WO2026001945A1 - 一种氧气高炉冶炼高比例钒钛铁矿的方法 - Google Patents

一种氧气高炉冶炼高比例钒钛铁矿的方法

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Publication number
WO2026001945A1
WO2026001945A1 PCT/CN2025/102992 CN2025102992W WO2026001945A1 WO 2026001945 A1 WO2026001945 A1 WO 2026001945A1 CN 2025102992 W CN2025102992 W CN 2025102992W WO 2026001945 A1 WO2026001945 A1 WO 2026001945A1
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WIPO (PCT)
Prior art keywords
blast furnace
vanadium
iron
gas
titanium
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Pending
Application number
PCT/CN2025/102992
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English (en)
French (fr)
Inventor
黄云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pangang Group Xichang Steel and Vanadium Co Ltd
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Pangang Group Xichang Steel and Vanadium Co Ltd
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Application filed by Pangang Group Xichang Steel and Vanadium Co Ltd filed Critical Pangang Group Xichang Steel and Vanadium Co Ltd
Priority to EP25817723.7A priority Critical patent/EP4715068A1/en
Publication of WO2026001945A1 publication Critical patent/WO2026001945A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/04—Making slag of special composition
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/06—Making pig-iron in the blast furnace using top gas in the blast furnace process
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2

Definitions

  • This invention relates to the field of metallurgical technology, specifically to a method for smelting high-proportion vanadium-titanium iron ore in an oxygen blast furnace.
  • Blast furnace ironmaking process The technology is mature and can achieve an annual production capacity of more than one million tons per unit.
  • its disadvantages are that it relies too much on high-quality metallurgical coke and requires the construction of coking, sintering and pelletizing facilities, resulting in large system investment; the blast furnace is difficult to operate and difficult to recover after abnormal furnace conditions and fluctuations; the cost, carbon emissions and energy consumption are high; at the same time, the N2 content in the traditional blast furnace accounts for more than 40% of the total gas phase, which is very easy to generate Ti(C,N), forming foamy slag in the furnace, which is not conducive to smooth production and index optimization.
  • Vanadium-titanium magnetite is a complex mineral containing multiple metal elements, primarily iron, vanadium, and titanium, forming a symbiotic magnetic iron ore. It is the world's most important raw material for vanadium production and a key mineral for refining Ti and Fe. However, vanadium-titanium magnetite is also recognized globally as one of the most difficult minerals to smelt, making its comprehensive utilization challenging.
  • the proportion of vanadium-titanium ore in blast furnaces is the ratio of the amount of vanadium-titanium ore in the iron-containing raw materials used to produce sinter and pellets to the sum of the total amount of iron-containing raw materials used to produce sinter and pellets and the amount of iron-containing lumps used in the blast furnace
  • the content of blast furnace slag TiO2
  • Ti(C,N), TiC, and TiN are generated, resulting in slag viscosity, difficulty in separating slag and iron, and foamy slag.
  • the process involves high carbon emissions and high energy consumption.
  • CO accounts for about 20-30% of the blast furnace top gas.
  • the chemical energy of this part of CO cannot be effectively utilized in the current technology, but is instead used for power generation through combustion.
  • the thermal energy conversion efficiency of blast furnace gas combustion power generation is less than 40%. Therefore, the system has high energy consumption and high carbon emissions.
  • the purpose of this invention is to provide a method for smelting high-proportion vanadium-titanium iron ore in an oxygen blast furnace, which solves the technical problems in the prior art of blast furnace smelting of vanadium-titanium iron ore, such as the difficulty in increasing the proportion of vanadium-titanium iron ore and the high carbon emissions and high costs of the process.
  • one embodiment of the present invention provides a method for smelting high-proportion vanadium-titanium iron ore in an oxygen blast furnace, comprising the following steps:
  • the blast furnace uses pure oxygen injection, with pure oxygen, hot coal gas, and pulverized coal injected into the tuyeres; iron and coke are added from the top of the furnace; the volume percentage of N2 in the top gas is less than 25%; the top gas is recycled after CO2 removal.
  • the iron material is in the form of pellets or the iron material is in the form of pellets and at least one of the following materials: sinter and lump ore;
  • the TiO2 content in the pellets is 3%-13%, and the iron raw material used to produce the pellets is vanadium-titanium iron ore.
  • the proportion of pellets in the blast furnace feed is >30%; the TiO2 content in the sinter is ⁇ 5%.
  • the blast furnace slag produced by smelting has a TiO2 mass fraction of >15% and ⁇ 45%, a vanadium-titanium iron ore ratio of >60%, and a blast furnace CO2 emission reduction of 30%.
  • the hot gas is gas heated by a gas heater.
  • the gas sources in the gas heater include coke oven gas, steam, and purified gas.
  • the flow rate of coke oven gas fed into the gas heater is 20 Nm3 /t to 200 Nm3 /t, and the molar ratio of steam to coke oven gas fed into the heater is 0.10 to 0.30:1.
  • the mass ratio of blast furnace iron charge to coke is 5.5-7.5:1, and the mass ratio of blast furnace iron charge to pulverized coal is 15-40:1; the blast furnace fuel ratio is ⁇ 400kg/t and the coke ratio is ⁇ 300kg/t during blast furnace smelting.
  • the distribution coefficient of vanadium in molten iron and slag during blast furnace smelting is [V]/( V2O5 ) > 1.1.
  • the flow rate of injected hot coal gas is 700 Nm3 /t-1280 Nm3 /t, and the flow rate of injected pure oxygen is 145 Nm3 /t-245 Nm3 /t.
  • the charging method for iron and coke is as follows: at the height of the blast furnace charge surface, a horizontal blast furnace cross-section is taken, and the circle containing the cross-section is divided into 11 equal-area rings. The rings are numbered sequentially from the inner ring to the outer ring.
  • the charging system is as follows: 60%-80% of the coke is distributed in rings 9-11 and 1-5, 20%-40% of the coke is distributed in rings 6-8, 70%-90% of the iron is distributed in rings 4-10, and 10%-30% of the iron is distributed in rings 1-3 and 11.
  • This invention solves the problems of viscous and foamy slag in vanadium-titanium iron ore smelting.
  • the volume percentage of N2 in the furnace top gas in the smelting method of this invention is less than 25%, significantly lower than the 45%-60% volume percentage of N2 in traditional blast furnace gas.
  • the smelting process of this invention features reduced N2 partial pressure, increased CO partial pressure, and reasonable furnace temperature control, all of which effectively inhibit Ti(C,N) formation, preventing slag-iron viscous slag and difficulty in slag-iron separation from the source, controlling foamy slag, and thus solving one of the problems affecting the increase of the proportion of vanadium-titanium iron ore in blast furnaces.
  • This invention solves the problem of poor metallurgical performance of vanadium-titanium sinter.
  • this invention solves a series of technical problems such as reduced drum strength, high reduction pulverization, and high return ore rate in vanadium-titanium sinter, leading to poor blast furnace operation, irregular furnace conditions, and increased fuel costs per ton of sintered iron.
  • it solves another problem affecting the increase of the proportion of vanadium-titanium iron ore in the blast furnace.
  • the invention significantly reduces ore blending costs.
  • the invention achieves a vanadium-titanium iron ore ratio of 60%-100% and a comprehensive titanium loading of raw materials into the furnace of 110-220 kg/t.
  • the average price difference between domestic vanadium-titanium iron ore and ordinary iron ore is 200 yuan/ton.
  • the ore blending cost can be reduced by 192 yuan per ton of hot metal.
  • This invention significantly increases the TiO2 mass percentage in the blast furnace slag.
  • the TiO2 mass percentage in the vanadium-titanium iron ore is ⁇ 12%, the TiO2 mass percentage in the blast furnace slag is ⁇ 23%.
  • This invention can achieve a TiO2 mass percentage in the blast furnace slag within the range of 15-45%.
  • the TiO2 mass percentage in the vanadium-titanium iron ore when the TiO2 mass percentage in the vanadium-titanium iron ore reaches 8%, the TiO2 mass percentage in the blast furnace slag can reach 27%; when the TiO2 mass percentage in the vanadium-titanium iron ore reaches 10%, the TiO2 mass percentage in the blast furnace slag can reach 30%; and when the TiO2 mass percentage in the vanadium-titanium iron ore is >12%, the TiO2 mass percentage in the blast furnace slag can reach 40%.
