阅读说明：本技术 一种钒氮合金生产过程中原料成型方法 (Raw material forming method in vanadium-nitrogen alloy production process ) 是由 张春雨 于 2021-06-07 设计创作，主要内容包括：一种钒氮合金生产过程中原料成型方法,包括以下步骤：(1)膨润土改性：将膨润土加入氢氧化钠溶液中,以400～500r/min的转速搅拌2-5小时,然后再进行喷雾干燥,即得改性膨润土；(2)将改性膨润土、聚乙烯醇、羧甲基纤维素混合,搅拌30分钟以上,得到混合物；(3)二次复合处理；(4)将五氧化二钒、碳粉、复合粘结剂混合,置于密闭容器中,先抽真空,再通入氮气加压,保压一段时间,即成。本发明所得原料的密度为2.8g/cm～(3)以上,甚至可达3.0 g/cm～(3)以上,能满足特定领域对钒氮合金原料的要求,特别是高密度的要求。(A raw material forming method in a vanadium-nitrogen alloy production process comprises the following steps: (1) modifying bentonite: adding bentonite into a sodium hydroxide solution, stirring for 2-5 hours at a rotating speed of 400-500 r/min, and then carrying out spray drying to obtain modified bentonite; (2) mixing modified bentonite, polyvinyl alcohol and carboxymethyl cellulose, and stirring for more than 30 minutes to obtain a mixture; (3) performing secondary composite treatment; (4) mixing vanadium pentoxide, carbon powder and a composite binder, placing the mixture in a closed container, vacuumizing, introducing nitrogen to pressurize, and maintaining the pressure for a period of time. The density of the raw material obtained by the invention is 2.8g/cm 3 Above, even up to 3.0 g/cm 3 The requirements of the specific field on the vanadium-nitrogen alloy raw material, particularly the requirement of high density, can be met.)

1. A raw material forming method in a vanadium-nitrogen alloy production process is characterized by comprising the following steps:

(1) modifying bentonite: adding bentonite into a sodium hydroxide solution, stirring for 2-5 hours at a rotating speed of 400-500 r/min, and then carrying out spray drying to obtain modified bentonite;

(2) mixing modified bentonite, polyvinyl alcohol and carboxymethyl cellulose, and stirring for more than 30 minutes to obtain a mixture;

(3) secondary composite treatment:

adding phenolic resin and glycerol into the mixture obtained in the step (2), adjusting the temperature to be 100-150 ℃ in an inert atmosphere, keeping the temperature and stirring for 5-6 hours, and naturally cooling to room temperature to obtain a composite binder;

(4) and (3) mixing vanadium pentoxide, carbon powder and the composite binder obtained in the step (3), placing the mixture in a closed container, vacuumizing, introducing nitrogen to pressurize, and maintaining the pressure for a period of time.

2. The raw material forming method in the vanadium-nitrogen alloy production process according to claim 1, wherein in the step (1), the mass fraction of the sodium hydroxide solution is 2-4%.

3. The raw material forming method in the vanadium-nitrogen alloy production process according to claim 1 or 2, wherein in the step (2), the mass ratio of the modified bentonite to the polyvinyl alcohol to the carboxymethyl cellulose is 5-6: 2-4: 0.5-1.

4. The raw material forming method in the vanadium-nitrogen alloy production process according to claim 1 or 2, wherein in the step (3), the mass ratio of the mixture obtained in the step (2), the phenolic resin and the glycerol is 10-20: 3-4: 1-2.

5. The raw material forming method in the vanadium-nitrogen alloy production process according to claim 1 or 2, wherein in the step (3), the inert atmosphere is nitrogen.

6. The method for molding the raw material in the vanadium-nitrogen alloy production process according to claim 1 or 2, wherein in the step (4), vanadium pentoxide, carbon powder and the composite binder obtained in the step (3) are mixed in a mass ratio of 100: 20-40: 1-5, and mixing.

7. The raw material forming method in the vanadium-nitrogen alloy production process according to claim 1 or 2, wherein in the step (4), vacuum is pumped to 1-2 Pa.

8. The raw material forming method in the vanadium-nitrogen alloy production process according to claim 1 or 2, wherein in the step (4), nitrogen is introduced to a pressure of 0.09Mpa or more.

9. The raw material forming method in the vanadium-nitrogen alloy production process according to claim 8, wherein in the step (4), nitrogen gas is introduced to a pressure of 0.095 to 1.2 Mpa.

10. The raw material forming method in the vanadium-nitrogen alloy production process according to claim 1 or 2, wherein in the step (4), the dwell time is 20 minutes or more.

