JPS63502995A - Materials that alloy metals with vanadium - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Materials that alloy metals with vanadium Technical field The present invention relates to ferrous metallurgy, and more particularly to materials that alloy the metal with vanadium. Regarding.

Background technology For pyrometallurgical production of vanadium-containing products (cast iron, steel and vanadium-containing alloys) Demand for vanadium-containing alloys (silicon vanadium, ferrovanadium, etc.) is increasing significantly. Alloys of vanadium, especially ferrovanadium production requires marginal and fairly expensive vanadium pentoxide, and vanadium-containing Alloys are primarily used to alloy cast iron and steel with vanadium. others Therefore, research has begun on new vanadium-containing materials for alloys. Regarding this Vanadium, which causes the oxidation of vanadium cast iron as a vanadium-containing material for alloys, It has been proposed to use Muslag (SU.

A, 196064. SU%A, 358374; SU%A.

394437).

The slag contains the following in mass percentage:

Iron oxide 41.6 Silicon oxide 16.4 Special edition Showa 63-502995 (2) Vanadium oxide 15.8 Manganese oxide 9.1 Titanium oxide 7.4 Chromium oxide 2.8 Calcium oxide 1.5 Metal phase 8-12 Impurities (MgO, A1203, R20) remaining.

The above slag is manufactured by N.B. Rekishev (N, P.

Lekishev et al., “Vanadium in Ferrous Metallurgy” um in Ferrous Metallurgy) J 1983, Mosque It is described on page 36. However, calcium and vanadium oxides The metal alloys with vanadium due to its high oxidation degree and low content As time increases, the overall efficiency of preparing vanadium-containing products decreases.

The same thing applies to vanadium in vanadium slag produced in China and SAR. The same can be said of its use as a containing material.

Vanadium slag produced in China is (in mass percentage) vanadium oxide 1 0-15%, iron oxide 33-45%, titanium oxide 8-13.5%, silicon oxide 7. 6-35.4%, manganese oxide 2.7-5.7%, calcium oxide 0.9-1. 5%, but these slags are depleted in vanadium and the accompanying reagent (fluid) (Sokolova K.H.). ova K, H,) Overseas production and consumption of vanadium (Produc tion and Con5uIlpt1on of VanadiumAbr oad), Bullet 1nst1tuta +Chermetinf ormatsiya - published October 1981, pages 3-15).

The vanadium slag produced in SAR contains (by mass percentage) 27. 8%, iron oxide 22.4%, calcium oxide 0.5%, magnesium oxide 0.3% , contains 17.3% silicon oxide, 3.5% aluminum oxide, 3.5% carbon, and the remainder part is impurity (Ti02, Mn02, Cr20)), and the The chemical composition of these slags makes them more suitable for alloying metals with vanadium. However, the lack of literature data on alloy metals indicates that calcium and and low magnesium oxide content, resulting in high flux and reducing agent consumption. This suggests that there is.

It consists of a slag (containing vanadium) component and a metal component, and these components can be formed into any form. The use of slag-metallic materials having a uniform shape and structure is not known in the art. Ru.

These materials have the following compositions (mass percentages):

Iron oxide 5-15 Silicon oxide 3-7 Calcium oxide 2-5 Vanadium oxide 0.3-0.8 Titanium oxide 2-5.0 Carbon 1.0-3.0 Reducible iron remainder.

These materials are made into bilayer particles with a diameter of 5 to 10+a+s. particle surface The layer contains a significant amount of carbon, and the inner layer is filled with a homogeneous solution of oxides and cement. (Soviet inventor certificate No. 926024, C21C1106, issued in 1982) . The above alloying materials require longer alloying process times and production of vanadium-containing products. Disadvantageously, its rate of dissolution in the metal is low due to its reduced capacity.

Therefore, effective vanadium-containing materials used to alloy metals with vanadium The problem arises of finding out.

Disclosure of invention The purpose of the present invention is to reduce the time of the alloying process and to reduce the alloying process without deteriorating the properties. Alloying vanadium with metals that improve the production capacity of dium-containing products It's about finding the material.