  • the increased TiO2 mass percentage in the blast furnace slag significantly enhances the slag's utilization value.
  • This invention uses pure oxygen injection. After CO2 is removed from the furnace top gas, it is heated and injected back into the furnace, increasing the amount of reducing gas CO in the furnace and reducing the amount of solid fuel that needs to be burned at the tuyeres (the purpose of burning solid fuel at the tuyeres is to provide heat and CO reducing gas). Solid fuel consumption is reduced by 30-40%, and the overall fuel and power costs are reduced by about 50-100 yuan/ton of molten iron (prices vary in different regions, resulting in different cost reduction figures).
  • Figure 1 is a smelting process flow diagram of an embodiment of the present invention.
  • 1-blast furnace 2-gas purification facilities
  • 3-gas pipeline network 4-gas heating furnace.
  • This invention provides a method for smelting high-proportion vanadium-titanium iron ore in an oxygen blast furnace.
  • the apparatus involved includes a blast furnace 1, a gas purification facility 2, and a gas heating furnace 4.
  • the smelting method includes the following steps: adding blast furnace iron charge and coke into the blast furnace 1, using pure oxygen injection in the blast furnace 1, and injecting pure oxygen, hot gas, and pulverized coal into the tuyeres for smelting, producing liquid slag and molten iron, which are then discharged from the furnace through the slag-iron taphole.
  • Hot coal gas is blown into blast furnace 1 through the direct injection pipe of the air supply branch pipe, and then through the large tuyeres, the second tuyeres, and the small tuyeres in sequence; pulverized coal is injected into blast furnace 1 through the pulverized coal injection gun located in the direct injection pipe of the air supply branch pipe, and the pulverized coal injected into the pulverized coal injection gun is blown into blast furnace 1 through the large tuyeres, the second tuyeres, and the small tuyeres in sequence; oxygen is blown into blast furnace 1 through the small tuyeres.
  • blast furnace coke and iron charge are charged into the blast furnace from the top of the blast furnace via a charging device, wherein the iron charge is pellets or iron charge is pellets and at least one of the following materials: sintered ore and lump ore; blast furnace fuel includes, but is not limited to, pulverized coal and coke;
  • the gas produced by the combustion of oxygen and fuel in front of the tuyere, the hot gas injected into the tuyere sleeve, and the gas produced by the chemical reaction in the hearth together form the furnace belly gas.
  • the furnace belly gas During the upward movement of the furnace belly gas, it undergoes a physical and chemical reaction with the descending iron material to generate liquid slag and molten iron.
  • the slag and molten iron are discharged from the slag and iron taphole.
  • the furnace top gas produced by the reaction inside the furnace is discharged from the furnace top gas pipeline. After being de-dustened, de- CO2ened , and de- H2Oened by the gas purification facility 2, the furnace top gas becomes purified gas.
  • the purified gas reaches the gas pipeline network 3. Part of the purified gas is transmitted to other users for use, and the other part is mixed with coke oven gas and water vapor and transported into the gas heater 4. After heating, it becomes hot gas.
  • the entire smelting process described above achieves carbon recycling.
  • vanadium-titanium iron ore Due to the poor sintering characteristics of vanadium-titanium iron ore, the quality of the sinter produced is inferior, mainly manifested in low drop strength, low drum strength, low yield, and severe low-temperature reduction pulverization. Therefore, this limits the industrial application of vanadium-titanium iron ore.
  • the proportion of vanadium-titanium iron ore in the sinter is too high, it can lead to a series of problems such as high blast furnace return rate, increased fuel cost per ton of iron, poor blast furnace permeability, and unsmooth furnace operation.
  • this invention prioritizes the addition of vanadium-titanium iron ore to the pellet feed, with a small amount of the surplus added to the sinter feed, and controls the TiO2 content in the sinter to be ⁇ 5%.
  • the proportion of vanadium-titanium iron ore in the iron material is selected to the maximum value. For example, 100% vanadium-titanium iron ore is used for pelleting, and no other iron material other than vanadium-titanium iron ore is added.
  • the TiO2 content in the pellet is determined by the TiO2 content in the vanadium-titanium iron ore. Based on the current status of vanadium-titanium iron ore resources at home and abroad, the TiO2 content in the pellet is in the range of 3%-13%.
  • the proportion of vanadium-titanium iron ore in the blast furnace is increased by increasing the proportion of pellets (the proportion of pellets refers to the mass percentage of pellets in the blast furnace feed).
  • the optimal proportion of pellets in the blast furnace feed is 100%.
  • the pellet production line capacity is insufficient, sintered ore can be used to replace the insufficient portion.
  • the minimum capacity of the pellet production line should ensure that the proportion of pellets in the blast furnace feed is greater than 30%.
  • the proportion of vanadium-titanium iron ore should not be too large in order to reduce the negative impact of TiO2 on the quality of sinter and blast furnace production.
  • the TiO2 content in the finished sinter should be controlled at ⁇ 5%.
  • the blast furnace vanadium-titanium iron ore ratio can be 100%, and 15% ⁇ TiO2 mass fraction in blast furnace slag ⁇ 45%.
  • the pellet ratio is limited, it affects the increase of TiO2 mass fraction in blast furnace slag and the increase of the proportion of vanadium-titanium iron ore in blast furnace.
  • the proportion of vanadium-titanium iron ore in the blast furnace can be 60-100%.
  • the titanium load in the furnace can be 110-220 kg/t.
  • Blast furnace temperature is fundamental to stable blast furnace production and a crucial indicator for assessing furnace conditions.
  • excessively low furnace temperatures can lead to a thinning of the softening zone, uneven initial gas flow distribution, and problems such as localized gas pipes in the charge column, uneven charging, uneven charge distribution, and material collapse.
  • Excessively high temperatures can result in the formation of large amounts of Ti(C,N), leading to viscous slag and iron, foamy slag, difficulty in separating slag and iron, hearth adhesion, increased blast furnace pressure differential, and production disruptions.
  • This invention regulates furnace temperature by adjusting the mass ratio of iron charge to fuel, the amount of pulverized coal injected, and the temperature of hot gas.
  • the furnace temperature level is fed back by detecting the mass fractions of [Si] and [Ti] in the molten iron.
  • the sum of the [Si] and [Ti] mass fractions in molten iron should be controlled to be less than 0.8% and less than 0.4%.
  • the sum of the [Si] and [Ti] mass fractions in molten iron should be controlled to be less than 0.7% and less than 0.3%.
  • the mass fraction of TiO2 in blast furnace slag is less than 20% and less than 25%
  • the sum of the mass fractions of [Si] and [Ti] in molten iron should be controlled to be less than 0.10% and less than 0.6%.
  • the sum of the mass fractions of [Si] and [Ti] in molten iron should be controlled to be less than 0.05% and less than 0.55%.
  • the blast furnace charge and coke are charged from the top of the furnace at a mass ratio of 5.5-7.5:1, and the charge and pulverized coal are charged and injected into the furnace at a mass ratio of 15-40:1.
  • the amount of pulverized coal injected into the blast furnace can be adjusted to reduce the ratio of iron to pulverized coal; when the furnace temperature is temporarily too high, the amount of pulverized coal injected into the blast furnace can be adjusted to increase the ratio of iron to pulverized coal.
  • the amount of coke fed into the blast furnace can be adjusted to reduce the ratio of iron to coke; when the furnace temperature is consistently high, the amount of coke fed into the blast furnace can be adjusted to increase the ratio of iron to coke.
  • a blast furnace fuel ratio of ⁇ 400 kg/t and a coke ratio of ⁇ 300 kg/t can be achieved.
  • Typical values are a coal ratio of 50-100 kg/t and a coke ratio of 260-280 kg/t.
  • the charging system of a blast furnace plays a crucial role in the distribution of gas flow, energy utilization, and smooth operation of the furnace.