Technical Field

The invention relates to a raw material forming method in a vanadium-nitrogen alloy production process.

Background

Vanadium is used as an important metal resource in China, is called industrial monosodium glutamate, has main products of vanadium pentoxide, vanadium trioxide, vanadium-nitrogen alloy, ferrovanadium alloy, vanadium-aluminum alloy and the like, and can be widely used in the fields of steel, chemical industry, national defense, electronics, manufacturing, energy storage, medicine, catalysis and the like.

The vanadium-nitrogen alloy is a novel alloy additive, and can replace ferrovanadium to be used for producing microalloyed steel. The vanadium nitride added into the steel can improve the comprehensive mechanical properties of the steel, such as strength, toughness, ductility, thermal fatigue resistance and the like, and enables the steel to have good weldability. Under the condition of achieving the same strength, the vanadium nitride is added, so that the adding amount of vanadium is saved by 30-40%, and the cost is further reduced.

The vanadium-nitrogen alloy is a blank made of vanadium pentoxide, carbon powder, an active agent and the like, and is reacted at a high temperature of 1500-1800 ℃ under the protection of normal pressure and nitrogen atmosphere to generate the vanadium-nitrogen alloy. When producing vanadium-nitrogen alloy, the vanadium-nitrogen raw material for producing vanadium-nitrogen alloy is formed, and the quality and yield of vanadium-nitrogen alloy are directly affected by the formation of vanadium-nitrogen raw material. The density of the vanadium-nitrogen raw material is another important factor besides the nitrogen content in the vanadium-nitrogen alloy, which affects the performance of the vanadium-nitrogen alloy.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects in the prior art, particularly overcoming the defect that the density of a vanadium-nitrogen raw material is not high enough in the prior art, and provides a raw material forming method in the production process of a vanadium-nitrogen alloy, wherein the density of the obtained vanadium-nitrogen alloy raw material is high.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a raw material forming method in a vanadium-nitrogen alloy production process comprises the following steps:

(1) modifying bentonite: adding bentonite into a sodium hydroxide solution, stirring for 2-5 hours at a rotating speed of 400-500 r/min, and then carrying out spray drying to obtain modified bentonite;

further, in the step (1), the mass fraction of the sodium hydroxide solution is 2-4%. Researches show that the bentonite is added into sodium hydroxide solution with certain concentration, the internal pore structure of the bentonite can be improved, and spray drying is combined to obtain the modified bentonite. In the subsequent use of the binder, the addition amount of the binder can be reduced, but better binding effect can be obtained, and the density of the obtained raw material can also be increased to a certain extent.

(2) Mixing modified bentonite, polyvinyl alcohol and carboxymethyl cellulose, and stirring for more than 30 minutes to obtain a mixture;

further, in the step (2), the mass ratio of the modified bentonite to the polyvinyl alcohol to the carboxymethyl cellulose is 5-6: 2-4: 0.5-1.

(3) Secondary composite treatment:

and (3) adding the mixture obtained in the step (2) into phenolic resin and glycerol, adjusting the temperature to be 100-150 ℃ in an inert atmosphere, keeping the temperature and stirring for 5-6 hours, and naturally cooling to room temperature to obtain the composite binder.

Further, in the step (3), the mass ratio of the mixture obtained in the step (2), the phenolic resin and the glycerol is 10-20: 3-4: 1-2.

Further, in the step (3), the inert atmosphere is nitrogen.

Researches show that the invention adopts the step (2) and the step (3) for mixing twice, so that the mixing is more uniform, and the performance of the obtained adhesive is better.

(4) And (3) mixing vanadium pentoxide, carbon powder and the composite binder obtained in the step (3), placing the mixture in a closed container, vacuumizing, introducing nitrogen to pressurize, and maintaining the pressure for a period of time.

Further, in the step (4), vanadium pentoxide, carbon powder and the composite binder obtained in the step (3) are mixed according to a mass ratio of 100: 20-40: 1-5, and mixing.

Further, in the step (4), vacuumizing to 1-2 Pa; mainly discharges other gases in the closed container, and also fully discharges other gases in the raw materials.

Further, in the step (4), nitrogen gas is introduced to a pressure of 0.09MPa or more (preferably 0.095 to 1.2MPa, more preferably 0.1 to 0.12 MPa). Introducing nitrogen for pressurization, similar to chemical vapor deposition, on one hand, nitrogen molecules penetrate into the raw materials to generate van der Waals force, so that the attraction among the molecules is tighter, and the density of the raw materials is increased; on the other hand, the density of the raw material is higher when a certain pressure is applied. The molding density of the raw materials can be increased under the dual principle. And the nitrogen element is also an element which needs to be increased in content in the vanadium-nitrogen alloy finished product, and other adverse effects cannot be brought. The pressure is too low, the nitrogen deposition is limited, and the requirement cannot be met; too big, it is limited to nitrogen gas deposition's effect, promotes a little, can increase manufacturing cost, brings the production potential safety hazard.

