阅读说明：本技术 一种氮化钒铌铁合金及其制备方法和应用 (Vanadium nitride niobium iron alloy and preparation method and application thereof ) 是由 刘克忠 翁玉娟 贾怡晗 王清晨 王朝晖 孟立新 王彬彬 刘健 曹长山 刘亚亮 池 于 2020-06-28 设计创作，主要内容包括：本发明提供了一种氮化钒铌铁合金及其制备方法和应用,属于合金材料技术领域。本发明提供的方法在氮气气氛中将原料混合粉经自蔓延燃烧合成反应得到氮化钒铌铁合金,按质量比计,所述氮化钒铌铁合金N/(V+Nb)的比值高(为0.25～0.31),既能充分发挥钒的析出强化作用,又能充分发挥铌的细晶强化作用,降低成本；同时出钢过程加入一种合金即可,操作简便。此外,本发明提供的方法不需外加热源,设备简单,工序简单,实现了氮化钒铌铁合金的低成本制备,制备得到的氮化钒铌铁合金均匀性和稳定性好,能够满足钢铁冶炼的需要,经济和社会效益显著。(The invention provides a vanadium nitride niobium iron alloy and a preparation method and application thereof, belonging to the technical field of alloy materials. According to the method, the raw material mixed powder is subjected to self-propagating combustion synthesis reaction in a nitrogen atmosphere to obtain the vanadium nitride ferroniobium alloy, and the ratio of N/(V + Nb) of the vanadium nitride ferroniobium alloy is high (0.25-0.31) in terms of mass ratio, so that the precipitation strengthening effect of vanadium can be fully exerted, the fine-grain strengthening effect of niobium can be fully exerted, and the cost is reduced; meanwhile, only one alloy is added in the tapping process, and the operation is simple and convenient. In addition, the method provided by the invention has the advantages of no need of an external heat source, simple equipment and simple process, realizes the low-cost preparation of the vanadium nitride ferroniobium alloy, ensures that the prepared vanadium nitride ferroniobium alloy has good uniformity and stability, can meet the requirements of steel smelting, and has remarkable economic and social benefits.)

1. The preparation method of the vanadium nitride niobium iron alloy is characterized by comprising the following steps of:

putting the raw material mixed powder into a reactor, igniting the raw material mixed powder by an ignition device in a nitrogen atmosphere, and carrying out self-propagating combustion synthesis reaction to obtain vanadium nitride niobium iron alloy;

wherein the vanadium nitride niobium iron alloy comprises the following components:

5-60 wt.% of vanadium, 5-60 wt.% of niobium, 1-15 wt.% of silicon, 1-4 wt.% of manganese, 1-10 wt.% of aluminum, 5-20 wt.% of nitrogen, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron.

2. The production method according to claim 1, wherein the raw material mixed powder includes ferrovanadium powder, ferroniobium powder, ferrosilicon powder, ferromanganese powder, and aluminum powder.

3. The method according to claim 2, wherein the composition of the ferrovanadium alloy powder comprises: 25-90 wt.% of vanadium, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferrovanadium alloy powder is as follows: the vanadium iron alloy powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the vanadium iron alloy powder, and the vanadium iron alloy powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the vanadium iron alloy powder;

the components of the niobium-iron alloy powder comprise: 30-70 wt.% of niobium, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the niobium-iron alloy powder is as follows: the ferroniobium powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the ferroniobium powder, and the ferroniobium powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the ferroniobium powder.

4. The production method according to claim 2, wherein the ferrosilicon alloy powder has a composition including: 72-80 wt.% of silicon, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferrosilicon alloy powder is as follows: the ferrosilicon powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the ferrosilicon powder, and the ferrosilicon powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the ferrosilicon powder;

the ferromanganese alloy powder comprises the following components: 65-70 wt.% of manganese, less than or equal to 6.5 wt.% of carbon, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferromanganese alloy powder is as follows: the ferromanganese alloy powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the ferromanganese alloy powder, and the ferromanganese alloy powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the ferromanganese alloy powder;

the aluminum powder comprises the following components: 97-99 wt.% of aluminum, and the balance unavoidable impurities; the granularity of the aluminum powder is 74-150 mu m.

5. The method according to any one of claims 1 to 4, wherein the raw material mixed powder further comprises a diluent.

6. The method of claim 5, wherein the diluent comprises a vanadium niobium iron nitride powder having a particle size of <5 mm; the content of the diluent in the raw material mixed powder is 1-20 wt.%.

7. The method according to claim 1, wherein the pressure in the reactor is 1 to 16MPa, and the pressure in the reactor is provided by nitrogen.

8. The preparation method according to claim 1, wherein the time of the self-propagating combustion synthesis reaction is 5-30 min.

9. The vanadium nitride niobium iron alloy prepared by the preparation method of any one of claims 1 to 8, wherein the particle size is 5 to 50 mm.