  • Blast furnace charging is achieved through top charging equipment, currently available in two types: minute-type top charging and bell-less top charging. Even with the same type of charging equipment, the parameters vary significantly depending on the blast furnace's volume. For example, even with a bell-less top charging system, different charging angles result in different points of impact of the charge within the furnace. Therefore, a standardized method is needed to regulate the distribution of the charge within the furnace. This invention focuses on bell-less top charging and provides a reasonable charging method.
  • the specific charging method is as follows: At the blast furnace burden height, take a horizontal blast furnace cross-section and divide the circle containing the cross-section into 11 equal-area rings, numbered from the inner ring to the outer ring as ring 1, ring 2, ring 3, ring 4, ring 5, ring 6, ring 7, ring 8, ring 9, ring 10, and ring 11.
  • the charging regime is as follows: 60%-80% of the coke is distributed in rings 9-11 and rings 1-5; 20%-40% of the coke is distributed in rings 6-8; 70%-90% of the iron is distributed in rings 4-10; and 10%-30% of the iron is distributed in rings 1-3 and ring 11.
  • the strength of the iron ore fed into the blast furnace is required to ensure good permeability.
  • the compressive strength of the pellets must be ⁇ 2500N, which increases processing costs, energy consumption, and carbon emissions.
  • This invention by adopting the above-mentioned charging system, increases the proportion of vanadium-titanium ore, allowing the blast furnace to achieve suitable permeability, smooth charging, and high iron production even under lower iron ore strength conditions.
  • Experimental verification shows that by adopting the above charging system, the compressive strength of the pellets can be reduced to as low as 1800N without affecting normal blast furnace production and technical and economic indicators.
  • the combustion reaction of carbon in front of the tuyere is the main source of heat and reducing agent in the blast furnace.
  • the substances injected into the tuyere of a traditional blast furnace include hot air, oxygen, and pulverized coal.
  • the traditional blast furnace process introduces a large amount of N2 . This portion of N2 does not participate in the reduction reaction of iron oxides, but it plays a role in increasing the blast energy, stirring, and activating the hearth.
  • the method for smelting high-proportion vanadium-titanium iron ore in an oxygen blast furnace of the present invention differs from the injection process of a traditional blast furnace.
  • the substances injected into the tuyeres include hot coal gas, oxygen, and pulverized coal. Only a small amount of carbon needs to be burned to meet the heat and reducing agent requirements within the furnace. However, to meet the requirements for reasonable blast kinetic energy and hearth activity, it is necessary to control the amount of gas in the furnace belly. Production tests show that controlling the amount of gas in the furnace belly in the oxygen blast furnace for smelting high-proportion vanadium-titanium iron ore within the range of 1200 Nm3 /t to 1750 Nm3 /t is more suitable. Based on this furnace belly gas volume parameter and the amount of coke to be burned in the furnace, the tuyeres injection parameters are further determined as follows:
  • the amount of hot coal gas injected into the furnace is 700 Nm3 /t - 1280 Nm3 /t, and the amount of oxygen injected into the furnace is 145 Nm3 /t - 245 Nm3 /t.
  • the hot coal gas is the gas heated by the coal gas heater, which includes coke oven gas, steam, and purified coal gas.
  • the input amount of coke oven gas into the coal gas heater is 20 Nm3 /t - 200 Nm3/t, and the molar ratio of steam to coke oven gas is 0.10-0.30 mol: 1 mol.
  • This invention involves mixing a portion of coke oven gas, steam, and purified gas and feeding it into a gas heater.
  • the purpose of adding steam to the mixture is to induce a series of reforming reactions between the steam and the coke oven gas, causing complex hydrocarbons to reform into H2 and CO, for example, CH4 + H2O ⁇ CO + H2 , C2H2 + H2O ⁇ CO + H2 .
  • the proportion of steam added is determined based on the composition of the coke oven gas and thermodynamic and kinetic calculations of the reactions within the heater. The optimal range is a molar ratio of steam to coke oven gas in the gas heater of 0.10-0.30:1.
  • the blast furnace top gas becomes purified gas after dust removal, CO2 removal and H2O removal.
  • the amount of this purified gas is greater than the amount of purified gas required by the gas heating furnace, and the surplus is used by external users, thus realizing the semi-sealed circulation and recovery of gas.
  • the compressed air used for pulverized coal injection contains approximately 79% N2 , and the furnace top equipment requires sealing and purging with N2 , and coke oven gas also contains 6%-10% N2 , this invention cannot yet achieve smelting in a zero-nitrogen environment. After removing dust, CO2 , and H2O from the coal gas, N2 enrichment is easily caused during recycling.
  • the volume percentage of N2 in the furnace top gas after system equilibrium is ⁇ 25%, with an optimal range of 7-15%. This is a significant reduction compared to the 45%-60% volume percentage of N2 in traditional blast furnace gas.
  • the purpose of supplementing the heating furnace with coke oven gas reforming gas is twofold: first, to increase the blast energy and ensure the activity of the hearth; and second, to dilute the N2 content of the gas in the furnace.
  • Thermodynamic calculations show that the formation of Ti(C,N) in the blast furnace during the smelting of vanadium-titanium iron ore is closely related to the N2 content.
  • the starting temperatures of reactions (1) and (2) are 1136°C and 1108°C, respectively, meaning that TiN is formed slightly earlier than TiC. In fact, pure TiN and TiC rarely exist in the blast furnace; instead, they form complex solid solutions that promote each other's formation.
  • a portion of coke oven gas, steam, and purified gas are mixed and fed into a gas heater, where they are heated to become hot gas.
  • the temperature range of the hot gas is 900°C-2300°C. Within this range, the higher the temperature of the hot gas, the more beneficial it is to reducing the solid fuel ratio and carbon emissions in the blast furnace.
  • the solid fuel ratio includes both the coal ratio and the coke ratio.
  • the gas heater can be electrically heated, heated by a hot blast stove, or heated by plasma gas. The ultimate goal is to obtain high-temperature gas at low cost. Depending on current technology, different heating equipment can achieve different hot gas temperatures. The most economical method is recommended to use a hot blast stove, which achieves a gas temperature of 1250-1280°C.
  • Example 1 Smelting of high-titanium slag from high-titanium vanadium-titanium iron ore resources
  • Table 2 Composition of Pelletite Produced from Vanadium-Titanium Iron Ore in Example 1
  • the blast furnace iron charge consists of 100% blast furnace pellets, with no added sinter or lump ore, and the blast furnace vanadium-titanium iron ore proportion is 100%.
  • the composition of the generated blast furnace slag is shown in Table 3.
  • the fuel and power costs of the smelting method of the present invention were reduced by 57 yuan/ton of iron. Furthermore, since the price of vanadium-titanium iron ore is lower than that of ordinary iron ore, the ore blending cost of the present invention was reduced by 420 yuan/ton, and CO2 emissions were reduced by 33.3%.
  • Example 2 Smelting of titanium slag from high-titanium vanadium-titanium iron ore resources
  • Table 5 Composition of Pelletite Produced from Vanadium-Titanium Iron Ore in Example 2
  • vanadium-titanium iron ore Due to insufficient output from the pellet production line, but to obtain better metallurgical performance of the sinter, for vanadium-titanium iron ore with a TiO2 content >8%, it is recommended that the proportion of pellets in the blast furnace iron charge be >50%.
  • the blast furnace ore mix should be 60% pellets and 40% sinter, without adding lump ore.
  • the TiO2 content of the sinter should be controlled to ⁇ 3.5%. Therefore, vanadium-titanium iron ore is prioritized for pellet production, with the remainder used for sintering.
  • the iron raw materials for sintering production consist partly of vanadium-titanium iron ore and partly of other iron ores.
  • the metallurgical performance of the vanadium-titanium sinter can be significantly improved.
  • Special control of the MgO content in the sinter is no longer required, saving on the amount of high-MgO flux added during sintering production, thereby reducing production costs.
  • the sinter composition is shown in Table 6, which allows for a vanadium-titanium iron ore proportion of >75% in the blast furnace.
  • the sinter drum strength increased from an average of 72.0% to an average of 77.3%, and the sinter drum strength after implementation is >76%; the low-temperature reduction differentiation rate of sinter improved from an average of 55% to an average of 26.1%, and the low-temperature reduction pulverization rate of sinter after implementation is ⁇ 30%.
