CN114774612A - Method for vanadium-titanium ore gas-based shaft furnace reduction-electric furnace melting reduction - Google Patents
Method for vanadium-titanium ore gas-based shaft furnace reduction-electric furnace melting reduction Download PDFInfo
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- CN114774612A CN114774612A CN202210396685.0A CN202210396685A CN114774612A CN 114774612 A CN114774612 A CN 114774612A CN 202210396685 A CN202210396685 A CN 202210396685A CN 114774612 A CN114774612 A CN 114774612A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
Abstract
A method for vanadium-titanium ore gas-based shaft furnace reduction-electric furnace melting reduction belongs to the field of vanadium-titanium ore comprehensive utilization, and particularly relates to a method for vanadium-titanium ore gas-based shaft furnace reduction-electric furnace melting reduction. The vanadium-titanium pellet ore is reduced in a gas-based shaft furnace to obtain vanadium-titanium direct reduced iron; melting and reducing vanadium-titanium directly reduced iron in an electric furnace to obtain vanadium-containing molten iron and titanium slag, and is characterized in that reducing gas is blown into a molten layer in the electric furnace, the reducing gas reacts with vanadium and iron oxide to generate vanadium, iron metal liquid and titanium slag, and the vanadium and iron metal liquid enters the molten iron; the molten layer comprises a molten iron layer, a slag iron transition layer and a slag layer. The invention can reduce the power consumption of electric furnace smelting, improve the titanium slag grade, uniformly distribute carbon in high-carbon iron and have better reduction effect of vanadium and iron oxides.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of schreyerite, and particularly relates to a schreyerite gas-based shaft furnace reduction-electric furnace melting reduction method.
Background
The vanadium titano-magnetite resource reserves in China are huge, the overall development and utilization are mainly carried out by a blast furnace process, and the non-blast furnace method yield is low. The recycling rate of the whole titanium and vanadium is not high, and the resource waste is serious. In the prior art, a non-blast furnace method is superior to a blast furnace method, can realize smelting of all vanadium-titanium ore, and has higher recovery rates of iron, vanadium and titanium. The non-blast furnace smelting method adopts a pre-reduction (rotary kiln, rotary hearth furnace and gas-based shaft furnace) -electric furnace method, wherein the gas-based shaft furnace has the most development prospect due to large equipment yield and environment-friendly technology, and the specific process of the gas-based shaft furnace-electric furnace method is as follows: the vanadium-titanium magnetite concentrate is reduced, and the reduction product is added with coke, semi-coke or coal to be melted and deeply reduced and smelted in an electric furnace.
In the prior art, the gas-based shaft furnace reduction-electric furnace method mainly comprises patent application numbers CN201910859500.3, CN201210377607.2, CN201310216599.8, CN202010327329.4 and CN201310372684.3, and the patents mainly comprise vanadium titano-magnetite oxidized pellet preparation, gas-based shaft furnace reduction and electric furnace melting and separating parts. Among them, the electric furnace deep reduction of patent CN201910859500.3 is: and (3) loading the vanadium titano-magnetite pre-reduced pellets into an electric furnace for deep reduction, adding a flux and carbon, and separating to obtain vanadium-containing molten iron and titanium-containing slag, wherein the melting temperature is 1550-1650 ℃. The melting composition of the metallized pelletizing electric furnace of patent CN201310372684.3 is as follows: the method comprises the following steps of (1) loading metallized pellets into a melting electric furnace, wherein the melting temperature is 1600-1700 ℃, the carbon distribution amount is 2-6%, the slag alkalinity is 0.7-1.3, and the melting time is 50-70 min, discharging molten titanium slag through a slag outlet after smelting, and discharging vanadium-containing molten iron through an iron outlet; the disadvantages of the two patents mentioned above are: when the vanadium oxide is deeply reduced in the electric furnace, a carbon preparation method is adopted, which not only increases the power consumption, but also reduces the titanium slag grade. The patent CN201210377607.2 is that the reduced product is sent into an electric furnace to be melted and separated from slag iron, the melting temperature is 1500-1700 ℃, molten iron and slag are obtained, deep reduction is not carried out, vanadium and titanium enter the slag, and how to extract vanadium is not mentioned. In patent CN201310216599.8, the hot direct reduced iron is hot fed to a melting electric furnace for melting reduction, titanium slag is separated and vanadium-containing molten iron is obtained, and how to reduce vanadium oxide is not described. In the patent CN202010327329.4, vanadium slag is enriched in an electric furnace through 'slag remaining and tapping' n times, and after a certain amount of vanadium slag is reached, a flux and a reducing agent are added to carry out slag reduction operation, so that vanadium-rich molten iron and final slag are obtained. The process has the disadvantages that 1, along with the increase of the slag retention times, the capacity of the electric furnace is gradually reduced, and the yield of molten iron in a single furnace is gradually reduced; 2. electric furnaces are divided into an electric arc furnace and an ore-smelting furnace, and one electric furnace is unreasonable and can generate extremely high power consumption as a melting furnace and a reducing furnace.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for vanadium-titanium ore gas-based shaft furnace direct reduction-electric furnace melting reduction.
