阅读说明：本技术 一种利用废富物料生产多晶相钒系合金的方法 (Method for producing polycrystalline phase vanadium series alloy by utilizing waste rich material ) 是由 张国桢 于 2021-06-23 设计创作，主要内容包括：本发明公开了一种利用废富物料生产多晶相钒系合金的方法,通过利用废富物料,降低生产成本,减少污染排放,更加节能高效,主要包括以下步骤：a.准备原料,并对原辅材料化学分析、分类,控制入炉粒度；b.起弧：将钒渣以及焦粉混合均匀,取其中一部分作为打底,铺设在适配有电抗器的电弧炉中,进行起弧熔炼；c.初步冶炼：起弧完成后,加入剩下的钒渣、焦粉混合物料进行初步冶炼；d.碱度指标调节：补充石灰,调整金属液的碱度指标,营造有利于还原进行的还原环境；e.二次还原：检测初步熔炼阶段氧化铁的还原情况,再加入适量的后备还原剂；f.合金化：二次还原后的电弧炉中,铁水状况平稳、温度平稳,加入添加剂,充分精炼。g.成型、冷却。(The invention discloses a method for producing a polycrystalline phase vanadium series alloy by utilizing waste rich materials, which reduces the production cost and the pollutant discharge by utilizing the waste rich materials, is more energy-saving and efficient and mainly comprises the following steps: a. preparing raw materials, carrying out chemical analysis and classification on the raw and auxiliary materials, and controlling the grain size of the raw and auxiliary materials; b. arcing: uniformly mixing vanadium slag and coke powder, taking a part of the mixture as a bottoming, laying the bottoming in an electric arc furnace which is suitable for a reactor, and carrying out arc starting smelting; c. primary smelting: after the arcing is finished, adding the remaining vanadium slag and coke powder mixed material for primary smelting; d. alkalinity index adjustment: supplementing lime, adjusting the alkalinity index of the molten metal and creating a reduction environment which is beneficial to reduction; e. and (3) secondary reduction: detecting the reduction condition of the ferric oxide in the preliminary smelting stage, and adding a proper amount of backup reducing agent; f. alloying: in the electric arc furnace after the secondary reduction, the molten iron is stable in condition and temperature, and the additive is added and fully refined. g. And (5) molding and cooling.)

1. A method for producing polycrystalline phase vanadium series alloy by utilizing waste rich materials is characterized by comprising the following steps: the method comprises the following steps:

a. preparing raw materials, carrying out chemical analysis and classification on the raw and auxiliary materials, and controlling the grain size of the raw and auxiliary materials;

the raw materials comprise: controlling the granularity of the vanadium slag, the coke powder and the additive to be 5-50 mm;

b. arcing;

uniformly mixing vanadium slag and coke powder, taking a part of the mixture as a bottoming, laying the bottoming in an electric arc furnace which is suitable for a reactor, and carrying out arc starting smelting;

c. performing primary smelting;

after the arc striking is finished, adding the remaining vanadium slag and coke powder mixed material for primary smelting, stably supplying power, and adjusting the secondary voltage of the electric furnace, wherein the long arc operation is adopted in the stage;

d. refining;

controlling the furnace temperature at 1300-1700 ℃, and adding the additive into the furnace for smelting;

e. and (5) molding and cooling.

2. The method for producing the polycrystalline phase vanadium-based alloy by using the waste rich material according to the claim 1, is characterized in that: the refining process comprises the following three steps:

alkalinity index adjustment: controlling the furnace temperature to be about 1400 ℃, melting a large amount of materials in the furnace, supplementing lime in the process, adjusting the alkalinity index of the molten metal, and creating a reduction environment which is beneficial to reduction;

and (3) secondary reduction: detecting the reduction condition of the ferric oxide in the preliminary smelting stage, adding a proper amount of backup reducing agent, and controlling the temperature at 1500 ℃ for 30-40 minutes;

alloying: and (3) adding an additive into the electric arc furnace after the secondary reduction, fully refining for 40-50 minutes, and controlling the temperature to be 1500-1650 ℃.

3. The method for producing the polycrystalline phase vanadium-based alloy by using the waste rich material according to the claim 1, is characterized in that: the vanadium slag is a waste rich material, wherein the content of FeO is 40-70%; the content of V2O5 is 2.5-8.5%.

4. The method for producing the polycrystalline phase vanadium-based alloy from the waste rich material according to the claim 2, wherein: the alkalinity index is: CaO2/SiO2, and the alkalinity index range of the molten metal is 2.0-2.5.

5. The method for producing the polycrystalline phase vanadium-based alloy from the waste rich material according to the claim 2, wherein: the backup reductant comprises: any one or more of aluminum, corundum and ferrosilicon.