  • the composition of the generated blast furnace slag is shown in Table 7.
  • Table 7 The composition of the generated blast furnace slag basicity R2 in high-proportion vanadium-titanium iron ore smelting needs to be controlled to be ⁇ 1.12.
  • the fuel and power costs used in the smelting method of the present invention were reduced by 57 yuan/ton of iron. Furthermore, since the price of vanadium-titanium iron ore is lower than that of ordinary iron ore, the ore blending cost was reduced by 13 yuan/ton of iron, and CO2 emissions were reduced by 31.5%.
  • Example 3 Smelting of titanium slag from low-titanium vanadium-titanium iron ore resources
  • Table 8 Composition of Low-Titanium Vanadium-Titanium Iron Ore from Example 3
  • Table 9 Composition of Pelletite Produced from Vanadium-Titanium Iron Ore in Example 3
  • the blast furnace iron charge consists of 100% blast furnace pellets, with no added sinter or lump ore, and the blast furnace vanadium-titanium iron ore proportion is 100%.
  • the composition of the generated blast furnace slag is shown in Table 10.
  • the fuel and power costs of the smelting method of the present invention were reduced by 53 yuan/ton of iron.
  • the ore blending cost of the present invention was reduced by 310 yuan/ton, and CO2 emissions were reduced by 35.2%.
  • Example 4 Smelting of titanium slag from low-titanium vanadium-titanium iron ore resources
  • Table 11 Composition of Low-Titanium Vanadium-Titanium Iron Ore from Example 4
  • the ore blending ratio for the blast furnace is 55% acidic pellets and 45% basic sinter, without the addition of lump ore.
  • the aforementioned vanadium-titanium iron ore to produce pellets, no other iron-containing raw materials or fluxes are added during the pellet blending process.
  • a binder is added during the pellet blending process.
  • the composition of the produced pellets is shown in Table 12.
  • Table 12 Composition of pellets produced from vanadium-titanium iron ore in Example 4.
  • Vanadylene ore is preferentially used for pellet production, with the remainder used for sintering.
  • the TiO2 content of the sinter is controlled to be ⁇ 3.5% to obtain better metallurgical properties. After equilibrium, it is found that when the proportion of vanadium-titanium iron ore in the iron feedstock for sintering is 100%, the TiO2 content of the sinter can be ⁇ 3.5%. At this point, the proportion of vanadium-titanium iron ore in the blast furnace is 100%.
  • the composition of the sinter is shown in Table 13.
  • Table 13 Composition of Sinter Produced from Vanad-Titanium Iron Ore in Example 4
  • the fuel and power costs of the smelting method of the present invention were reduced by 53 yuan/ton of iron.
  • the ore blending cost of the present invention was reduced by 310 yuan/ton, and CO2 emissions were reduced by 35.2%.
  • Example 5 Example of Top Gas Circulation
  • composition of coke oven gas in steel plants is shown in Table 15 below.
  • the composition of the reducing gas obtained after reforming coke oven gas and steam in the heating furnace is shown in Table 16 below.
  • the coke oven gas flow rate is 75 m3 /t and the steam flow rate is 15.9 m3 /t.
  • the composition of the furnace gas generated in the furnace which comes from carbon combustion at the tuyere, direct reduction, and hot coal gas from the heating furnace, is shown in Table 17 below.
  • the furnace gas volume is 1500 m3 /t.
  • the gas in the furnace belly undergoes a reduction reaction with the iron oxides inside the furnace, producing metallic iron, H2O , and CO2 .