10. Use of the vanadium nitride niobite alloy according to claim 9 as an additive for iron and steel smelting.

Technical Field

The invention relates to the technical field of alloy materials, in particular to a vanadium nitride niobium iron alloy and a preparation method and application thereof.

Background

In the field of alloy materials, vanadium and niobium are two important microalloying elements, the action mechanisms in steel are different, vanadium has the strongest precipitation strengthening effect in steel, niobium has the strongest fine-grain strengthening effect in steel, and in order to fully utilize the strengthening effects of vanadium and niobium, a composite vanadium-niobium alloy needs to be developed.

Disclosure of Invention

The invention aims to provide a vanadium nitride niobium ferroalloy and a preparation method and application thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of a vanadium nitride niobium iron alloy, which comprises the following steps:

putting the raw material mixed powder into a reactor, igniting the raw material mixed powder by an ignition device in a nitrogen atmosphere, and carrying out self-propagating combustion synthesis reaction to obtain vanadium nitride niobium iron alloy;

wherein the vanadium nitride niobium iron alloy comprises the following components:

5-60 wt.% of vanadium, 5-60 wt.% of niobium, 1-15 wt.% of silicon, 1-4 wt.% of manganese, 1-10 wt.% of aluminum, 5-20 wt.% of nitrogen, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron.

Preferably, the raw material mixed powder comprises ferrovanadium powder, ferroniobium powder, ferrosilicon powder, ferromanganese powder and aluminum powder.

Preferably, the composition of the ferrovanadium alloy powder comprises: 25-90 wt.% of vanadium, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferrovanadium alloy powder is as follows: the vanadium iron alloy powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the vanadium iron alloy powder, and the vanadium iron alloy powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the vanadium iron alloy powder;

the components of the niobium-iron alloy powder comprise: 30-70 wt.% of niobium, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the niobium-iron alloy powder is as follows: the ferroniobium powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the ferroniobium powder, and the ferroniobium powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the ferroniobium powder.

Preferably, the ferrosilicon alloy powder comprises the following components: 72-80 wt.% of silicon, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferrosilicon alloy powder is as follows: the ferrosilicon powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the ferrosilicon powder, and the ferrosilicon powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the ferrosilicon powder;

the ferromanganese alloy powder comprises the following components: 65-70 wt.% of manganese, less than or equal to 6.5 wt.% of carbon, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferromanganese alloy powder is as follows: the ferromanganese alloy powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the ferromanganese alloy powder, and the ferromanganese alloy powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the ferromanganese alloy powder;

the aluminum powder comprises the following components: 97-99 wt.% of aluminum, and the balance unavoidable impurities; the granularity of the aluminum powder is 74-150 mu m.

Preferably, the raw material mixed powder further comprises a diluent.

Preferably, the diluent comprises vanadium niobium iron nitride powder, the particle size of the vanadium niobium iron nitride powder being <5 mm; the content of the diluent in the raw material mixed powder is 1-20 wt.%.

Preferably, the pressure in the reactor is 1-16 MPa, and the pressure in the reactor is provided by nitrogen.

Preferably, the time of the self-propagating combustion synthesis reaction is 5-30 min.

The vanadium nitride niobium iron alloy prepared by the preparation method provided by the invention has the granularity of 5-50 mm.

The invention provides the application of the vanadium nitride niobium iron alloy in the technical scheme as an additive of the vanadium nitride niobium iron alloy for steel smelting.

The invention provides a preparation method of a vanadium nitride niobium iron alloy, which comprises the following steps: putting the raw material mixed powder into a reactor, igniting the raw material mixed powder by an ignition device in a nitrogen atmosphere, and carrying out self-propagating combustion synthesis reaction to obtain vanadium nitride niobium iron alloy; wherein the vanadium nitride niobium iron alloy comprises the following components: 5-60 wt.% of vanadium, 5-60 wt.% of niobium, 1-15 wt.% of silicon, 1-4 wt.% of manganese, 1-10 wt.% of aluminum, 5-20 wt.% of nitrogen, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron. According to the method, the raw material mixed powder is subjected to self-propagating combustion synthesis reaction in a nitrogen atmosphere to obtain the vanadium nitride ferroniobium alloy, and the ratio of N/(V + Nb) of the vanadium nitride ferroniobium alloy is high (0.25-0.31) in terms of mass ratio, so that the precipitation strengthening effect of vanadium can be fully exerted, the fine-grain strengthening effect of niobium can be fully exerted, and the cost is reduced; meanwhile, only one alloy is added in the tapping process, and the operation is simple and convenient. In addition, the method provided by the invention has the advantages of no need of an external heat source, simple equipment and simple process, realizes the low-cost preparation of the vanadium nitride ferroniobium alloy, ensures that the prepared vanadium nitride ferroniobium alloy has good uniformity and stability, can meet the requirements of steel smelting, and has remarkable economic and social benefits.