The method for direct reduction of the vanadium-titanium ore gas-based shaft furnace and electric furnace melting reduction is carried out according to the following steps:
reducing the vanadium-titanium pellet ore in a gas-based shaft furnace to obtain vanadium-titanium direct reduced iron; melting and reducing vanadium-titanium directly reduced iron in an electric furnace to obtain vanadium-containing molten iron and titanium slag, and is characterized in that reducing gas is blown into a molten layer in the electric furnace, the reducing gas reacts with vanadium and iron oxide to generate vanadium, iron metal liquid and titanium slag, and the vanadium and iron metal liquid enters the molten iron; the molten layer comprises a molten iron layer, a slag iron transition layer and a slag layer.
One of the purposes of the invention is to reduce the power consumption of electric furnace smelting.
The second purpose of the invention is to reduce the influence of the newly added materials on the grade of the titanium slag to the maximum extent.
Compared with the prior art, the method has the following beneficial effects:
1. reducing the power consumption of electric furnace smelting: the reducing gas brought by the reducing gas spray gun and the carbon brought by the high-carbon vanadium-titanium direct reduced iron are used as reducing agents of vanadium and iron oxide in the direct reduced iron, so that the gangue brought by coal serving as the reducing agents and the corresponding amount of the matched flux are avoided, and the power consumption consumed by melting the gangue and the flux is avoided;
2. improving the grade of the titanium slag: the reducing agent for directly reducing vanadium oxide in iron is pure carbonAnd/or H2And/or CO and/or CH4The vanadium-containing molten iron is not polluted, and the grade of titanium slag is not influenced;
3. the carbon in the high-carbon iron is uniformly distributed, and the reduction effect of the oxides of vanadium and iron is better;
4. CO reducing gas is introduced into the electric furnace, and when the CO reducing gas reacts with oxides of vanadium and iron, heat can be released, and the power consumption is further reduced.
Drawings
FIG. 1 is a schematic view of an electric furnace 1 in step two of experiment one;
FIG. 2 is a schematic illustration of a gas based shaft furnace 2 in step one of experiment one;
fig. 3 is a schematic view of the gas-based shaft furnace 2 in step one of experiment two.
Detailed Description
The first specific implementation way is as follows: the embodiment is a method for direct reduction of a vanadium-titanium ore gas-based shaft furnace and electric furnace melting reduction, which is specifically carried out according to the following steps:
reducing the vanadium-titanium pellet ore in a gas-based shaft furnace to obtain vanadium-titanium direct reduced iron; melting and reducing vanadium-titanium directly reduced iron in an electric furnace to obtain vanadium-containing molten iron and titanium slag, and is characterized in that reducing gas is blown into a molten layer in the electric furnace, the reducing gas reacts with vanadium and iron oxide to generate vanadium, iron metal liquid and titanium slag, and the vanadium and iron metal liquid enters the molten iron; the molten layer comprises a molten iron layer, a slag iron transition layer and a slag layer.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the electric furnace, reducing gas is blown from the slag iron transition layer. The rest is the same as the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the vanadium-titanium direct reduced iron is high-carbon direct reduced iron. The rest is the same as the first embodiment.
The fourth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the electric furnace adopts closed, continuous feeding, periodic slag tapping and periodic tapping operation. The rest is the same as the first embodiment.
The fifth concrete implementation mode: book blockThe first embodiment is different from the first embodiment in that: the reducing gas blown into the electric furnace is H2And/or CO and/or CH4. The rest is the same as the first embodiment.