Technical Field

The invention belongs to the field of metal smelting, and particularly relates to a method for producing a polycrystalline phase vanadium series alloy by using waste rich materials.

Background

Polycrystal phase low vanadium alloy is an important steel-making alloy additive, usually adopt vanadium pentoxide electrical silicothermic process smelting process, the production technology of this method is mature, the equipment level is advanced, the product quality is stable, the vanadium recovery rate adopting the electrical silicothermic process abroad is above 95%, the vanadium iron product quality and vanadium recovery rate adopting the vanadium pentoxide electrical silicothermic process produced domestically have certain difference with the foreign advanced level, in addition, there are many enterprises at home and abroad adopting the electrical aluminothermic process to prepare the vanadium iron alloy, compared with the electrical silicothermic process, its smelting time is short, the furnace condition is easy to control, the worker labor intensity is low, the product quality is stable, the environmental pollution is small, the comprehensive cost is low, generally vanadium trioxide or vanadium pentoxide, iron particles, aluminum powder and other materials are installed in the electric arc furnace, the electric heating is carried out, the reaction is promoted, the high vanadium iron smelting by the electrical aluminothermic process can also make the recovery rate of vanadium reach 95%, FIG. 1 shows a flow chart of a process for smelting ferrovanadium by an electro-aluminothermic method in the prior art.

In the prior art, in order to fully reduce vanadium oxide, excessive aluminum powder is generally added, which causes high aluminum content in gold: the slag has high melting point and higher smelting temperature, and is not beneficial to smooth smelting; iron inclusion in slag and the like. At present, in order to remove aluminum in alloy treatment, vanadium pentoxide is generally adopted as an oxidant to oxidize aluminum; the method not only increases the cost, but also causes higher vanadium content in the slag, and the vanadium-rich slag needs to be returned to the furnace for use, thereby increasing the difficulty of smelting operation.

The patent document with the application number of 201310291195.5 discloses a process for smelting ferrovanadium by an electro-aluminothermic method, which mainly adopts lime, aluminum, vanadium pentoxide and other raw materials, mixes iron, borax and fluorite to form a mixture, and then carries out smelting through a traditional electric arc furnace, but the vanadium pentoxide of the technology is added in the form of vanadium flakes, the cost of the vanadium flakes is relatively high, and the cost of the whole product is increased.

Disclosure of Invention

The invention aims to provide a method for producing a polycrystalline phase vanadium series alloy by utilizing waste rich materials, which effectively reduces the production cost by using waste residues with lower cost.

In order to achieve the purpose, the technical scheme is as follows:

a method for producing polycrystalline phase vanadium series alloy by utilizing waste rich materials comprises the following steps:

a. preparing raw materials, carrying out chemical analysis and classification on the raw and auxiliary materials, and controlling the grain size of the raw and auxiliary materials;

the raw materials comprise: controlling the granularity of the vanadium slag, the coke powder and the additive to be 5-50 mm;

b. arcing;

uniformly mixing vanadium slag and coke powder, taking a part of the mixture as a bottoming, laying the bottoming in an electric arc furnace which is suitable for a reactor, and carrying out arc starting smelting;

c. performing primary smelting;

after the arc striking is finished, adding the remaining vanadium slag and coke powder mixed material for primary smelting, stably supplying power, and adjusting the secondary voltage of the electric furnace, wherein the long arc operation is adopted in the stage;

d. refining;

controlling the furnace temperature at 1300-1700 ℃, and adding the additive into the furnace for smelting;

e. and (5) molding and cooling.

Further, the refining process is divided into the following three steps:

alkalinity index adjustment: controlling the furnace temperature to be about 1400 ℃, melting a large amount of materials in the furnace, supplementing lime in the process, adjusting the alkalinity index of the molten metal, and creating a reduction environment which is beneficial to reduction;

and (3) secondary reduction: detecting the reduction condition of the ferric oxide in the preliminary smelting stage, adding a proper amount of backup reducing agent, and controlling the temperature at 1500 ℃ for 30-40 minutes;

alloying: in the electric arc furnace after the secondary reduction, the molten iron is stable in condition and stable in temperature, the additive is added, the mixture is fully refined for 40-50 minutes, and the temperature is controlled at 1500-1650 ℃.

Further, the vanadium slag is a waste rich material, and the content of FeO in the vanadium slag is 40-70%; the content of V2O5 is 2.5-8.5%.

Further, the alkalinity index is: CaO2/SiO2, and the alkalinity index range of the molten metal is 2.0-2.5.

Further, the backup reductant comprises: any one or more of aluminum, corundum and ferrosilicon.