Detailed Description

The invention provides a preparation method of a vanadium nitride niobium iron alloy, which comprises the following steps:

putting the raw material mixed powder into a reactor, igniting the raw material mixed powder by an ignition device in a nitrogen atmosphere, and carrying out self-propagating combustion synthesis reaction to obtain vanadium nitride niobium iron alloy;

wherein the vanadium nitride niobium iron alloy comprises the following components:

5-60 wt.% of vanadium, 5-60 wt.% of niobium, 1-15 wt.% of silicon, 1-4 wt.% of manganese, 1-10 wt.% of aluminum, 5-20 wt.% of nitrogen, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron.

In the invention, the vanadium nitride niobium iron alloy comprises 5-60 wt.% of vanadium, preferably 10-50 wt.%; 5-60 wt.%, preferably 10-50 wt.% niobium; 1-15 wt.%, preferably 2-10 wt.% of silicon; 1-4 wt.%, preferably 2-3 wt.% manganese; 1-10 wt.%, preferably 2-9 wt.% aluminum; 5-20 wt.% of nitrogen, preferably 8-18 wt.%; the inevitable impurities are less than or equal to 2 wt.%, and the balance is iron.

In the invention, the raw material mixed powder comprises ferrovanadium powder, ferroniobium powder, ferrosilicon powder, ferromanganese powder and aluminum powder. The invention adds silicon to improve the nitrogen content of the product, manganese mainly improves the specific gravity of the product, and aluminum improves the heat quantity needed by the product synthesis.

In the present invention, the composition of the ferrovanadium alloy powder preferably includes: 25-90 wt.% of vanadium, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferrovanadium alloy powder is preferably as follows: the vanadium iron alloy powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the vanadium iron alloy powder, and the vanadium iron alloy powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the vanadium iron alloy powder;

the components of the ferrocolumbium powder preferably include: 30-70 wt.% of niobium, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the grain size distribution of the ferrocolumbium powder is preferably as follows: the niobium-iron alloy powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the niobium-iron alloy powder, and the niobium-iron alloy powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the niobium-iron alloy powder;

the ferrosilicon alloy powder preferably comprises the following components: 72-80 wt.% of silicon, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferrosilicon alloy powder is preferably as follows: the ferrosilicon powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the ferrosilicon powder, and the ferrosilicon powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the ferrosilicon powder;

the ferromanganese alloy powder preferably comprises the following components: 65-70 wt.% of manganese, less than or equal to 6.5 wt.% of carbon, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron; the particle size distribution of the ferromanganese alloy powder is preferably as follows: the ferromanganese alloy powder with the granularity of 74-420 mu m accounts for 20-75% of the total mass of the ferromanganese alloy powder, and the ferromanganese alloy powder with the granularity of less than 74 mu m accounts for 25-80% of the total mass of the ferromanganese alloy powder;

the aluminum powder preferably comprises the following components: 97-99 wt.% of aluminum, and the balance unavoidable impurities; the particle size of the aluminum powder is preferably 74-150 mu m.

The raw materials with the particle size distribution are adopted, so that the particle size is small, the reaction area is large, and the full contact of each component and nitrogen is favorably realized; in the embodiment of the invention, the required vanadium iron alloy, niobium iron alloy, ferrosilicon alloy and ferromanganese alloy can be crushed and ground to obtain the raw material powder with the required particle size.

In the invention, the raw material mixed powder preferably further comprises a diluent, the diluent preferably comprises nitrided vanadium niobium iron powder, the nitrided vanadium niobium iron powder is preferably from unqualified nitrided vanadium niobium iron powder products generated in the preparation process of nitrided vanadium niobium iron alloy, the granularity is usually less than 5mm, namely, nitrided vanadium niobium iron powder which is generated in the current preparation process and cannot be used as a commodity is used as the diluent in the next preparation process, and the production cost is favorably reduced; the content of the diluent in the raw material mixed powder is preferably 1-20 wt.%, and more preferably 1-15 wt.%. The invention can reduce the temperature of the self-propagating combustion synthesis reaction by using the diluent, is beneficial to the stable operation of the self-propagating combustion synthesis reaction, and can economically process the vanadium nitride niobium iron powder which can not be used as a commodity.

The invention preferably determines the proportion of each raw material according to the components of the required vanadium nitride niobium iron alloy. In the present invention, it is preferable that after the raw material powders are mixed, the obtained raw material mixed powder is placed in a reactor, and more preferably, the raw material mixed powder is placed in a reactor in a flat manner. The reactor is not specially limited, and the sealing condition can be ensured and the required pressure requirement can be met; the present invention preferably employs a high-pressure reactor as the reactor.