Further, in the step (4), the dwell time is 20 minutes or more. The time is too short, and nitrogen molecules cannot sufficiently permeate. The time is too long, the effect is improved to a limited extent, and the cost is increased. Therefore, 20 to 30 minutes is preferable.

Further, the operation in the step (4) is performed at normal temperature. On one hand, heating is not needed, energy is saved, and on the other hand, the operation is simple.

The invention adopts the specific adhesive, combines the processes of vacuumizing and introducing nitrogen for pressurizing, is similar to the chemical vapor deposition, and permeates nitrogen into the raw materials, thereby increasing the density of the raw materials on one hand and being beneficial to improving the nitrogen content in the vanadium-nitrogen alloy on the other hand. The density of the obtained raw material was 2.8g/cm³Above, even up to 3.0 g/cm³The requirements of the specific field on the vanadium-nitrogen alloy raw material, particularly the requirement of high density, can be met.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

Example 1

The raw material forming method in the vanadium-nitrogen alloy production process comprises the following steps:

(1) modifying bentonite: adding bentonite into a sodium hydroxide solution, stirring for 5 hours at the rotating speed of 450r/min, and then carrying out spray drying to obtain modified bentonite;

further, in the step (1), the mass fraction of the sodium hydroxide solution is 4%. Researches show that the bentonite is added into sodium hydroxide solution with certain concentration, the internal pore structure of the bentonite can be improved, and spray drying is combined to obtain the modified bentonite. In the subsequent use of the binder, the addition amount of the binder can be reduced, but better binding effect can be obtained, and the density of the obtained raw material can also be increased to a certain extent.

(2) Mixing the modified bentonite, polyvinyl alcohol and carboxymethyl cellulose, and stirring for 30 minutes to obtain a mixture;

further, in the step (2), the mass ratio of the modified bentonite to the polyvinyl alcohol to the carboxymethyl cellulose is 5:4: 1.

(3) Secondary composite treatment:

and (3) adding phenolic resin and glycerol into the mixture obtained in the step (2), adjusting the temperature to 150 ℃ in an inert atmosphere, keeping the temperature and stirring for 6 hours, and naturally cooling to room temperature to obtain the composite binder.

Further, in the step (3), the mass ratio of the mixture obtained in the step (2), the phenolic resin and the glycerol is 20: 3: 1.

Further, in the step (3), the inert atmosphere is nitrogen.

Researches show that the invention adopts the step (2) and the step (3) for mixing twice, so that the mixing is more uniform, and the performance of the obtained adhesive is better.

(4) And (3) mixing vanadium pentoxide, carbon powder and the composite binder obtained in the step (3), placing the mixture in a closed container, vacuumizing, introducing nitrogen to pressurize, and maintaining the pressure for a period of time.

Further, in the step (4), vanadium pentoxide, carbon powder and the composite binder obtained in the step (3) are mixed according to a mass ratio of 100: 20: and 5, mixing.

Further, in the step (4), vacuumizing to 1 Pa; mainly discharges other gases in the closed container, and also fully discharges other gases in the raw materials.

Further, in the step (4), nitrogen gas was introduced to a pressure of 0.1 MPa. Introducing nitrogen for pressurization, similar to chemical vapor deposition, on one hand, nitrogen molecules penetrate into the raw materials to generate van der Waals force, so that the attraction among the molecules is tighter, and the density of the raw materials is increased; on the other hand, the density of the raw material is higher when a certain pressure is applied. The molding density of the raw materials can be increased under the dual principle. And the nitrogen element is also an element which needs to be increased in content in the vanadium-nitrogen alloy finished product, and other adverse effects cannot be brought. The pressure is too low, the nitrogen deposition is limited, and the requirement cannot be met; too big, it is limited to nitrogen gas deposition's effect, promotes a little, can increase manufacturing cost, brings the production potential safety hazard.

Further, in the step (4), the dwell time was 20 minutes. The time is too short, and nitrogen molecules cannot sufficiently permeate. The time is too long, the effect is improved to a limited extent, and the cost is increased.

Further, the operation in the step (4) is performed at normal temperature. On one hand, heating is not needed, energy is saved, and on the other hand, the operation is simple.