The invention has at least the following beneficial effects:

(1) the vanadium slag is directly used as a reaction raw material, compared with the prior art that the vanadium flake is used as a raw material, the cost is obviously lower, the vanadium flake in the prior art needs to be additionally prepared, the cost is high, a large amount of resources need to be consumed in the smelting process, the green production is not facilitated, and the vanadium slag is waste materials which are inevitably generated in the vanadium-titanium product smelting process, so that the additional preparation is not needed.

(2) Through multi-stage temperature control and the cooperation of multi-level reduction design, carry out effectual regulation to the reactant in the stove, rather than once only add wait for the reaction to finish, solve the insufficient problem of reduction when vanadium slag is as reaction raw materials, improve the quality of product.

(3) The cost is lower, and main raw materials and reducing materials are waste materials, so that the cost is reduced from the source, the economic benefit is higher, the waste rich materials can be recycled, and the utilization rate of resources is improved.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.

In the drawings:

FIG. 1 is a schematic flow chart showing a prior art process for smelting ferrovanadium by a circuit aluminothermic method;

FIG. 2 schematically illustrates a process flow diagram of the present invention;

Detailed Description

The invention discloses a method for producing a polycrystalline phase vanadium series alloy by utilizing waste rich materials, which comprises the following steps:

a. preparing raw materials, carrying out chemical analysis and classification on the raw and auxiliary materials, and controlling the grain size of the raw and auxiliary materials.

In this example, the raw materials include: the vanadium slag, the coke powder and the additives are adjusted according to different products, and the granularity of the materials is controlled to be 5-50 mm.

Further, the vanadium slag is a waste rich material, and the content of FeO in the vanadium slag is 40-70%; the content of V2O5 is 2.5-8.5%.

b. And (4) arcing.

And uniformly mixing the vanadium slag and the coke powder, taking a part of the mixture as a bottoming, laying the mixture in an electric arc furnace which is suitable for a reactor, and carrying out arc starting smelting.

c. And (5) performing primary smelting.

After the arc striking is finished, adding the remaining vanadium slag and coke powder mixed material for primary smelting, stably supplying power, adjusting the secondary voltage of the electric furnace, and adopting long arc operation in the stage to improve the furnace temperature and the material melting amount, wherein the long arc operation is a method generally adopted by a person skilled in the art, so the detailed description is omitted.

It should be noted that: the effect of coke powder is to get rid of the iron oxide impurity in the vanadium slag, the iron oxide impurity is the material that is difficult to get rid of in the vanadium metal smelting, and vanadium slag itself is as useless rich material, the content of iron oxide is higher than prior art's semi-manufactured goods material, consequently mix coke powder just before smelting with vanadium slag, smelt together with vanadium slag, can fully contact with the metal solution after the melting, give play to the reduction effect better, if wait for vanadium slag after the melting add coke powder, coke powder just can not fully contact with the metal solution, just can not effectively get rid of iron oxide impurity wherein.

d. And adjusting alkalinity index.

Controlling the furnace temperature to be about 1400 ℃, melting a large amount of materials in the furnace, supplementing lime in the process, and adjusting the alkalinity index of the molten metal to 2.0-2.5, wherein in the embodiment, the alkalinity index is as follows: CaO2/SiO2 can form a reducing environment favorable for reduction in the alkalinity index range, and the reduction efficiency is improved.

e. And (5) carrying out secondary reduction.

Detecting the reduction condition of the iron oxide in the preliminary smelting stage, adding a proper amount of a backup reducing agent, controlling the temperature at 1500 ℃, and carrying out 30-40 minutes, wherein V2O5 can be melted and the backup reducing agent can be used for reducing the iron oxide at the temperature above 1500 ℃, and for smelting vanadium series alloy, the commonly used reducing agents include but are not limited to: ferrosilicon, aluminum and corundum; in addition, the slag can be removed when the slag amount is large.

It should be noted that: the reduction condition of the iron oxide is judged according to the content of the iron oxide in the sample, and the iron oxide in the primary smelting stage is considered to be fully reacted and can be subjected to secondary reduction when the content of the iron oxide is lower than 5 percent.

f. And (4) alloying.

In the electric arc furnace after the secondary reduction, the molten iron is stable in condition and stable in temperature, the additive is added, the mixture is fully refined for 40-50 minutes, and the temperature is controlled at 1500-1650 ℃.

The kind of the additive is flexibly adjusted according to different products, the relevant reaction principle is common knowledge, and therefore, the kind of the additive is not limited in the embodiment.

g. And (5) molding and cooling.

And pouring the obtained alloy liquid into a mould for forming and cooling to obtain a finished product.