  • the composition of the gas at the top of the furnace is shown in Table 18 below, and the gas volume at the top of the furnace is 1500 m3 /t.
  • the composition of the purified blast gas after removing CO2 , H2O , and dust from the top gas is shown in Table 19 below, with a purified gas volume of 989 m3 /t. It is evident that N2 is enriched in the purified gas. If a portion is not exported, N2 will further enrich and rise to over 25% after one or more cycles of recycling. Therefore, 55 m3 /t of the 989 m3 /t purified gas is exported to other users, and 934 m3 /t is fed into the heating furnace for heating and then supplied to the blast furnace for recycling. However, this 934 m3 /t of purified gas cannot meet the blast furnace's blast energy requirements, so a portion of coke oven gas reforming is added. The purpose of supplementing with coke oven gas reforming is twofold: firstly, to increase blast energy and ensure hearth activity; and secondly, to dilute the N2 content of the gas inside the furnace.
  • the 934 m3 /t of purified coal gas enters the next round of recycling:
  • the purified coal gas with an N2 content of 21.09% is mixed with the coke oven gas reforming gas with an N2 content of 4.7% to become high-temperature reducing gas, which is then fed into the furnace. It is then mixed with CO produced by carbon combustion and reduction reactions in the furnace to become the furnace belly gas with an N2 content of 13.91%. This cycle repeats, and the N2 content of the coal gas in the furnace remains stable at around 13.91%.
  • the smelting method of the present invention achieves blast furnace smelting with a vanadium-titanium iron ore ratio greater than 60%, a TiO2 mass fraction in blast furnace slag greater than 15% and less than 45%, and a CO2 emission reduction of more than 30%.

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Abstract

一种氧气高炉冶炼高比例钒钛铁矿的方法，包括以下步骤：高炉采用纯氧喷吹，风口处喷入纯氧、热煤气和煤粉，铁料和焦炭从炉顶加入，其中炉顶煤气中N2的体积百分比＜25％，炉顶煤气脱除CO2后循环利用。本发明氧气高炉冶炼高比例钒钛铁矿的方法能实现高炉钒钛铁矿比例大于60％、高炉炉渣中TiO2的质量分数＞15％且＜45％、CO2排放降低30％以上的冶炼，解决了现有高炉冶炼中提高钒钛铁矿比例时，存在炉渣粘稠、渣铁难以分离、炉况不顺、成本高、碳排放高等问题，从而使得钒钛资源的利用效率更高，冶炼成本和碳排放更低。

Description

一种氧气高炉冶炼高比例钒钛铁矿的方法
本申请要求于2024年6月27日提交中国专利局、申请号为202410846712.9、发明名称为“一种氧气高炉冶炼高比例钒钛铁矿的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及冶金技术领域，具体涉及到一种氧气高炉冶炼高比例钒钛铁矿的方法。
背景技术
目前技术成熟的炼铁工艺主要有高炉炼铁、熔融还原(HIsmelt、COREX、Finex)、直接还原(气基直接还原、煤基直接还原)等，但是这些工艺各有优缺点，主要有：
(1)高炉炼铁工艺：技术成熟，可以实现单座设备年产能高达百万吨以上，但其缺点是过度依赖优质冶金焦，需要配套建设焦化、烧结、球团，系统投资大；高炉操作难度大、炉况失常和波动后难以恢复；成本、碳排放和能耗高等；同时传统高炉炉内N2含量占气相总量的40％以上，极易生成Ti(C,N)，在炉内形成泡沫渣、不利于生产顺行和指标优化；
(2)熔融还原：①HIsmelt工艺热量传递效果不好，熔池铁水温度偏低仅1400℃-1450℃，烟气量高达2700Nm3/t铁、烟气温度达到1600℃，大量物理热随烟气排除炉外损失，铁损高、燃耗高、碳排放高；②COREX、Finex铁水[Si]含量高，煤气发生量过大、一次碳耗高；③碳的化学能利用率不充分，部分碳元素以CO的形式随煤气逸出，没能进一步利用其化学能；
(3)直接还原：①氢基竖炉对矿石品质要求高；②煤基直接还原需要固体燃料，因此碳耗高，且存在气基竖炉对矿石品质要求高的同样问题。
钒钛磁铁矿是一种多金属元素共生的复合矿，以含铁、钒、钛为主的共生磁性铁矿。钒钛磁铁矿是世界上生产钒的最主要原料资源，也是提炼Ti和Fe的主要矿物原料，同时钒钛磁铁矿也是世界公认的难冶炼矿种之一，其综合利用难度大。
目前钒钛铁矿的主要冶炼工艺是高炉冶炼法，高炉冶炼钒钛铁矿存在两方面技术难题：
一是，钒钛矿比例难以提高。现有技术中，当高炉钒钛铁矿比例(本发明所说的高炉钒钛铁矿比例，指生产烧结矿和球团矿所用的含铁原料中的钒钛铁矿量，与生产烧结矿和球团矿所用的含铁原料总量及高炉所用的含铁块矿量之和的比值)增加时，存在高炉炉渣(TiO2)含量增加，Ti(C,N)、TiC、TiN产生，造成炉渣粘稠、渣铁难以分离、泡沫渣等现象；同时，若是通过增加烧结原料中钒钛铁矿比例来增加高炉钒钛铁矿比例，则随着烧结矿中(TiO2)含量增加，会造成烧结矿转鼓强度降低、还原粉化增加、高炉顺行变差、炉况不顺，烧结返矿率增高、吨铁燃料成本上升等一系列技术问题。
二是，工序碳排放高、能耗高。高炉炉顶煤气中CO占比约20-30％，此部分CO的化学能在现有技术中没能有效利用，而是通过燃烧发电加以利用，高炉煤气燃烧发电的热能转化效率小于40％，因此，系统能耗高、碳排放高。
发明内容
本发明的目的是提供一种氧气高炉冶炼高比例钒钛铁矿的方法，用于解决现有技术中高炉冶炼钒钛铁矿存在钒钛铁矿比例难以提高以及工序碳排放高、成本高的技术问题。
为达上述目的，本发明的一个实施例中提供了一种氧气高炉冶炼高比例钒钛铁矿的方法，包括以下步骤：
高炉采用纯氧喷吹，风口处喷入纯氧、热煤气和煤粉；铁料和焦炭从炉顶加入；其中炉顶煤气中N2的体积百分比＜25％；炉顶煤气脱除CO2后循环利用；
铁料为球团矿或铁料为球团矿和如下材料中的至少一种：烧结矿和块矿；