The above purpose is to provide a particulate material containing metal components for alloying metals. According to the invention, the metal component has the following composition (mass percentage): Silicon oxide 10-24 Vanadium oxide 14-25 Manganese oxide 4-14 Titanium oxide 3~1° Chromium oxide 1-4 Calcium oxide or magnesium oxide 3-5° iron oxide balance It is covered with a shell consisting of slag components, and the ratio of metal components to slag components is (in mass percentage) Metal component 5-95 Slag component 95~5 This is achieved by proposing the use of a material characterized by:

Composition below (!total percentage) Carbon 0. 5-3.5 Metal 0.01~0.05 Iron remainder (However, the metals are vanadium, manganese, and chromium). It is advantageous to use materials.

The particle size of the above material is 0. It is best to maintain it within the range of 5 to 30.0+a+s. preferable.

The proposed material for alloying metals with vanadium has the following advantages when compared to known materials: It has the following advantages.

High dissolution rate, The time to alloy the metal with vanadium is short, the extraction of vanadium into the metal is high, The cost of alloying the metal with vanadium is low.

The main and crucial advantage of the proposed material is that it is compatible with liquids such as cast iron or steel. The purpose is to quickly dissolve in metals.

A metallic material used as an alloying agent immersed in the less agitated bottom of a liquid bath (ferroalloy, alloy composition) is completely dissolved in the metal over a sufficient period of time. and known slag-metal materials (the porosity of the iron being reduced is highly developed). (higher than 50%) as opposed to being completely on the metal surface. The material is immersed up to 80-90% of its volume and is therefore particularly suitable for decarburization or other Actively stirred with a circulating metal flow upon perturbation of the surface of the genus. In this case, the fire resistance is extremely The slag component, which is extremely high and strongly fixed to the metal component, is "encapsulated". The metal components are not destroyed by the carbon oxides formed. An explosion of materials like this The solution increases the reactive surface for interaction between the alloy material and the liquid metal, thus increasing the dissolution rate of the material. degree increases significantly. “Capturing” of metal components by refractory and chemically stable slag shell The positive effects of ``cellization'' are primarily achieved within a predetermined range of granularity. particles If the diameter is less than 0.5 mm (average diameter), the thickness of the slag shell is insufficient. Therefore, the above effect becomes weaker. Even when the diameter of the particles exceeds 3060 mm, the "capsule" The oxidation effect decreases, which is due to the large deformation (or decomposition) of the slag shell and the metal components. This is thought to be due to the early release of carbon oxides.

The oxides that enter the composition of the slag component from the particles have a dual role. on the other hand , for example, oxides of iron and silicon form the silicic acid component, and iron oxide and vanadium oxide Promotes the reduction of dium. On the other hand, the silicic acid component is vanadium oxide and titanium oxide. and is highly sorbed to chromium oxide, which forms spinelides, especially with iron oxides. At the same time, due to the presence of manganese oxide, the silicate component becomes metal. Proper wetting of the components facilitates the formation of a stable slag shell of the alloy material.

The proposed alloy material can be used as described above if the concentration limits of the components are within the desired range. It has a very positive effect.

The content of silicon oxide is less than 10% and the content of vanadium oxide is less than 14%. During this process, the slag shell becomes soft and decomposes quickly. A similar phenomenon occurs with silicon oxide. Also when the content of elemental element is higher than 24% and the content of vanadium oxide is higher than 25% be observed.

When the content of manganese oxide is 4 to 14% in the above range, the metal component of the slag shell complete wetting is easy, but the content of manganese oxide is less than 4% or more than 14% When it's high, there's a lot less wetness. Titanium oxide (3-10%) and slag shell The presence of chromium vanadium oxide (1-4%) leads to the formation of complex iron-vanadium dissolved in the silicic acid component. Umu's Spinelid is strengthened. Calcium oxide or magnesium oxide above Iron oxides and silicic acid oxides are also present in amounts of 3-50%; The silicic acid component of has a high sorption ability for the complex iron-vanadium subinelide. This promotes the formation of chemically stable silicic acid components.