The sixth specific implementation mode: the third difference between the present embodiment and the specific embodiment is that: the carbon content of the high-carbon direct reduced iron is more than 2.5 percent. The rest is the same as the third embodiment.
The seventh embodiment: the second difference between this embodiment and the second embodiment is that: the plurality of reducing gas passages are uniformly distributed on a slag iron transition layer of the electric furnace. The rest is the same as the second embodiment.
The specific implementation mode eight: the first difference between the present embodiment and the specific embodiment is: the gas-based shaft furnace adopts rich CH4The gas is raw material gas and adopts non-catalytic partial oxidation gas-making technology. The rest is the same as the first embodiment.
The specific implementation method nine: the fifth embodiment is different from the fifth embodiment in that: the reducing gas used by the electric furnace is CO gas. The rest is the same as the fifth embodiment.
The detailed implementation mode is ten: the seventh embodiment is different from the seventh embodiment in that: a reducing gas injection lance is inserted into the plurality of reducing gas passages. The rest is the same as the fifth embodiment.
The invention was verified with the following tests:
test one: the test is a method for vanadium-titanium ore gas-based shaft furnace direct reduction-electric furnace melting reduction, which is specifically carried out according to the following steps:
firstly, as shown in fig. 2, vanadium-titanium pellets are loaded from a charging port 25 at the top of a gas-based shaft furnace 2, reducing gas enters the gas-based shaft furnace 2 through a gas pipeline 23 at the reduction section of the gas-based shaft furnace, the vanadium-titanium pellets in the gas-based shaft furnace 2 react with the reducing gas entering through the gas pipeline 23 at the reduction section of the gas-based shaft furnace to be reduced into vanadium-titanium direct reduced iron, the vanadium-titanium direct reduced iron is discharged out of the furnace through a discharging device 26 at the lower part of the gas-based shaft furnace 2, and shaft furnace top gas generated by the reaction is discharged through a gas pipeline 24 at the top of the gas-based shaft furnace;
wherein the reducing gas entering through the gas pipeline 23 at the reducing section of the gas-based shaft furnace isThe effective component is CH4：7％、H2：52％、CO：27％、H2O+CO2: 13 percent of impurity gas, and the balance of impurity gas; blowing in CH-containing gas into the reduction zone 234The reducing gas can improve the carbon content of the vanadium-titanium direct reduced iron; in order to further improve the carbon content in the vanadium-titanium direct reduced iron, cooling gas (normal temperature, capable of cooling the reduced iron) is blown into the cooling section of the gas-based shaft furnace through a gas pipeline 21 of the cooling section of the gas-based shaft furnace, and the cooling gas is rich in CH4Blowing CO gas into a gas pipeline 22 at the transition section of the gas-based shaft furnace, and further reacting the gas with the vanadium-titanium direct reduced iron to further increase the carbon content of the vanadium-titanium direct reduced iron to 4%;
the reduction section is positioned in the middle of the gas-based shaft furnace 2 (a reduction section gas pipeline 23 is communicated with the lower part of the reduction section of the gas-based shaft furnace), the transition section is positioned below the reduction degree (a transition section gas pipeline 22 is communicated with the lower part of the transition section of the gas-based shaft furnace), and the cooling section is positioned below the transition section and above a discharge port 26 (a cooling section gas pipeline 21 is communicated with the lower part of the cooling section of the gas-based shaft furnace);
secondly, as shown in figure 1, continuously adding the obtained high-carbon vanadium-titanium direct reduced iron cold charge with the carbon content of 4% into the electric furnace 1 through a feeding pipe 17, gradually melting the direct reduced iron under the heating action of an electrode 18 in the electric furnace 1, and sequentially forming a solid furnace material smelting layer 15, a soft melting layer 14, a slag layer 13, a slag iron transition layer 12 and a liquid iron layer 11 from top to bottom; a plurality of reducing gas spray guns 121 are uniformly inserted into the slag iron transition layer 12, reducing gas reacts with vanadium and iron oxide in the slag iron transition layer 12 to generate vanadium and iron metal liquid and titanium slag, and the reducing gas continuously floats upwards to react with part of vanadium and iron oxide in the slag layer 13 and the soft melting layer 14 to generate vanadium and iron metal liquid and titanium slag. In the process that high-carbon direct reduced iron passes through the soft melting layer 14, the slag layer 13 and the slag iron transition layer 12, carbon in the high-carbon direct reduced iron with the carbon content of 4% reacts with vanadium and iron oxide to generate vanadium, iron metal liquid and titanium slag, and the vanadium and iron metal liquid enters molten iron; the vanadium-titanium direct reduction iron electric furnace adopts closed and continuous feeding, slag tapping at the slag outlet 131 at regular intervals and tapping at the tapping hole 111 at regular intervals, and aims to form a reducing atmosphere environment and improve the utilization rate of heat energy in the electric furnace. The reducing gas sprayed by the reducing gas spray gun 121 is CO gas, and the CO gas reduces the vanadium and the iron oxide into exothermic reaction, so that the reduction of power consumption is facilitated. The reducing gas spray guns 121 are uniformly distributed around the furnace body of the electric furnace 1, so that the reducing gas can uniformly enter the electric furnace 1 and fully contact with vanadium and iron oxide in the electric furnace 1, and the reducing effect is good; the 16 th in figure 1 is the top gas flue.