球团矿中TiO2含量为3％-13％，生产球团矿所用铁原料为钒钛铁矿，球团矿在高炉入炉铁料中的占比＞30％；烧结矿中TiO2含量＜5％；
冶炼生成的高炉炉渣中TiO2的质量分数＞15％且＜45％，高炉钒钛铁矿比例＞60％，高炉CO2排放降低30％。
本发明优选的方案之一，热煤气为煤气加热炉加热后的气体，煤气加热炉中气体来源包括焦炉煤气、水蒸气以及净化煤气，其中送入煤气加热炉的焦炉煤气流量为20Nm3/t-200Nm3/t，送入加热炉的水蒸气与焦炉煤气物质的量之比为0.10-0.30：1。
本发明优选的方案之一，高炉冶炼过程中，
当高炉炉渣中TiO2的质量分数＞15％且≤18％时，铁水中[Si]和[Ti]的质量分数之和≥0.4％且≤0.8％；
当高炉炉渣中TiO2的质量分数＞18％且≤20％时，铁水中[Si]和[Ti]的质量分数之和≥0.3％且≤0.7％；
当高炉炉渣中TiO2的质量分数＞20％且≤25％时，铁水中[Si]和[Ti]的质量分数之和≥0.10％且≤0.6％；
当高炉炉渣中TiO2的质量分数＞25％时，铁水中[Si]和[Ti]的质量分数之和≥0.05％且≤0.55％。
本发明优选的方案之一，高炉铁料与焦炭的质量比为5.5-7.5:1，高炉铁料与煤粉的质量比为15-40:1；高炉冶炼中高炉燃料比＜400kg/t，焦比＜300kg/t。
本发明优选的方案之一，高炉冶炼过程中钒元素在铁水和炉渣中的分配系数[V]/(V2O5)＞1.1。
本发明优选的方案之一，喷入热煤气的流量为700Nm3/t-1280Nm3/t，喷入纯氧的流量为145Nm3/t-245Nm3/t。
本发明优选的方案之一，铁料和焦炭的装料方法为：在高炉料面高度，取水平方向的高炉截面，将截面所在圆等分成11个等面积的圆环，从内环到外环依次进行编号，布料制度为：60％-80％的焦炭分布于9环-11环和1环-5环，20％-40％的焦炭分布于6环-8环，70％-90％的铁料分布于4环-10环，10％-30％的铁料分布于1环-3环和11环。
综上所述，本发明的有益效果为：
1.解决了钒钛铁矿冶炼炉渣粘稠、泡沫渣的问题。本发明冶炼方法中的炉顶煤气中N2的体积百分比小于25％，与传统高炉煤气中N2的体积百分比45％-60％相比有显著降低。与传统高炉比，本发明冶炼过程中，N2分压降低、CO分压增加、炉温控制合理，均有效抑制了Ti(C,N)生成，从源头防止了渣铁粘稠、渣铁难以分离，控制了泡沫渣，进而解决了影响高炉钒钛铁矿比例提高的难题之一。
2.解决了钒钛烧结矿冶金性能差的问题。本发明通过配矿结构优化，控制烧结矿中TiO2含量＜5％、将钒钛铁矿尽量多地加入球团配料中，解决了钒钛烧结矿转鼓强度降低、还原粉化高、返矿率高带来的高炉顺行变差、炉况不顺，烧结吨铁燃料成本上升等一系列技术问题，进而解决了影响高炉钒钛铁矿比例提高的另一难题。
3.本发明配矿成本显著降低。通过配矿结构优化，本发明实现钒钛铁矿比例60％-100％、入炉综合原料钛负荷达到110-220kg/t，国内钒钛铁矿与普通铁矿差价平均为200元/吨，按钒钛铁矿比例60％、铁水矿耗1.6t/t保守计算，每吨铁水可降低配矿成本192元。
4.本发明炉渣中TiO2质量百分比显著提升。传统高炉冶炼钒钛铁矿，当钒钛铁矿中TiO2质量百分比＜12％时，高炉渣中TiO2质量百分比＜23％，本发明可实现高炉渣中TiO2质量百分比在15-45％范围内，其中，当钒钛铁矿中TiO2质量百分比达到8％时，可实现高炉渣中TiO2质量百分比达到27％；当钒钛铁矿中TiO2质量百分比达到10％时，可实现高炉渣中TiO2质量百分比达到30％；当钒钛铁矿中TiO2质量百分比＞12％时，可实现高炉渣中TiO2质量百分比达到40％。高炉渣中TiO2质量百分比增加，大幅提升了炉渣利用价值。
5.高炉燃料成本降低、CO2排放降低。本发明采用纯氧喷吹，炉顶煤气脱除CO2后加热回喷至炉内，增加了炉内还原性气体CO量、减少了风口需要燃烧的固体燃料量，(风口燃烧固体燃料的目的是提供热量和提供CO还原气)，固体燃料消耗降低30-40％，燃料和动力成本综合降低约50-100元/吨铁水(不同地区价格不同，造成降本数据有差异)。
附图说明
图1为本发明一个实施例的冶炼工艺流程图。
其中，1-高炉，2-煤气净化设施，3-煤气管网，4-煤气加热炉。
具体实施方式
本发明提供了一种氧气高炉冶炼高比例钒钛铁矿的方法，其涉及到的装置包括高炉1、煤气净化设施2和煤气加热炉4，冶炼方法包括以下步骤：将高炉铁料和焦炭加入高炉1中，高炉1采用纯氧喷吹，风口处喷入纯氧、热煤气和煤粉进行冶炼，冶炼生成液态的炉渣和铁水，炉渣和铁水通过渣铁口排出炉外。
具体的工艺流程和工艺参数如下：
(1)工艺流程
如图1所示，氧气高炉冶炼高比例钒钛铁矿的工艺流程为：
①热煤气经送风支管的直吹管，再依次经风口大套、二套、小套，吹入高炉1内；煤粉通过从位于送风支管直吹管的喷煤枪喷入，喷煤枪喷入的煤粉依次经风口大套、二套、小套，吹入高炉1内；氧气从风口小套吹入高炉1；
②高炉焦炭和铁料经上料设备从高炉炉顶装入炉内，其中铁料为球团矿或铁料为球团矿和如下材料中的至少一种：烧结矿和块矿；高炉燃料包括但不限于煤粉和焦炭；
③风口前氧气和燃料燃烧产生的煤气、风口小套喷入的热煤气和炉缸化学反应产生的煤气，共同形成炉腹煤气，炉腹煤气上行的过程中和下降的铁料发生物理化学反应，生成液态的炉渣和铁水，炉渣和铁水从渣铁口排出炉外；
④炉内反应产生的炉顶煤气从炉顶煤气管道排出，炉顶煤气经煤气净化设施2脱尘、脱CO2和脱H2O后，成为净化煤气，净化煤气到达煤气管网3，一部分净化煤气传输给其他用户进行使用，另一部分净化煤气与焦炉煤气和水蒸汽混合输送入煤气加热炉4，经加热后，成为热煤气。上述整个冶炼过程实现了碳循环。
(2)物料结构和造渣制度
由于钒钛铁矿的烧结特性较差，其制备得到的烧结矿质量较劣，主要表现在落下强度低、转鼓强度低、成品率低以及低温还原粉化严重等方面。因此，限制了钒钛铁矿的工业应用，当烧结矿中钒钛铁矿配料比例过大时，会造成高炉返矿率高、吨铁燃料成本上升、高炉透气性变差以及炉况不顺等系列问题。要提高钒钛铁矿入高炉比例，同时又要控制成本和稳定炉况，本发明将钒钛铁矿优先添加在球团配料中，富余部分少量添加在烧结配料中，并且控制烧结矿中TiO2含量＜5％。具体地：
①在球团配料过程中，钒钛铁矿在铁料中的占比选择最大值，例如100％钒钛铁矿造球，不再配加钒钛铁矿以外的其他铁料，球团矿中TiO2含量由钒钛铁矿中TiO2含量决定，依据国内外钒钛铁矿资源现状，球团矿TiO2含量在3％-13％范围内；
②高炉配料过程中，通过提高球团矿配比(球团矿配比是指球团矿在高炉入炉铁料中的质量占比)，提高高炉钒钛铁矿比例；球团矿在高炉铁料中比例最佳值为100％，球团产线产能不足时，可用烧结矿替代不足部分，球团产线最低产能应确保球团矿在高炉铁料中比例大于30％。
③当高炉球团矿配比已达上限，但还需进一步提高高炉钒钛铁矿比例时，例如当球团产线产量仅能确保球团矿在高炉铁料中最大占比是30％，但高炉期望的钒钛铁矿比例大于60％时，选择在烧结矿中补充添加钒钛铁矿；
④烧结配料过程中，钒钛铁矿配比不宜过大，以减轻TiO2对烧结矿质量和高炉生产的负面影响，按照烧结成品矿中TiO2含量＜5％控制。
按照以上方法进行配矿，当球团矿配比不受限，即满足球团配比＝100％时，可实现高炉钒钛铁矿比例100％，15％＜高炉炉渣中TiO2质量分数＜45％。当球团矿配比受限时，会影响高炉炉渣中TiO2质量分数提升和高炉钒钛铁矿比例提升，具体地，当30％＜球团矿配比＜100％时，对于矿石中TiO2含量＜5.0％的低钛型钒钛铁矿，可实现钒钛矿比例100％，15％＜高炉炉渣中TiO2质量分数＜22％；当30％＜球团矿配比＜100％时，对于5％≤矿石中TiO2含量＜8％的中钛型钒钛铁矿，可实现高炉钒钛铁矿比例100％，16％＜高炉炉渣中TiO2质量分数＜26％；当30％＜球团矿配比＜100％时，对于矿石中TiO2含量≥8％的高钛型钒钛铁矿，可实现高炉钒钛铁矿比例＞60％，23％＜高炉炉渣中TiO2质量分数＜45％。
以上总结为：可实现15％＜高炉炉渣中TiO2质量分数＜45％，高炉钒钛铁矿比例＞60％。
通过以上配矿，实现了高炉钒钛铁矿比例60-100％，对于矿石中TiO2含量＞8％的钒钛铁矿，通过将钒钛球团矿配比调整到50％以上，可以实现入炉钛负荷110-220kg/t。
(3)热制度
