CN109778059B - Porous ferromolybdenum alloy and preparation method and application thereof - Google Patents
Porous ferromolybdenum alloy and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of iron alloy preparation, and mainly provides a porous ferromolybdenum alloy, a preparation method and an application thereof, wherein the porous ferromolybdenum alloy comprises, by mass, 40% -66% of molybdenum and 30% -56% of iron, and pores are distributed in the porous ferromolybdenum alloy, and the density of the porous ferromolybdenum alloy is 6.5-8.0 g/cm3. The ferromolybdenum alloy is obtained by reducing molybdenum concentrate, iron concentrate, a reducing agent, a pore-forming agent and a binder at a certain ratio at a high temperature by adopting a two-stage reduction and two-stage heat preservation method, and is applied to an electric arc furnace or a converter for steel smelting. The porous ferromolybdenum alloy prepared by the method has the characteristics of large porosity, looseness, porosity, density close to that of molten steel, and easiness in dissolving in the molten steel, so that the molybdenum yield of the alloy steel is improved, and the method has the characteristics of low smelting energy consumption and low smelting cost.
Description
Technical Field
The invention belongs to the field of iron alloy preparation, and mainly provides a porous ferromolybdenum alloy and a preparation method and application thereof.
Background
With the development of modern industry and the progress of science and technology, people put higher and higher requirements on the types and the service performance of metal materials. In order to improve and enhance the service performance of steel, some special elements are purposefully added in the smelting process, so that the smelted steel is expected to become alloy steel with various special service performances, and the smelting process is called as steel-making alloying. The use of molybdenum in the steel industry is still predominant for consumers, accounting for approximately 80%. Of these, cast iron and rolls are about 6%, tool steel and high speed steel are about 8%, stainless steel is about 23%, and alloy steel is about 43%. Molybdenum is used as an alloying element of the steel, and can improve the re-passivation capability of the steel, thereby improving the pitting corrosion resistance and the crevice corrosion resistance of the stainless steel, improving the high temperature resistance strength of the steel, greatly improving the high temperature durability and the creep deformation performance of the steel, enhancing the acid and alkali resistance and the wear resistance of the steel, improving the hardenability, the weldability and the like of the steel.
Currently, most alloy steel smelting enterprises realize the molybdenum alloying of steel or molten iron by adding a ferromolybdenum alloy into a smelting furnace in the process of smelting molybdenum-containing alloy steel. However, the existing ferro-molybdenum alloy has great defects, the ferro-molybdenum has great density, and the density of 60MoFe is about 9.0g/cm3And the molybdenum is added into molten steel and rapidly settles at the bottom of the furnace when the density is larger than that of molten iron, the homogenization time is longer, a small amount of ferromolybdenum can be accumulated at the bottom of the furnace, the segregation of molybdenum and the reduction of yield are caused, the utilization rate of ferromolybdenum is low, the consumption of smelting energy is large, and the smelting cost is high. Therefore, the development of the ferro-molybdenum alloy with better service performance has great significance.
Disclosure of Invention
The invention provides a porous ferromolybdenum alloy and a preparation method and application thereof, aiming at solving the problem of low ferromolybdenum alloy utilization rate caused by high density, low porosity, high specific gravity and the like in ferromolybdenum alloy steelmaking.
The technical scheme adopted by the invention is as follows:
the porous ferromolybdenum alloy comprises, by mass, 40% -66% of molybdenum, 30% -56% of iron and the balance of impurities; the porous ferromolybdenum alloy is provided with pores and has the density of 6.5-8.0 g/cm3。
Mixing molybdenum oxide, iron ore concentrate, a reducing agent, a pore-forming agent and a binder to form a mixed raw material, reducing the mixed raw material at 830-1300 ℃, and cooling to room temperature to obtain the porous ferromolybdenum alloy; wherein, the content of the pore-forming agent is 0.5 to 20 percent of the mass of the mixed raw material, the content of the binder is 1 to 4 percent of the mass of the mixed raw material, and the reducing agent is sufficient.
The mixed raw materials are subjected to two-stage reduction and two-stage heat preservation to synthesize the porous ferromolybdenum alloy.
The reduction process of the mixed raw materials is as follows:
when the temperature of the mixed raw materials is increased to 830-900 ℃, preserving the heat for 20-60 min; and after the heat preservation is finished, raising the temperature to 1170-1300 ℃, preserving the heat for 10-40 min, and then cooling to room temperature.
The molybdenum oxide is MoO3And MoO2The molybdenum content in the molybdenum oxide is more than 50 percent, and the iron grade in the iron ore concentrate is more than 50 percent.
The reducing agent is one or a mixture of more of coke powder, coal powder and graphite.