The invention adopts the specific adhesive, combines the processes of vacuumizing and introducing nitrogen for pressurizing, is similar to the chemical vapor deposition, and permeates nitrogen into the raw materials, thereby increasing the density of the raw materials on one hand and being beneficial to improving the nitrogen content in the vanadium-nitrogen alloy on the other hand. The density of the obtained raw material was 3.08g/cm³。

Example 2

The raw material forming method in the vanadium-nitrogen alloy production process comprises the following steps:

(1) modifying bentonite: adding bentonite into sodium hydroxide solution, stirring for 3 hours at the rotating speed of 400r/min, and then carrying out spray drying to obtain modified bentonite;

further, in the step (1), the mass fraction of the sodium hydroxide solution is 2%. Researches show that the bentonite is added into sodium hydroxide solution with certain concentration, the internal pore structure of the bentonite can be improved, and spray drying is combined to obtain the modified bentonite. In the subsequent use of the binder, the addition amount of the binder can be reduced, but better binding effect can be obtained, and the density of the obtained raw material can also be increased to a certain extent.

(2) Mixing the modified bentonite, polyvinyl alcohol and carboxymethyl cellulose, and stirring for 40 minutes to obtain a mixture;

further, in the step (2), the mass ratio of the modified bentonite to the polyvinyl alcohol to the carboxymethyl cellulose is 6:2: 0.5.

(3) Secondary composite treatment:

and (3) adding phenolic resin and glycerol into the mixture obtained in the step (2), adjusting the temperature to 150 ℃ in an inert atmosphere, keeping the temperature and stirring for 6 hours, and naturally cooling to room temperature to obtain the composite binder.

Further, in the step (3), the mass ratio of the mixture obtained in the step (2), the phenolic resin and the glycerol is 20: 3: 1.

Further, in the step (3), the inert atmosphere is nitrogen.

Researches show that the invention adopts the step (2) and the step (3) for mixing twice, so that the mixing is more uniform, and the performance of the obtained adhesive is better.

(4) And (3) mixing vanadium pentoxide, carbon powder and the composite binder obtained in the step (3), placing the mixture in a closed container, vacuumizing, introducing nitrogen to pressurize, and maintaining the pressure for a period of time.

Further, in the step (4), vanadium pentoxide, carbon powder and the composite binder obtained in the step (3) are mixed according to a mass ratio of 100: 20: 1 and mixing.

Further, in the step (4), vacuumizing to 2 Pa; mainly discharges other gases in the closed container, and also fully discharges other gases in the raw materials.

Further, in the step (4), nitrogen gas was introduced to a pressure of 0.12 MPa. Introducing nitrogen for pressurization, similar to chemical vapor deposition, on one hand, nitrogen molecules penetrate into the raw materials to generate van der Waals force, so that the attraction among the molecules is tighter, and the density of the raw materials is increased; on the other hand, the density of the raw material is higher when a certain pressure is applied. The molding density of the raw materials can be increased under the dual principle. And the nitrogen element is also an element which needs to be increased in content in the vanadium-nitrogen alloy finished product, and other adverse effects cannot be brought. The pressure is too low, the nitrogen deposition is limited, and the requirement cannot be met; too big, it is limited to nitrogen gas deposition's effect, promotes a little, can increase manufacturing cost, brings the production potential safety hazard.

Further, in the step (4), the dwell time was 30 minutes. The time is too short, and nitrogen molecules cannot sufficiently permeate. The time is too long, the effect is improved to a limited extent, and the cost is increased.

Further, the operation in the step (4) is performed at normal temperature. On one hand, heating is not needed, energy is saved, and on the other hand, the operation is simple.

The invention adopts the specific adhesive, combines the processes of vacuumizing and introducing nitrogen for pressurizing, is similar to the chemical vapor deposition, and permeates nitrogen into the raw materials, thereby increasing the density of the raw materials on one hand and being beneficial to improving the nitrogen content in the vanadium-nitrogen alloy on the other hand. The density of the obtained raw material was 2.98g/cm³。

Example 3

The raw material forming method in the vanadium-nitrogen alloy production process comprises the following steps:

(1) modifying bentonite: adding bentonite into sodium hydroxide solution, stirring at a rotating speed of 400r/min for 2 hours, and then carrying out spray drying to obtain modified bentonite;

further, in the step (1), the mass fraction of the sodium hydroxide solution is 2%. Researches show that the bentonite is added into sodium hydroxide solution with certain concentration, the internal pore structure of the bentonite can be improved, and spray drying is combined to obtain the modified bentonite. In the subsequent use of the binder, the addition amount of the binder can be reduced, but better binding effect can be obtained, and the density of the obtained raw material can also be increased to a certain extent.

