nitrogen atmosphere, the flow rate of nitrogen being 35cm 3 And/s, then heating to a maximum temperature of 850 ℃ and carrying out primary gas-phase carburizing reaction with a reducing gas, wherein the flow rate of the reducing gas is 310cm 3 Reaction time is 4h, and finally the temperature is increased to 1500 ℃ and the carbon-containing gas is subjected to secondary reactionGas phase carburizing reaction, the flow rate of the carbon-containing gas is 230cm 3 Reaction time was 2h.
The raw material is added with grain inhibitor accounting for 5 weight percent of the raw material.
The grain inhibitor is boron carbide.
The organic resin is polyamide resin.
The organic resin was 4wt% of the raw material.
The reducing gas includes hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide or methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1:1.
Comparative example 1 (one-time reduction)
A tungsten carbide powder production process comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 670 deg.C under flowing nitrogen atmosphere, the flow rate of nitrogen being 35cm 3 And/s, then heating to a maximum temperature of 1800 ℃ to carry out a gas-phase carburizing reaction with a reducing gas with a flow rate of 360cm 3 Reaction time was 4h.
The raw material is added with grain inhibitor accounting for 5 weight percent of the raw material.
The grain inhibitor is boron carbide.
The organic resin is polyamide resin.
The organic resin was 4wt% of the raw material.
The reducing gas is hydrogen.
Comparative example 2 (no inhibitor)
A tungsten carbide powder production process comprises the following steps:
heating raw material containing tungsten oxide and organic resin to 670 deg.C under flowing nitrogen atmosphere, the flow rate of nitrogen being 35cm 3 And/s, then heating to a maximum temperature of 850 ℃ and carrying out primary gas-phase carburizing reaction with a reducing gas, wherein the flow rate of the reducing gas is 310cm 3 Reaction time is 4h, and finally the temperature is raised to 1500 ℃ and carbon-containing gas is introducedPerforming secondary gas phase carburization reaction, wherein the flow rate of the carbon-containing gas is 230cm 3 Reaction time was 2h.
The organic resin is polyamide resin.
The organic resin was 4wt% of the raw material.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide or methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1:1.
Comparative example 3 (carbon black was used as the carbon source)
A tungsten carbide powder production process comprises the following steps:
heating the raw material containing tungsten oxide and carbon black to 670 deg.C under flowing nitrogen atmosphere, wherein the flow rate of nitrogen is 35cm 3 And/s, then heating to a maximum temperature of 850 ℃ and carrying out primary gas-phase carburizing reaction with a reducing gas, wherein the flow rate of the reducing gas is 310cm 3 Reaction time is 4h, and finally, the temperature is increased to 1500 ℃ to carry out secondary gas phase carburization reaction with carbon-containing gas, and the flow rate of the carbon-containing gas is 230cm 3 Reaction time was 2h.
The raw material is added with grain inhibitor accounting for 5 weight percent of the raw material.
The grain inhibitor is boron carbide.
The carbon black represents 4wt% of the feedstock.
The reducing gas is hydrogen.
The carbon-containing gas is hydrogen, carbon monoxide or methane. The total volume of the carbon monoxide and the methane accounts for 2% of the volume of the carbon-containing gas, and the volume ratio of the carbon monoxide to the methane is 1:1.
The test pieces of the above examples and comparative examples were subjected to performance test, the test methods are as follows, and the test results are shown in Table 1.
(1) And detecting free carbon by adopting an SK-S double-tube high-temperature carbon-fixing instrument.
(2) Oxygen content measurements were performed using a TCH-600 nitroxide analyzer manufactured by LECO Inc. of America.
Table 1 results of performance testing of examples and comparative examples samples
As can be seen from the above table, the performance of the example pattern is better than the comparative example, probably for the following reasons: analysis of comparative example 1 shows that the use of two gas phase carburizations in the examples reduces the free carbon residue and thus improves the performance of tungsten carbide powder. The carbon source of the primary gas-phase carburization reaction is organic resin, the carbon source of the secondary gas-phase carburization reaction is carbon-containing gas, the primary reduction carburization reaction of the traditional reaction is divided into two steps, the carbonization reaction rate is reduced, bursting in the crystal grain forming process is reduced, meanwhile, the reaction is more thorough, the purity of tungsten carbide is higher, the oxygen content is very low, and the reduction atmosphere is excellent. Analysis of comparative example 2 shows that the B element in the grain inhibitor can enable the raw material to form a liquid state at a low temperature, thereby reducing the temperature rise time and reducing the growth of grains at a high temperature, thereby refining the grains and accelerating the reaction process. Analysis of comparative example 3 shows that the performance of using organic matters as carbon sources can be achieved and possibly superior to that of using carbon black as a carbon source in the prior art, and thus, a new scheme using organic carbon sources as a carbon source can be adopted.
The above additional technical features can be freely combined and superimposed by a person skilled in the art without conflict.
The foregoing is only a preferred embodiment of the present invention, and all technical solutions for achieving the object of the present invention by substantially the same means are included in the scope of the present invention.