The pore-forming agent is one or a mixture of more of carboxymethyl cellulose CMC, starch and polyethylene glycol.
The binder is one or a mixture of bentonite, water glass, carboxymethyl cellulose CMC and starch.
The particle size of the mixed raw materials is less than 1.5 mm.
The application of the porous ferromolybdenum alloy is used for alloy steel smelting, and when the alloy steel is smelted, the massive porous ferromolybdenum alloy is added into a smelting furnace.
Compared with the prior art, the invention has the following beneficial effects:
the porous ferromolybdenum alloy comprises, by mass, 40% -66% of molybdenum, 30% -56% of iron and the balance of impurities, wherein pores are distributed in the porous ferromolybdenum alloy, and the density is 6.5-8.0 g/cm3(ii) a The density of the molybdenum-iron alloy is lower and close to that of molten steel, and loose and porous pores are easy to dissolve in the molten steel, can be fully utilized in the molten steel, reduce the bottom sinking phenomenon of the ferromolybdenum alloy, and have the characteristics of low energy consumption and low smelting cost in smelting, thereby improving the molybdenum yield in the alloy steel smelting process and reducing the segregation degree of molybdenum elements.
The method for preparing the porous ferromolybdenum alloy disclosed by the invention starts from ferromolybdenum alloy steelmaking, and prepares a porous ferromolybdenum alloy, the performance of the porous ferromolybdenum alloy is superior to that of a conventional ferromolybdenum alloy, the ferromolybdenum alloy is obtained by smelting molybdenum oxide, iron ore concentrate, a reducing agent, a pore-forming agent and a binder at a high temperature according to a certain proportion, and the obtained ferromolybdenum alloy is stable and has a small particle size; the preparation method is simple, and the prepared porous ferromolybdenum alloy has the characteristics of large porosity, looseness, porosity and low density, is easy to dissolve in molten steel, can be fully utilized in the molten steel, reduces the bottom sinking phenomenon of the ferromolybdenum alloy, and has the characteristics of low energy consumption and low smelting cost.
Furthermore, the invention adopts a two-stage reduction and two-stage heat preservation method to reduce the mixed raw materials, and the reduction at lower temperature mainly generates MoO3Generation of MoO2Reaction of (1), reduction at higher temperature mainly occurs MoO2The reduction method can obtain the stable ferromolybdenum alloy with smaller grain diameter, and can be applied to an electric arc furnace or a converter for steel production.
The porous ferromolybdenum alloy is used for alloy steel smelting, when the alloy steel is smelted, the blocky porous ferromolybdenum alloy is added into a smelting furnace, because the porous ferromolybdenum alloy has low density and density close to that of molten steel, bottom sinking can not be directly and quickly caused, and because the porous ferromolybdenum alloy is porous, the loose and porous structure of the porous ferromolybdenum alloy is favorable for being dissolved in the molten steel, so that the molybdenum yield in the alloy steel smelting process is improved, and the segregation degree of molybdenum elements is reduced.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The process for preparing the porous ferromolybdenum alloy in the embodiment is as follows:
in the synthesis raw materials: the content of molybdenum concentrate (trademark YMo52.0-A) with the molybdenum grade of 52 percent accounts for 33.58 percent of the total mass of the synthetic raw materials, the content of iron concentrate (grade No. H55) with the iron grade of 55 percent accounts for 43.74 percent of the total mass of the synthetic raw materials, the content of reducing agent (coke powder) accounts for 13.32 percent of the total mass of the synthetic raw materials, the content of pore-forming agent (polyethylene glycol) accounts for 5.43 percent of the total mass of the synthetic raw materials, and the content of binder (water glass) accounts for 3.93 percent of the total mass of the synthetic raw materials; the granularity of the synthetic raw material is required to be controlled below 1.5 mm. And adding the raw materials into a metallurgical furnace for reduction, continuing heating for reduction when the temperature is increased to 850 ℃ and preserving heat for 30min, and preserving heat for 20min when the reduction temperature is increased to 1170 ℃, and cooling to room temperature to obtain the porous ferromolybdenum alloy. The porous ferromolybdenum alloy prepared in the embodiment comprises the following chemical components in percentage by weight: the content of molybdenum is 40.5%, the content of iron is 55.8%, and the balance is impurities.