(2) Mixing the modified bentonite, polyvinyl alcohol and carboxymethyl cellulose, and stirring for 30 minutes to obtain a mixture;

further, in the step (2), the mass ratio of the modified bentonite to the polyvinyl alcohol to the carboxymethyl cellulose is 5:2: 1.

(3) Secondary composite treatment:

and (3) adding phenolic resin and glycerol into the mixture obtained in the step (2), adjusting the temperature to 100 ℃ in an inert atmosphere, keeping the temperature and stirring for 5 hours, and naturally cooling to room temperature to obtain the composite binder.

Further, in the step (3), the mass ratio of the mixture obtained in the step (2), the phenolic resin and the glycerol is 20: 3: 2.

Further, in the step (3), the inert atmosphere is nitrogen.

Researches show that the invention adopts the step (2) and the step (3) for mixing twice, so that the mixing is more uniform, and the performance of the obtained adhesive is better.

(4) And (3) mixing vanadium pentoxide, carbon powder and the composite binder obtained in the step (3), placing the mixture in a closed container, vacuumizing, introducing nitrogen to pressurize, and maintaining the pressure for a period of time.

Further, in the step (4), vanadium pentoxide, carbon powder and the composite binder obtained in the step (3) are mixed according to a mass ratio of 100: 30: 2 and mixing.

Further, in the step (4), vacuumizing to 1 Pa; mainly discharges other gases in the closed container, and also fully discharges other gases in the raw materials.

Further, in the step (4), nitrogen gas was introduced to a pressure of 0.09 MPa. Introducing nitrogen for pressurization, similar to chemical vapor deposition, on one hand, nitrogen molecules penetrate into the raw materials to generate van der Waals force, so that the attraction among the molecules is tighter, and the density of the raw materials is increased; on the other hand, the density of the raw material is higher when a certain pressure is applied. The molding density of the raw materials can be increased under the dual principle. And the nitrogen element is also an element which needs to be increased in content in the vanadium-nitrogen alloy finished product, and other adverse effects cannot be brought. The pressure is too low, the nitrogen deposition is limited, and the requirement cannot be met; too big, it is limited to nitrogen gas deposition's effect, promotes a little, can increase manufacturing cost, brings the production potential safety hazard.

Further, in the step (4), the dwell time was 25 minutes. The time is too short, and nitrogen molecules cannot sufficiently permeate. The time is too long, the effect is improved to a limited extent, and the cost is increased.

Further, the operation in the step (4) is performed at normal temperature. On one hand, heating is not needed, energy is saved, and on the other hand, the operation is simple.

The invention adopts the specific adhesive, combines the processes of vacuumizing and introducing nitrogen for pressurizing, is similar to the chemical vapor deposition, and permeates nitrogen into the raw materials, thereby increasing the density of the raw materials on one hand and being beneficial to improving the nitrogen content in the vanadium-nitrogen alloy on the other hand. The density of the obtained raw material was 2.85g/cm³。

Comparative example 1

In step (1) of this comparative example, bentonite, polyvinyl alcohol, and carboxymethyl cellulose were directly mixed without modifying bentonite to obtain a binder, and the other operations and parameters were the same as those in example 1. The density of the obtained raw material was 2.65g/cm³。

Comparative example 2

This comparative example was conducted under the same operating parameters as in example 1 except for the first mixing in step (2) and step (3).

Mixing the step (2) and the step (3) for the first time: (2) mixing modified bentonite, polyvinyl alcohol, carboxymethyl cellulose, phenolic resin and glycerol, and stirring for 30 minutes to obtain a mixture;

in the step (2), the mass ratio of the modified bentonite to the polyvinyl alcohol to the carboxymethyl cellulose is 5:4: 1.

(3) And (3) adjusting the temperature of the mixture obtained in the step (2) to 150 ℃ in an inert atmosphere, keeping the temperature and stirring for 6 hours, and then naturally cooling to room temperature to obtain the composite binder.

The density of the obtained raw material was 2.52g/cm³。

Comparative example 3

The comparative example was conducted under the same operating parameters as example 1, except that no composite binder was added in step (4).

The density of the obtained raw material was 2.36g/cm³。

Comparative example 4

This comparative example was conducted under the same operating parameters as in example 1, except that no vacuum was applied in step (4).

The density of the obtained raw material was 2.56g/cm³。

Comparative example 5

This comparative example was conducted in the same manner as example 1 except that no nitrogen gas was used for pressurization in step (4).

The density of the obtained raw material was 2.26g/cm³。