In the production process, the multi-stage temperature control is set, and because the temperature of the electric arc furnace is relatively controllable in the metal smelting process, the electric arc furnace has the basis of realizing multi-stage temperature regulation, the whole smelting process is divided into different stages in the smelting process, the temperature is adjusted according to the adaptability of the different stages instead of being completely controlled by adopting uniform temperature, so that the smooth proceeding of each reaction process can be ensured, and the energy consumption can be reduced when the electric arc furnace runs at relatively low temperature.

The whole smelting process is not added with the material all at one time, but add partial vanadium slag at first and make the end, the vanadium slag melts and other materials are added in succession after the temperature is stable, therefore the stage that the vanadium slag melts is as the preliminary smelting stage, because contain more impurity in the vanadium slag, wherein inevitable contains the higher impurity of melting point, consequently, need fully heat in the stage of preliminary smelting, guarantee to melt completely, just mix vanadium slag and burnt powder in the preliminary smelting stage simultaneously, the grass can guarantee that the burnt powder is abundant to contact with the molten metal after the melting, if add burnt powder after the melting, burnt powder can float on the molten metal, in time stir and also can not guarantee good contact, thereby image reduction effect.

The subsequent stage is a refining stage, the molten alloy liquid is deeply reduced by matching with a multi-level reduction design in the refining process, and then a preset product can be obtained, because the raw material is vanadium slag which contains more impurities, in order to ensure the smooth proceeding of the reaction, the reduction process is divided into multiple steps, and generally, the alkalinity index is adjusted by lime to form a furnace charge crystalline phase reduction environment; the temperature is raised through secondary reduction, and the metal liquid is reduced by using a back-up reducing agent such as ferrosilicon, aluminum and the like, wherein V2O5 is mainly reduced, alloying is to add components required by a corresponding product into the metal liquid to be smelted into alloy, and certainly, a small amount of reducing agent can be added in the alloying step to improve the reduction effect; the process flow and the used raw and auxiliary materials can be finished by adopting waste rich materials, and the process flow has important contribution to solving the product cost.

In addition, the reducing agent is also a waste rich material, so that the cost can be further reduced under the condition of not influencing the use effect.

Experimental example 1

Target products: low ferrovanadium (FeV, V: 1.5% -4%)

The reaction principle is as follows: FeO + V2O5+ FeSi → FeV

Experimental materials: 1000kg of vanadium slag, 400-600 kg of coke powder, 30-50 kg of ferrosilicon, 50-70 kg of slaked lime (containing Ca (OH)2> 95%), 10kg of fluorite and an electric arc furnace (the nominal capacity is 1.5-12 t).

Experimental example 2

Target products: ferro-silico-manganese-vanadium (FeMnV, V: 4% -7%, Mn: 10% -15%)

The reaction principle is as follows: FeO + V2O5+ MnSi → FeMnV

Experimental materials: 1000kg of vanadium slag, 400-600 kg of coke powder, 50-70 kg of hydrated lime (containing Ca (OH)2> 95%), 80-100 kg of silicon-manganese alloy and a proper amount of ferrosilicon, and an electric arc furnace (the nominal capacity is 1.5-12 t).

Experimental example 3

Target products: silicon ferrovanadium (FeSiV, V: 20-25%, Si: 20-26%)

The reaction principle is as follows: FeO + V2O5+ Al + FeSi → FeSiV

Experimental materials: 1000kg of vanadium slag, 400-600 kg of coke powder, 50-70 kg of hydrated lime (containing Ca (OH)2> 95%), 100kg of aluminum (or 400kg of corundum), 80kg of ferrosilicon and an electric arc furnace (the nominal capacity is 1.5-12 t).

The experimental results are as follows:

the parameters of the finished product obtained by the application example are as follows:

TABLE 1 Main parameters of the products obtained in the examples

Note 1: because no relevant national standard exists, the standard value in the percentage of the main valuable elements is the industry standard or the standard value which is passed in the industry, and only reference is made.

Note 2: the market prices in the tables refer to the market prices of the corresponding products during the experiment, which do not represent a constant and inconvenient price, since the market prices fluctuate under various conditions and the raw material prices also fluctuate.

Analysis of results

It can be seen from the above experiments that the waste rich materials can be reused by the method of the embodiment, the utilization rate of resources is improved, the contents of iron oxide and vanadium pentoxide in the treated waste residues are greatly reduced, which shows that valuable elements in the waste rich materials are fully utilized, on the other hand, in the actually prepared product, the main valuable elements corresponding to the product can meet the standard value, so that the requirement of actual production is met, and in the aspect of cost, the method has a larger profit margin compared with the existing market price.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.