The detection shows that the ferro-molybdenum alloy has a grade of 40.5%, pores are distributed, and the density is 7.5g/cm3。
Example 2
The process for preparing the porous ferromolybdenum alloy in the embodiment is as follows;
in the synthesis raw materials: the content of molybdenum oxide powder (trade name YMo55.0-A) with the molybdenum grade of 55 percent accounts for 37.78 percent of the total mass of the synthetic raw materials, the content of iron ore concentrate (grade name H59) with the iron grade of 59 percent accounts for 37.37 percent of the total mass of the synthetic raw materials, the content of reducing agent (coal powder) accounts for 13.65 percent of the total mass of the synthetic raw materials, the content of pore-forming agent (mixture of carboxymethyl cellulose CMC and polyethylene glycol) accounts for 10.71 percent of the total mass of the synthetic raw materials, and the content of binder (starch) accounts for 0.49 percent of the total mass of the synthetic raw materials; the particle size of the synthetic raw material is required to be controlled below 1.500 mm. And adding the raw materials into an electric furnace for reduction, continuing heating for reduction after the temperature is raised to 830 ℃, preserving the heat for 45min, raising the reduction temperature to 1200 ℃, preserving the heat for 30min, and cooling to room temperature to obtain the porous ferromolybdenum alloy. The porous ferromolybdenum alloy prepared in the embodiment comprises the following chemical components in percentage by weight: the content of molybdenum is 47.7%, the content of iron is 50.6%, and the balance is impurities.
Through detection, the ferro-molybdenum alloy has a grade of 47.7%, pores are distributed, and the density is 6.9g/cm3。
Example 3
The process for preparing the porous ferromolybdenum alloy in the embodiment is as follows;
in the synthesis raw materials: the content of molybdenum concentrate (trade name YMo55.0-B) with the molybdenum grade of 55.0 percent is 40.89 percent of the total mass of the synthetic raw materials, the content of iron concentrate (grade number C63) with the iron grade of 63 percent is 25.93 percent of the total mass of the synthetic raw materials, the content of reducing agent (mixture of coke powder and coal powder) is 13.14 percent of the total mass of the synthetic raw materials, the content of pore-forming agent (carboxymethyl cellulose CMC) is 18.08 percent of the total mass of the synthetic raw materials, and the content of binder (carboxymethyl cellulose CMC) is 1.96 percent of the total mass of the synthetic raw materials; the particle size of the synthetic raw material is required to be controlled below 1.500 mm. And adding the raw materials into an electric furnace for reduction, continuing heating for reduction when the temperature is increased to 870 ℃, preserving heat for 50min, continuing heating for reduction when the reduction temperature is increased to 1260 ℃, preserving heat for 30min, and cooling to room temperature to obtain the porous ferromolybdenum alloy. The porous ferromolybdenum alloy prepared in the embodiment comprises the following chemical components in percentage by weight: the content of molybdenum is 57.3%, the content of iron is 41.6%, and the balance is impurities.
Through detection, the ferro-molybdenum alloy has a grade of 57.3%, pores are distributed, and the density is 7.2g/cm3。
Example 4
The process for preparing the porous ferromolybdenum alloy in the embodiment is as follows;
in the synthesis raw materials: the content of molybdenum concentrate (trade name YMo55.0-A) with the molybdenum grade of 55.0 percent is 44.56 percent of the total mass of the synthetic raw materials, the content of iron concentrate (grade number H62) with the iron grade of 62 percent is 18.32 percent of the total mass of the synthetic raw materials, the content of reducing agent (mixture of coke powder, coal powder and graphite) is 13.21 percent of the total mass of the synthetic raw materials, the content of pore-forming agent (polyethylene glycol) is 22.17 percent, the content of binder (bentonite) is 1.74 percent of the total mass of the synthetic raw materials, and the granularity of the synthetic raw materials is required to be controlled to be less than 1.500 mm. And adding the raw materials into an electric furnace for reduction, continuing heating for reduction after the temperature is increased to 900 ℃ and preserving heat for 60min, and cooling to room temperature to obtain the porous ferromolybdenum alloy after the reduction temperature is increased to 1300 ℃ and preserving heat for 40 min. The porous ferromolybdenum alloy prepared in the embodiment comprises the following chemical components in percentage by weight: the content of molybdenum is 65.6%, the content of iron is 30.4%, and the balance is impurities.