Claims (3)

1. The production process of the tungsten carbide powder is characterized by comprising the following steps of:
heating a raw material containing tungsten oxide and organic resin to at least 600 ℃ in flowing nitrogen atmosphere, then heating to the highest temperature of 850 ℃ and carrying out primary gas-phase carburizing reaction with reducing gas, and finally heating to 1200-1600 ℃ and carrying out secondary gas-phase carburizing reaction with carbon-containing gas; the raw materials are added with grain inhibitors accounting for 1-5wt% of the raw materials; the grain inhibitor is boron carbide; the organic resin is one or more of acrylic resin, phenolic resin, rosin resin and polyamide resin;
the carbon-containing gas is hydrogen, carbon monoxide and methane, and the total volume of the carbon monoxide and methane accounts for 1-3% of the volume of the carbon-containing gas.
2. A tungsten carbide powder production process according to claim 1, wherein the organic resin comprises 1-6wt% of the raw material.
3. A tungsten carbide powder production process according to claim 1, wherein the reducing gas comprises hydrogen.
CN202210837446.4A 2022-07-15 2022-07-15 Tungsten carbide powder production process Active CN115285995B (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5372797A (en) * 1991-11-20 1994-12-13 The Dow Chemical Company Low temperature method for synthesizing micrograin tungsten carbide
CN1247520A (en) * 1997-03-31 2000-03-15 Omg美国公司 Process for preparing transition metal carbides from partially reduced transition metal compounds
CN1254628A (en) * 1999-08-13 2000-05-31 武汉工业大学 Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt
CN1326424A (en) * 1998-11-13 2001-12-12 H·C·施塔克公司 Method for producing wolfram carbides by gas-phase carburetion
CN1481345A (en) * 2000-12-20 2004-03-10 �����ͺչ�ҵ���޹�˾ Method for producing tungsten carbide
CN1837040A (en) * 2006-04-14 2006-09-27 北京科技大学 Method for self-propagating high-temperature synthesis of nano-tungsten carbide powder
CN107089662A (en) * 2017-06-16 2017-08-25 重庆大学 A kind of method that CH4 reduction and carbonizations WO3 prepares WC powders
CN107973299A (en) * 2017-11-30 2018-05-01 株洲三鑫硬质合金生产有限公司 A kind of production system and its production technology of high temperature base WC powder
CN108423684A (en) * 2018-05-21 2018-08-21 北京科技大学 A kind of environment-protection nano tungsten carbide powder preparation method
CN108892141A (en) * 2018-09-06 2018-11-27 北京科技大学 A kind of high-purity, ultrafine tungsten carbide preparation method

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5372797A (en) * 1991-11-20 1994-12-13 The Dow Chemical Company Low temperature method for synthesizing micrograin tungsten carbide
CN1247520A (en) * 1997-03-31 2000-03-15 Omg美国公司 Process for preparing transition metal carbides from partially reduced transition metal compounds
CN1326424A (en) * 1998-11-13 2001-12-12 H·C·施塔克公司 Method for producing wolfram carbides by gas-phase carburetion
CN1254628A (en) * 1999-08-13 2000-05-31 武汉工业大学 Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt
CN1481345A (en) * 2000-12-20 2004-03-10 �����ͺչ�ҵ���޹�˾ Method for producing tungsten carbide
CN1837040A (en) * 2006-04-14 2006-09-27 北京科技大学 Method for self-propagating high-temperature synthesis of nano-tungsten carbide powder
CN107089662A (en) * 2017-06-16 2017-08-25 重庆大学 A kind of method that CH4 reduction and carbonizations WO3 prepares WC powders
CN107973299A (en) * 2017-11-30 2018-05-01 株洲三鑫硬质合金生产有限公司 A kind of production system and its production technology of high temperature base WC powder
CN108423684A (en) * 2018-05-21 2018-08-21 北京科技大学 A kind of environment-protection nano tungsten carbide powder preparation method
CN108892141A (en) * 2018-09-06 2018-11-27 北京科技大学 A kind of high-purity, ultrafine tungsten carbide preparation method

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