炉温是高炉稳定生产的基础，也是判断炉况的重要指标。对于钒钛铁矿冶炼来说，炉温过低会造成炉内软熔带变薄、初始煤气流分布不均以及料柱出现局部煤气管道、下料不顺、偏料、崩滑料等现象；炉温过高会造成Ti(C,N)大量生成，渣铁粘稠、泡沫渣、渣铁难以分离、炉缸粘结、高炉压差上升以及生产无法正常进行等现象。通过对炉内温度场分布进行模拟分析，对Ti(C,N)生成的热力学和动力学条件进行计算，得出：要确保炉况顺行，需要依据不同的高炉炉渣中TiO2质量分数，确定炉温控制目标范围。
另一方面，对于钒钛铁矿冶炼来说，需要尽量让钒元素还原并溶解在铁水中，以提高钒资源的利用率。炉温高低是决定钒元素在铁水和炉渣中分配系数Lv高低的重要因素。保持合适的炉温才能取得较好的钒分配系数Lv，其中，钒分配系数Lv＝[V]/(V2O5)，[V]指铁水中的钒元素质量百分含量，(V2O5)指炉渣中的V2O5质量百分含量。
本发明通过调整入炉铁料和燃料质量比、喷煤量和热煤气温度来调剂炉温，通过铁水中[Si]和[Ti]的质量分数检测反馈炉温水平。具体地：
①合理炉温控制范围
当15％＜高炉炉渣中TiO2质量分数≤18％时，应控制0.4％≤铁水中[Si]和[Ti]质量分数之和≤0.8％；
当18％＜高炉炉渣中TiO2质量分数≤20％时，应控制0.3％≤铁水中[Si]和[Ti]质量分数之和≤0.7％；
当20％＜高炉炉渣中TiO2质量分数≤25％时，应控制0.10％≤铁水中[Si]和[Ti]的质量分数之和≤0.6％；
当高炉炉渣中TiO2的质量分数＞25％时，应控制0.05％≤铁水中[Si]和[Ti]的质量分数之和≤0.55％。
②合理的矿焦比和矿煤比
高炉铁料和焦炭从炉顶按铁料：焦炭为5.5-7.5：1的质量比例装入，铁料和煤粉按铁料：煤粉为15-40：1的质量比例装入和喷入炉内。
当炉温临时偏低时，可调整高炉入炉喷煤量，使得铁料与煤粉的比值降低；当炉温临时偏高时，可调整高炉入炉喷煤量，使得铁料与煤粉的比值增大；
当炉温长期偏低时，可调整高炉入炉焦炭量，使得铁料与焦炭的比值降低；当炉温长期偏高时，可调整高炉入炉焦炭量，使得铁料与焦炭的比值增大。
按照以上参数控制，搭配合理的装料制度和喷吹参数，可实现高炉燃料比＜400kg/t，焦比＜300kg/t，典型取值范围是煤比50-100kg/t，焦比260-280kg/t。钒元素在铁水和炉渣中的分配系数[V]/(V2O5)＞1.1。
(4)装料制度
高炉的装料制度对高炉的煤气流分布、高炉能量利用率以及炉况顺行起着重要作用。高炉的装料是通过炉顶装料设备实现的，目前装料设备分钟式炉顶和无料钟炉顶两种，不同容积的高炉，同类型的装料设备参数差异也非常大，例如：同样是无料钟炉顶，不同的布料角度对应的炉料在炉内的落点是不同的，因此，需要有统一的方法规定炉料在炉内的分布。本发明重点针对无料钟炉顶，给出合理布料方法。
具体的布料方法如下：在高炉料面高度，取水平方向的高炉截面，将截面所在圆等分成11个等面积的圆环，从内环到外环分别编号为1环、2环、3环、4环、5环、6环、7环、8环、9环、10环和11环。布料制度是：60％-80％的焦炭分布于9环-11环和1环-5环，20％-40％的焦炭分布于6环-8环，70％-90％的铁料分布于4环-10环，10％-30％的铁料分布于1环-3环和11环。
由于钒钛烧结矿和球团矿，在高炉内还原过程均比普通矿粉化严重，因此，为了使得氧气高炉具备良好的透气性，对入炉铁矿的强度要求较高，一般要求球团矿抗压强度≥2500N，这就增加了原料的加工成本、能耗和碳排放。本发明通过采取以上布料制度，使得钒钛矿比例提高后，即使在较低的铁矿强度条件下，高炉仍能获得适宜的透气性、顺畅的下料、较高的铁产量。经过试验验证，通过采取以上布料制度，球团矿抗压强度最低可以降低到1800N，而不影响高炉正常生产和技术经济指标。
(5)风口喷吹参数
高炉生产中，风口前碳素的燃烧反应(反应产物CO)是高炉热量和还原剂的主要来源。传统高炉风口喷吹的物质包括热大气、氧气和煤粉，在燃烧释放相同热量和CO条件下，传统高炉工艺带入了大量的N2，此部分N2没有参与铁氧化物的还原反应，但起到增加鼓风动能、搅拌和活跃炉缸的作用。
特别是在钒钛矿冶炼过程中，要抑制Ti(C,N)的生成，对鼓风动能的要求更加严格，鼓风动能不足会造成炉缸局部不活跃，在炉缸不活跃的部位Ti元素在炉内停留时间增加，使得Ti(C,N)生成量增加，进而使得炉渣粘稠、渣铁难以分离。炉腹煤气量是影响鼓风动能和炉缸活跃度的重要参数。
本发明的氧气高炉冶炼高比例钒钛铁矿的方法，与传统高炉的喷吹工艺流程不同，本发明中高炉风口喷吹的物质包括热煤气、氧气和煤粉。仅需要燃烧较少的碳素即可满足炉内热量和还原剂需求。但为了满足合理的鼓风动能和炉缸活跃度需求，需要控制合理的炉腹煤气量，生产试验表明，氧气高炉冶炼高比例钒钛铁矿炉腹煤气量控制在1200Nm3/t-1750Nm3/t范围较合适。依据此炉腹煤气量参数和炉内需要燃烧的焦炭量，进一步确定风口喷吹参数，具体如下：
本发明中喷入炉内的热煤气量为700Nm3/t-1280Nm3/t，喷入炉内的氧气量为145Nm3/t-245Nm3/t。其中，热煤气为煤气加热炉加热后的气体，煤气加热炉中包括焦炉煤气、水蒸气以及净化煤气，输送入煤气加热炉的焦炉煤气的输入量为20Nm3/t-200Nm3/t，输送入煤气加热炉的水蒸气与焦炉煤气物质的量之比为0.10-0.30mol：1mol。
本发明将一部分焦炉煤气、水蒸汽和净化煤气混合输送入煤气加热炉，其中混合气中加入水蒸气的目的是水蒸气和焦炉煤气发生系列重整反应，使得复杂碳氢化合物重整生成H2和CO，例如CH4+H2O→CO+H2，C2H2+H2O→CO+H2。水蒸气的混入比例依据焦炉煤气的成分、加热炉内反应热力学和动力学计算确定，最佳取值范围为：煤气加热炉内水蒸气和焦炉煤气物质的量之比是0.10-0.30：1。
按照以上喷吹参数控制，高炉产生的炉顶煤气经脱除粉尘、脱CO2和脱H2O后成为净化煤气，此净化煤气的量大于煤气加热炉所需要的净化煤气量，富余部分供外部用户使用，即实现了煤气半密封循环回收。
由于用于喷吹煤粉的压缩空气中含有79％左右的N2，炉顶设备需要用N2进行密封和吹扫，焦炉煤气中也含有6％-10％的N2。因此，本发明还无法实现在零氮气环境下冶炼。煤气脱除粉尘、CO2和H2O后，循环利用的过程中容易造成N2富集。但是，按照上述喷吹参数进行控制，通过煤气半密封循环回收，即将N2富集的净化煤气外输一部分，供其他用户使用，补充一部分N2含量低的焦炉煤气重整气，加热后喷入炉内，使得系统平衡后炉顶煤气中N2的体积百分比＜25％，更优范围为7-15％，这与传统高炉煤气中N2的体积百分比45％-60％相比有显著降低。
在加热炉中补充焦炉煤气重整气的作用有两点：一是增加鼓风动能、确保炉缸活跃度，二是稀释炉内煤气的N2含量。
经过热力学计算表明：高炉冶炼钒钛铁矿，炉内Ti(C,N)的生成与N2含量有密切关系，反应(1)和(2)的开始温度分别是1136℃和1108℃，即TiN生成略早于TiC，实际上在高炉中绝少存在纯TiN和TiC，而是形成复杂固溶体互相促进生成。
TiO2+3C＝TiC+2CO         ΔGθ＝524130-333.55T(J/mol)        (1)
析出TiC的临界为：
析出TiN的临界为：
析出Ti(C,N)的临界为：
传统高炉由于N2含量较高，当炉渣(TiO2)质量占比达到23％时，炉内生成的Ti(C,N)就会让高炉无法正常生产。本发明中的N2分压降低、CO分压增加，同时，通过监控铁水中[Si]和[Ti]质量分数之和控制炉温T，均有效抑制了Ti(C,N)生成。试验表明：控制炉顶煤气中N2体积占比＜25％，可满足炉渣(TiO2)质量占比达到45％时，渣铁分离效果和炉渣流动性仍然良好，高炉仍可稳定正常生产。
此外，本发明的冶炼方法中一部分焦炉煤气、水蒸汽和净化煤气混合输送入煤气加热炉，经加热后成为热煤气，热煤气的温度范围为900℃-2300℃。在900℃-2300℃范围内，热煤气的温度越高，越有利于降低高炉固体燃料比和碳排放，其中，固体燃料比包括煤比和焦比。同时，煤气加热炉可以采用电加热方式，也可采用热风炉加热方式，也可采用等离子气体加热方式，其最终目的是低成本地获得高温煤气，依据当前技术水平，不同加热设备可以获得的热煤气温度不同。最经济的方法是，推荐采用热风炉加热方式，获得1250-1280℃煤气温度。
实施例1：高钛型钒钛铁矿资源高钛渣冶炼
某地高钛型钒钛铁矿成分如表1所示：
表1：实施例1钒钛铁矿成分表
采用上述钒钛铁矿生产球团矿，配矿过程不再添加其他含铁原料，生产的球团矿的成分如表2所示：