After the raw material mixed powder is placed in a reactor, the reactor is preferably sealed and then vacuumized to-0.06 to-0.08 MPa, then nitrogen is filled into the reactor until the pressure in the reactor is 1 to 16MPa, and finally the raw material mixed powder is ignited by an ignition device to carry out self-propagating combustion synthesis reaction, so that the vanadium nitride niobium iron alloy is obtained. The reactor is sealed, vacuumized and filled with nitrogen, so that the oxidation of the vanadium nitride niobium iron alloy in the self-propagating combustion synthesis reaction process can be avoided to the greatest extent. In the invention, the nitrogen is preferably high-purity nitrogen, the purity is preferably more than or equal to 99.99 percent, and more preferably 99.99-99.999 percent; after the nitrogen is filled, the pressure in the reactor is preferably 1-16 MPa, and more preferably 3-12 MPa. The ignition device of the present invention is not particularly limited, and an ignition device known to those skilled in the art may be used. In the invention, when the raw material mixed powder is ignited by the ignition device, an ignition agent is not used, and the ignition is ensured to be successful; in order to improve the ignition success rate, an ignition agent can be used, the ignition agent preferably comprises one or more of aluminum powder, titanium powder and carbon powder, and if the ignition agent is used, the ignition agent can be removed according to a conventional method in the field after the subsequent self-propagating combustion synthesis reaction is finished, so that the product quality is not influenced.

In the invention, after the raw material mixed powder is ignited, the raw material mixed powder can start and spontaneously and continuously carry out self-propagating combustion synthesis reaction until the reaction is finished, and the vanadium nitride niobium iron alloy is obtained. In the process of the self-propagating combustion synthesis reaction, the pressure in the reactor is preferably maintained at 1-16 MPa, and more preferably at 3-12 MPa by controlling the introduction amount of nitrogen. The invention preferably maintains the pressure of the nitrogen in the reactor in the range, has high concentration of the nitrogen, can accelerate the reaction process, shorten the reaction time and improve the production efficiency. In the invention, the reaction time of the self-propagating combustion synthesis reaction is preferably 5-30 min, more preferably 15-30 min, the reaction time is counted from the ignition of the raw material mixed powder until the raw material mixed powder is completely combusted, specifically, the reaction time is influenced by the combustion speed and the size of the reactor, and the combustion speed can be regulated and controlled by regulating and controlling the nitrogen pressure in the reactor and the granularity of the raw material mixed powder, so that the reaction is ensured to be carried out stably, smoothly and efficiently.

After the self-propagating combustion synthesis reaction is finished, the invention preferably naturally cools the synthetic product (namely the vanadium nitride niobium iron alloy) in the reactor to be less than or equal to 100 ℃, then opens the reactor, takes out the obtained synthetic product, and the synthetic product is a solid which is densely sintered together or a solid which is loosely sintered together, and is crushed to obtain the vanadium nitride niobium iron alloy finished product with the granularity of 5-50 mm.

The vanadium nitride niobium iron alloy is prepared by a self-propagating combustion synthesis method, and has the characteristics of no need of an external heat source, rapid reaction and high production efficiency. Specifically, in the reaction process, nitrogen gas and ferrovanadium alloy powder and ferroniobium alloy powder (and auxiliary powder) are subjected to combustion synthesis reaction to generate vanadium nitride ferroniobium alloy, nitrogen, ferrovanadium and ferroniobium (and components in the auxiliary powder) form a solid solution compound, the nitrogen content is high, the property is stable at normal temperature, and the nitrogen is not easily oxidized; and the prepared vanadium nitride niobium iron alloy has good uniformity due to short reaction time and basically consistent physical and chemical conditions in the reaction process. In conclusion, the vanadium nitride niobium iron alloy prepared by the method has high nitrogen content, good uniformity and stability, greatly reduced cost and obvious economic and social benefits; the vanadium nitride niobium iron alloy provided by the invention can well meet the requirements of reducing the cost and simplifying the production in the steelmaking process.

The invention provides the vanadium nitride niobium iron alloy prepared by the preparation method in the technical scheme. The vanadium nitride niobium iron alloy comprises the following components: 5-60 wt.% of vanadium, 5-60 wt.% of niobium, 1-15 wt.% of silicon, 1-4 wt.% of manganese, 1-10 wt.% of aluminum, 5-20 wt.% of nitrogen, less than or equal to 2 wt.% of inevitable impurities, and the balance of iron. The vanadium nitride niobium iron alloy provided by the invention has high nitrogen content, good uniformity and stability and preferable apparent density of 4.30-5.30 g/cm³The particle size is preferably 5 to 50 mm.

The invention provides the application of the vanadium nitride ferroniobium alloy in the technical scheme as the vanadium nitride ferroniobium alloy additive for steel smelting, and preferably can be used as the vanadium nitride ferroniobium alloy additive of alloy steel, cast steel or low-alloy high-strength steel.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.