And (2) test II: the test is a method for direct reduction of a gas-based shaft furnace and melting reduction of an electric furnace, and is specifically carried out according to the following steps:
as shown in fig. 3, in contrast to the experiment one: in the first step, a cooling section is not arranged, the final product of the gas-based shaft furnace is high-carbon hot direct reduced iron, and the hot vanadium-titanium direct reduced iron is fed into an electric furnace 1; the raw material of the reducing gas entering through the gas base shaft furnace reducing section gas pipeline 23 is coke oven gas, the coke oven gas is heated to 1150 ℃ by adopting a non-catalytic partial oxidation process, and then is mixed with cold coke oven gas, so that CH in the reducing gas component entering through the gas base shaft furnace reducing section gas pipeline 234The amount reaches 13%. Room temperature CO gas is blown in through a gas pipeline 22 at the transition section of the gas-based shaft furnace, the carbon content of the directly reduced iron can be improved to more than 2.5 percent by the CO gas, and the heat is charged into the electric furnace 1. The rest is the same as test one.
Claims (10)
1. A vanadium-titanium ore gas-based shaft furnace direct reduction-electric furnace melting reduction method is characterized in that vanadium-titanium pellets are reduced in a gas-based shaft furnace to obtain vanadium-titanium direct reduced iron; melting and reducing vanadium-titanium directly reduced iron in an electric furnace to obtain vanadium-containing molten iron and titanium slag, and is characterized in that reducing gas is blown into a molten layer in the electric furnace, the reducing gas reacts with vanadium and iron oxide to generate vanadium, iron metal liquid and titanium slag, and the vanadium and iron metal liquid enters the molten iron; the molten layer comprises a molten iron layer, a slag iron transition layer and a slag layer.
2. The method of claim 1, wherein the reducing gas is blown into the electric furnace from a slag iron transition layer.
3. The method of claim 1, wherein the vanadium-titanium ore gas-based shaft furnace direct reduction-electric furnace melting reduction is high carbon direct reduced iron.
4. The method of claim 1, wherein the electric furnace is operated in a closed, continuous charging mode, periodic tapping and periodic tapping mode.
5. The method of claim 1, wherein the reducing gas blown into the electric furnace is H2And/or CO and/or CH4。
6. The method of claim 3, wherein the carbon content of the high-carbon direct reduced iron is more than 2.5%.
7. The method of claim 2, wherein the plurality of reducing gas passages are uniformly distributed in the transition layer of iron slag in the electric furnace.
8. The method of claim 1, wherein the gas-based shaft furnace is rich in CH and the electric furnace melting reduction method is used for the gas-based shaft furnace4The gas is raw material gas and adopts non-catalytic partial oxidation gas-making technology.
9. The method of claim 5, wherein the reducing gas used in the electric furnace is CO gas.
10. The method of claim 7, wherein a plurality of reducing gas lances are inserted into the plurality of reducing gas passages.
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| CN202210396685.0A CN114774612A (en) | 2022-04-15 | 2022-04-15 | Method for vanadium-titanium ore gas-based shaft furnace reduction-electric furnace melting reduction |
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| CN110484720A (en) * | 2019-09-11 | 2019-11-22 | 中南大学 | A kind of technique that drying grate roasting-gas-based shaft kiln prereduction-electric furnace restores comprehensive utilization of V-Ti magnetite deeply |
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2022
- 2022-04-15 CN CN202210396685.0A patent/CN114774612A/en active Pending
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