The ratio of metal to slag components in the proposed material allows metals to be alloyed with vanadium. A young cow is confirmed. The minimum particle size (0.5-1 mm) corresponds to an increasing content of metal components. C70-95%), and for larger grain sizes (20-30 dragons), the alloy material is 5-20% Advantageously, it includes a metallic component. Mutually soluble mineralization enters the composition of the material The compound-forming oxides create a strong and chemically stable slag shell on the surface of the particles. to prevent premature decomposition of the particles.

The slag shell and the metal components encapsulated in the shell are two components that are separated during the material formation process. The formation of a zone on the surface layer of the slag components that binds the components of the slag creates a strong bond. will be combined. In this case, the thickness is large and "difficult to separate". Usually a slag - In contrast to "burn-on" formation on metallic materials, this The transition layer contains large amounts of vanadium oxide and titanium oxide in addition to silicon and iron oxides. , giving rise to a soluble layer in the iron silicate. The content of carbon in the transition layer is relatively low ( 0.1 to 0.5%), the bond between the slag and the metal component is also strong.

The metallic iron with dissolved carbon inside the particles is shielded from the environment by the slag shell. This prevents oxidation of the iron during heating and melting, which also reduces the melting time. Decrease. The maximum dissolution rate is achieved through a range of concentrations of metallic iron.The slag shell of the material is May contain aluminum oxide and phosphorus oxide (total amount 3-5%), which are In a given material, it is an impurity and is introduced along with the additive used to introduce the main component. be able to. The above oxides, in the above amounts, do not adversely affect the dissolution rate of the material. stomach.

The above alloy material is prepared by the following method. Vanadium produced in oxygen converter Crush the rug to determine its size.

After dividing the vanadium slag into a 0.5~30° part, the magnetic part of this vanadium slag is subjected to magnetic separation. Therefore, it is separated from the non-magnetic fraction.

The particle size coated with slag shell is 0. Particle size of generation material of 5 to 30 dragons It is therefore separated and used to alloy cast irons, steels and alloys.

BEST MODE FOR CARRYING OUT THE INVENTION B. Vanadium-containing steel and cast iron as a loading material containing waste products of steel and cast iron. The material is melted in an electric arc furnace with a basic or acidic lining. Alloy material The material has the following composition (mass percentage): silicon oxide 15-20, barium oxide. Nadium 16-20, manganese oxide 6-8, titanium oxide 3-6, chromium oxide 1-1 3. Calcium oxide or magnesium 25-40% and the balance is iron oxide 80-95% vanadium slag, and the following composition (mass percentage): carbon 0.5-2.0, vanadium 0.01-0.05 and the balance iron. Using a granular material with a particle size of 15 to 30 fins coated with a shell containing 5 to 20% Ru. A loading of this material in an amount that meets the minimum concentration limit for vanadium in the final metal. Put it in the furnace with the ingredients. Completely melts the charging material and forms lime or acid slag After heating the metal, the slag is deoxidized using coke and ferrosilicon. Vanadium is then introduced in the same amount as calculated for the average content in the final material. The metal is further alloyed with vanadium by the materials mentioned above that can be incorporated.

and the above materials such as strength, yield, impact strength, hardness, rigidity and relative wear resistance. By studying the working properties of alloyed metals, by using alloy materials. , steel and cast iron castings alloyed with alloy materials known for their reliability and durability. 10-30% improvement compared to that, and the cost of alloying with vanadium is 50-100% It can be seen that this decreases. The absorption of vanadium by metals from alloys of materials is 85 ~ It is 88%.

mouth, steel or cast iron, with a slag content of 5-30% and a metal content of 70-95% (The composition of each component is the same as the composition described in method A) Particles with a particle size of 15 to 30 A similar slag-metal material is melted in an electric arc furnace. Bananajiu (100%) is introduced into the metal along with the material during loading or at the beginning of the oxidation process. If melting is carried out without removing the slag, 85-87% of the vanadium added to the furnace will become gold. The reliability and durability of the metal improves by 20-30%. alloy material The cost of production is 50-100% compared to alloying the metal with known ferric alloys. Reduced.