Through detection, the ferro-molybdenum alloy has a grade of 65.6%, pores are distributed, and the density is 7.5g/cm3。
Claims (8)
1. The preparation method of the porous ferromolybdenum alloy is characterized by comprising the following steps: mixing molybdenum oxide, iron ore concentrate, a reducing agent, a pore-forming agent and a binder to form a mixed raw material, reducing the mixed raw material at the temperature of 830-1300 ℃, and then cooling to room temperature to obtain the porous ferromolybdenum alloy; wherein, the content of the pore-forming agent is 0.5 to 20 percent of the mass of the mixed raw material, the content of the binder is 1 to 4 percent of the mass of the mixed raw material, and the reducing agent is sufficient;
the mixed raw materials are subjected to two-stage reduction and two-stage heat preservation to synthesize porous ferro-molybdenum alloy;
the reduction process of the mixed raw materials is as follows:
when the temperature of the mixed raw materials is increased to 830-900 ℃, preserving the heat for 20-60 min; after the heat preservation is finished, raising the temperature to 1170-1300 ℃, preserving the heat for 10-40 min, and then cooling to room temperature;
the content of molybdenum in the porous ferromolybdenum alloy is 40-66%, the content of iron is 30-56%, and the balance is impurities; the porous ferromolybdenum alloy is provided with pores and has the density of 6.5-8.0 g/cm3。
2. The method of claim 1, wherein the molybdenum oxide is MoO3And MoO2The molybdenum content in the molybdenum oxide is more than 50 percent, and the iron grade in the iron ore concentrate is more than 50 percent.
3. The method for preparing the porous ferromolybdenum alloy according to claim 1, wherein the reducing agent is one or a mixture of several of coke powder, coal powder and graphite.
4. The method for preparing the porous ferromolybdenum alloy according to claim 1, wherein the pore-forming agent is one or a mixture of several of carboxymethyl cellulose CMC, starch and polyethylene glycol.
5. The method for preparing a porous ferromolybdenum alloy as claimed in claim 1, wherein the binder is one or more selected from bentonite, water glass, carboxymethyl cellulose CMC and starch.
6. The method of claim 1, wherein the mixed raw material has a grain size of less than 1.5 mm.
7. A porous ferromolybdenum alloy obtained by the method of any one of claims 1 to 6.
8. The use of the porous ferromolybdenum alloy as claimed in claim 7 wherein said porous ferromolybdenum alloy is used in alloy steel smelting, and bulk pieces of said porous ferromolybdenum alloy are added to a smelting furnace during alloy steel smelting.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3865573A (en) * | 1973-05-23 | 1975-02-11 | Kennecott Copper Corp | Molybdenum and ferromolybdenum production |
| US3907554A (en) * | 1973-06-15 | 1975-09-23 | Kenneth Joseph Boaden | Additive for steel baths |
| JPH04371501A (en) * | 1991-06-21 | 1992-12-24 | Kawasaki Steel Corp | Iron-based powder mixture for powder metallurgy |
| DE19622097A1 (en) * | 1996-06-01 | 1997-12-04 | Treibacher Ind Ag | Iron@-molybdenum@ alloy |
| CN1433483A (en) * | 2000-02-04 | 2003-07-30 | 特莱巴赫工业有限公司 | Porous agglomerates containning iron and at least one further element from groups 5 or 6 of the periodic table for use as alloying agent |
| CN104053799A (en) * | 2011-11-25 | 2014-09-17 | 法罗雷格林加股份公司 | Iron and molybdenum containing pellets |
| US9540707B2 (en) * | 2011-11-25 | 2017-01-10 | Ab Ferrolegeringar | Iron and molybdenum containing agglomerates |
| CN107326256A (en) * | 2017-06-13 | 2017-11-07 | 东北大学 | The method for preparing ferro-molybdenum with wash heat refining is reduced based on aluminothermy self- propagating gradient |
-
2019
- 2019-01-21 CN CN201910055235.3A patent/CN109778059B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3865573A (en) * | 1973-05-23 | 1975-02-11 | Kennecott Copper Corp | Molybdenum and ferromolybdenum production |
| US3907554A (en) * | 1973-06-15 | 1975-09-23 | Kenneth Joseph Boaden | Additive for steel baths |
| JPH04371501A (en) * | 1991-06-21 | 1992-12-24 | Kawasaki Steel Corp | Iron-based powder mixture for powder metallurgy |
| DE19622097A1 (en) * | 1996-06-01 | 1997-12-04 | Treibacher Ind Ag | Iron@-molybdenum@ alloy |
| CN1433483A (en) * | 2000-02-04 | 2003-07-30 | 特莱巴赫工业有限公司 | Porous agglomerates containning iron and at least one further element from groups 5 or 6 of the periodic table for use as alloying agent |
| CN104053799A (en) * | 2011-11-25 | 2014-09-17 | 法罗雷格林加股份公司 | Iron and molybdenum containing pellets |
| US9540707B2 (en) * | 2011-11-25 | 2017-01-10 | Ab Ferrolegeringar | Iron and molybdenum containing agglomerates |
| CN107326256A (en) * | 2017-06-13 | 2017-11-07 | 东北大学 | The method for preparing ferro-molybdenum with wash heat refining is reduced based on aluminothermy self- propagating gradient |
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