C. An alloy containing 35-45% vanadium and 1-25% silicon in an electric arc furnace. melt. 82% vanadium pentoxide, lime, ferrosilicon and aluminum A granular alloy material with a particle size of about 15 to 30 is introduced into the charge material containing the material. Alloy material The material has the following composition (mass percentage): silicon oxide 14 to 18, vanadium oxide Mu16-20, Manganese oxide 6-8, Titanium oxide 6-10, Chromium oxide 1-3, Calcium oxide and/or magnesium 30-50% with the balance being iron oxide A certain slag component 70-95% and the following composition (mass percentage), i.e. carbon 0.5 ~1,2, metal component 5-3 having 0.01-0.05 vanadium and the balance being iron It has 0%.

The assimilation of vanadium by the metal of the proposed alloy rice husk is 95.4%.

To further understand the invention, for alloying steel, cast iron and alloys with vanadium A specific example using a vanadium-containing alloy material will be shown below.

Example 1 Carbon steel containing chromium and vanadium is remelted in an industrial electric arc furnace. It melted. 80% waste products of chromium-containing steel, 2.6% carbon, 0.0 phosphorus Carbon containing 4%, 0.023% sulfur and 0.06% vanadium, balance iron A charging material with 20% semi-finished products was used. 5% lime and 2-3% crushed chamotte introduced into the charge material. After melting this charge material, it is in the form of granules with a particle size of 0.5+am. The alloy material contains (in mass percentage) 0.57-0.62 carbon, 0.018-0 phosphorus ．． 021, 1520-1 on the surface of metal containing vanadium 0.015-0.020 Added at 540°C. The metal components of the alloy material are (in mass percentage) carbon2o4, vanadium Containing 0.03 chromium, 0.03 chromium, and 0.04 manganese, the balance is iron, and the particles The slag component collected in an amount of 95% of the weight of (in mass percentage) silicon oxide 10 , vanadium oxide 25, manganese oxide 14, titanium oxide 10, chromium oxide 4, acid It contained 3 calcium oxides, and the remainder was iron oxide. This alloy material is used in the final steel. Average vanadium content! (0.12%). Take a bath for a short time (10~ After ``overboiling'' (for 15 minutes), the slag is treated with ferrosilicon (2-5 kg/1). I understood. The assimilation of vanadium is 88.4% and the relative wear resistance of the prepared steel compared to the same steel alloyed with ferrovanadium] and the alloy cost 80 reduced by %.

Example 2 Carbon steel containing chromium and vanadium is remelted in an industrial electric arc furnace. It melted. 70% waste products of chromium-containing steel, 2.5% carbon, 0.0 phosphorus 3%, 0.021% sulfur and 0.05% vanadium, balance iron. Using a charge with 20% semi-finished products and a charge with 10% steel scrap . Lime (4°5%) and ground chamotte (2%) were also introduced into the charge. loading After melting the material, the alloy material in granular form with a grain size of 10 to 20 μm (in mass percentage) Contains 0.54 carbon, 0.017 phosphorus, 0.019 sulfur and 0.02 vanadium. It was added to the surface of the metal at 1550°C. The metal component of the alloy material is (in mass percentage) carbon Contains 3.2 elements, 0.03 vanadium, 0.03 chromium, 0.05 manganese, and the remainder is iron, and the slag components collected in an amount of 5% of the particle weight (in mass percentage) are Silicon oxide 18, vanadium oxide 14, manganese oxide 4, titanium oxide 3, chromium oxide It contained 1% of calcium oxide, 50% of calcium oxide, and the remainder was iron oxide. This alloy material is final It was used in an amount such that the average vanadium content in the steel was 0.12%. Take a bath for 15~ After "overboiling" for 20 minutes, the slag was treated with ground ferrosilicon.

The vanadium assimilation is 87.2% and the relative wear resistance of the final steel is ferrovanadium. 14% improvement over the same steel alloyed with dium, and alloying cost reduced by 120% .

Example 3 Carbon steel containing chromium and vanadium is remelted in an industrial electric arc furnace. It melted. 75% waste products of chromium-containing steel, 2.7% carbon, 0.0 phosphorus 4%, 25% carbon semi-finished product containing 0.020% sulfur and 0.05% vanadium. A loading material with Loaded with lime (5%) and crushed chamotte (2,5%) It was introduced into the filling material. After melting the charge material, the alloy material in granular form with a grain size of 3 m11 is , carbon (in mass percentage) 0.51. Phosphorus 0.020, Sulfur 0.018 and Banana It was added to the surface of a metal containing 0.02 dium at 1570°C. The metal components of alloy materials are (in mass percentage) 2.9 carbon, 0.04 vanadium, 0.02 chromium, manganese 0.02, the remainder is iron, and the slag composition was collected in an amount of 85% of the particle weight. (in mass percentage) 24 silicon oxides, 18 vanadium oxides, 6 manganese oxides, Contains 6 titanium oxide, 3 chromium oxide, and 24 calcium oxide, with the remainder being iron oxide. It was. The average vanadium content of this alloy material in the final steel is 0.12%. Use in quantity. After "overboiling" the bath for 10 to 15 minutes, the slag is ground into ferro. Treated with silicone.

The vanadium assimilation is 87% and the relative wear resistance of the final steel is ferrovanadium. 16% improvement over the same steel alloyed with aluminum, and the cost of the alloy was reduced by 80%.

Example 4 Inductive roll cast iron alloyed with 0.5% vanadium with acid lining Melted in an oven. The charging materials are pig iron (60%) and roll cast iron scrap (4 0%). The metal was heated to 1500-1520°C. Granular and grain size 10 to 15 alloy materials in an amount such that the average content of vanadium is 0.45% was introduced little by little onto the cast iron surface. The iron content of the alloy material (in mass percentage) is 3. 1. Contains 0.03% vanadium, traces of chromium, traces of manganese, the remainder is iron oxide , and the slag components collected in an amount of 90% of the particle weight are oxidized (in mass percentage) Silicon 18, Vanadium oxide 18, Manganese oxide 6, Titanium oxide 6, Chromium oxide 3. Contained 30% of calcium oxide, and the remainder was iron oxide.

The slag was deoxidized with ferrosilicon and held for 10 minutes before tapping the metal.

The assimilation of vanadium reached 86.2%, and the roll alloyed with vanadium of the above material The wear resistance of the roll is 20% higher than that of a roll alloyed with vanadium. The cost of alloying with aluminum has been reduced by 80%.

Example 5 An alloy containing 35-45% vanadium and 5-25% silicon is melted in an electric arc furnace. Ta. Add the above alloying material in an amount of 20% (with respect to the vanadium charge material) to barium pentoxide. It was introduced into the charging material along with sodium, lime, ferrosilicon and silicon. this After introducing the material to the bottom of the furnace, the remaining charge material was fed. The metal components of alloy materials are traces of carbon 3.5, vanadium 0.05, chromium and manganese (in mass percentage) The slag component that is collected in an amount of 50% of the particle weight is contained in trace amounts and the remainder is iron. (in mass percentage) 14 silicon oxides, 20 vanadium oxides, 6 manganese oxides, Contains 4 titanium, 3 chromium oxide, 20 magnesium oxide, and 22 calcium oxide. The rest was iron.

The assimilation of vanadium by metal from the material amounted to 94.9%. Combining vanadium The cost of metallization is reduced by 40% compared to alloy solutions using only vanadium pentoxide. Ta.

Industrial applicability The present invention involves alloying cast iron, steel or alloys with vanadium and producing vanadium-containing products. It can be used in pyrometallurgical manufacturing to prepare products.

international search report

Claims (3)

[Claims] 1. A material for alloying particulate metal containing a metal component with vanadium, The metal component has the following composition (mass percentage) Silicon oxide 10-24 Vanadium oxide 14-25 Manganese oxide 4-14 Titanium oxide 3-10 Chromium oxide 1-4 Calcium oxide or magnesium oxide 3-50 iron oxide balance It is covered with a shell of slag components, The ratio of the metal component to the slag component (in mass percentage) is from 5 to 95. Remaining slag component A material characterized by: 2. The metal component has the following composition (mass percentage): carbon 0.5 to 3.5 Metal 0.01-0.05 iron residue (However, the metals are vanadium, manganese, and chromium.) Materials described in Section 1. 3. Claims 1 and 2, wherein the particle size is 0.5 to 30.0 mm. Materials listed.