表2：实施例1钒钛铁矿生产的球团矿成分表
高炉铁料中高炉球团矿配比是100％球团矿，不添加烧结矿和块矿，高炉钒钛铁矿比例是100％。生成的高炉渣成分如表3所示：
表3：实施例1生产的高炉渣成分表
根据本发明的氧气高炉冶炼高比例钒钛铁矿的方法(包括热制度、装料方法和风口气体喷吹参数)进行冶炼，实际获得的结果为：铁水中的[V]含量为0.536％，焦比为260kg/t，煤比为100kg/t，钒元素在铁水和炉渣中的分配系数[V]/(V2O5)＝1.35＞1.3，入炉综合原料的钛负荷为180kg/t，炉渣(TiO2)含量达到31.25％，远高于当前国际领先水平(入炉钛负荷110-130kg/t，炉渣TiO2含量22-23％)。与传统高炉相比，本发明冶炼方法所使用的燃料和动力成本降低了57元/吨铁，进一步的，由于钒钛铁矿价格比普通铁矿价格低，从而使得本发明的配矿成本降低了420元/吨，CO2实物排放降低了33.3％。
实施例2：高钛型钒钛铁矿资源中钛渣冶炼
某地高钛型钒钛铁矿成分如表4所示：
表4：实施例2钒钛铁矿成分表
采用上述钒钛铁矿生产球团矿，配矿过程不再添加其他含铁原料，生产的球团矿的成分如表5所示：
表5：实施例2钒钛铁矿生产的球团矿成分表
由于球团矿产线产量不足，但为了获得较好的烧结矿冶金性能，对于此类矿石中TiO2含量＞8％的钒钛铁矿，推荐球团矿在高炉铁料中的占比＞50％，例如：高炉入炉矿石配比为60％球团矿和40％烧结矿，不配加块矿。控制烧结矿TiO2含量＜3.5，以获得较好的烧结矿冶金性能，为此，钒钛铁矿优先用于球团生产，剩余部分用于烧结生产。烧结生产的铁原料，一部分是钒钛铁矿，另一部分是其他铁矿。由于控制了钒钛烧结矿TiO2含量＜3.5，钒钛烧结矿冶金性能可以大幅改善，不需要再对烧结矿中MgO含量进行特殊控制，节约了烧结矿生产过程中高MgO熔剂的添加量，进而降低了生产成本。烧结矿成分如表6所示，以此能获得的高炉的钒钛铁矿比例＞75％。
表6：实施例2烧结矿成分表

与传统冶炼相比，实施后，烧结矿转鼓强度由平均72.0％，增加到平均77.3％，实施后烧结矿转鼓强度＞76％；烧结矿低温还原分化率由平均55％，改善到平均26.1％，实施后烧结矿低温还原粉化率＜30％。
生成的高炉渣成分如表7所示。试验验证，为了改善炉渣流动性，高比例钒钛铁矿冶炼需控制炉渣碱度R2＜1.12。
表7：实施例2生产的高炉渣成分表
根据本发明的氧气高炉冶炼高比例钒钛铁矿的方法(包括热制度、装料方法和风口气体喷吹参数)进行冶炼，实际获得的结果为：铁水中的[V]含量为0.313％，焦比为270kg/t，煤比为100kg/t，钒元素在铁水和炉渣中的分配系数[V]/(V2O5)＝1.38＞1.3，入炉综合原料的钛负荷为135kg/t，炉渣(TiO2)含量达到23.57％，优于当前国际领先水平。与传统高炉相比，本发明冶炼方法所使用的燃料和动力成本降低了57元/吨铁，进一步的，由于钒钛铁矿价格比普通铁矿价格低，配矿成本降低了13元/吨铁，CO2实物排放降低了31.5％。
实施例3：低钛型钒钛铁矿资源中钛渣冶炼
某地低钛型钒钛铁矿成分如表8所示：
表8：实施例3低钛型钒钛铁矿成分表
采用上述钒钛铁矿生产球团矿，配矿过程不再添加其他含铁原料，配矿过程添加熔剂和粘结剂，生产的球团矿的成分如表9所示：
表9：实施例3钒钛铁矿生产的球团矿成分表
高炉铁料中高炉球团矿配比是100％球团矿，不添加烧结矿和块矿，高炉钒钛铁矿比例是100％。生成的高炉渣成分如表10所示：
表10：实施例3生产的高炉渣成分表
根据本发明的氧气高炉冶炼高比例钒钛铁矿的方法(包括热制度、装料方法和风口气体喷吹参数)进行冶炼，实际获得的结果为：铁水中的[V]含量为0.767％，焦比为260kg/t，煤比为90kg/t，钒元素在铁水和炉渣中的分配系数[V]/(V2O5)＝1.51＞1.3。与传统高炉相比，本发明冶炼方法所使用的燃料和动力成本降低了53元/吨铁，进一步的，由于钒钛铁矿价格比普通铁矿价格低，从而使得本发明的配矿成本降低了310元/吨，CO2实物排放降低了35.2％。
实施例4：低钛型钒钛铁矿资源中钛渣冶炼
某地低钛型钒钛铁矿成分如表11所示：
表11：实施例4低钛型钒钛铁矿成分表
由于球团矿产线产量不足，高炉入炉矿石配比为55％酸性球团矿和45％碱性烧结矿，不配加块矿。采用上述钒钛铁矿生产球团矿，球团配矿过程不再添加其他含铁原料和熔剂，球团配矿过程添加粘结剂，生产的球团矿的成分如表12所示：
表12：实施例4钒钛铁矿生产的球团矿成分表
钒钛铁矿优先用于球团生产，剩余部分用于烧结生产，控制烧结矿TiO2含量＜3.5，以获得较好的烧结矿冶金性能，平衡后可得，烧结生产的铁原料中钒钛铁矿占比是100％时，可以满足烧结矿TiO2含量＜3.5。此时，高炉的钒钛铁矿比例是100％。烧结矿成分如表13所示：
表13：实施例4钒钛铁矿生产的烧结矿成分表
生成的高炉渣成分如表14所示：
表14：实施例4生产的高炉渣成分表
根据本发明的氧气高炉冶炼高比例钒钛铁矿的方法(包括热制度、装料方法和风口气体喷吹参数)进行冶炼，实际获得的结果为：铁水中的[V]含量为0.767％，焦比为260kg/t，煤比为90kg/t，钒元素在铁水和炉渣中的分配系数[V]/(V2O5)＝1.53＞1.3。与传统高炉相比，本发明冶炼方法所使用的燃料和动力成本降低了53元/吨铁，进一步的，由于钒钛铁矿价格比普通铁矿价格低，从而使得本发明的配矿成本降低了310元/吨，CO2实物排放降低了35.2％。
实施例5：炉顶煤气循环实施例
钢厂焦炉煤气成分见下表15。
表15：实施例5焦炉煤气成分
焦炉煤气与水蒸气在加热炉内重整后获得的还原气成分见下表16，焦炉煤气流量是75m3/t、水蒸气流量是15.9m3/t。
表16：实施例5焦炉煤气重整后的还原气成分
按照焦比0.26t/t、煤比0.07t/t，风口吹氧量191Nm3/t操作，来源于炉内风口碳素燃烧、直接还原、加热炉热煤气等，在炉内生成的炉腹煤气成分，见下表17，炉腹煤气量是1500m3/t。
表17：实施例5炉腹煤气成分
炉腹煤气在上升过程中与炉内铁氧化物发生还原反应，生成金属铁和H2O、CO2，煤气到达炉顶时，炉顶煤气成分，见下表18，炉顶煤气量是1500m3/t。
表18：实施例5炉顶煤气成分
炉顶煤气脱除CO2、H2O、粉尘后的净化煤气成分，见下表19，净化煤气量989m3/t。可见N2在净化煤气中被富集，若不外输一部分，N2会在下一轮或多轮循环利用后进一步富集上升至25％以上。因此，采取将净化煤气量989m3/t中的55m3/t的净化煤气向外输送给其他用户，934m3/t的净化煤气输送入加热炉加热后供给高炉循环利用，但此934m3/t的净化煤气不能满足高炉鼓风动能的需要，因此补充一部分焦炉煤气重整气。补充焦炉煤气重整气的作用有两点：一是增加鼓风动能、确保炉缸活跃度，二是稀释炉内煤气的N2含量。
表19：实施例5净化煤气成分
934m3/t的净化煤气进入下一轮循环利用过程：在煤气加热炉内，N2含量21.09％的净化煤气与N2含量4.7％的焦炉煤气重整气混合成为高温还原气送入炉内，再与炉内碳素燃烧和还原反应产生的CO混合成为N2含量13.91％的炉腹煤气，周而复始，炉内煤气N2含量稳定在13.91％左右。
综上所述，本发明的冶炼方法实现了高炉钒钛铁矿比例大于60％、高炉炉渣中TiO2的质量分数＞15％且＜45％、CO2排放降低30％以上的高炉冶炼。
虽然结合附图对本发明的具体实施方式进行了详细地描述，但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内，本领域技术人员不经创造性劳动即可做出的各种修改和变形仍属本专利的保护范围。

Claims (7)

  1. 一种氧气高炉冶炼高比例钒钛铁矿的方法，其特征在于，包括以下步骤：
    高炉采用纯氧喷吹，风口处喷入纯氧、热煤气和煤粉；铁料和焦炭从炉顶加入；其中炉顶煤气中N2的体积百分比＜25％；炉顶煤气脱除CO2后循环利用；
    所述铁料为球团矿或铁料为球团矿和如下材料中的至少一种：烧结矿和块矿；
    所述球团矿中TiO2含量为3％-13％，生产球团矿所用铁原料为钒钛铁矿，球团矿在高炉入炉铁料中的质量占比＞30％；所述烧结矿中TiO2质量分数＜5％；
    冶炼生成的高炉炉渣中TiO2的质量分数＞15％且＜45％，高炉钒钛铁矿比例＞60％，高炉CO2排放降低30％。
  2. 如权利要求1所述的一种氧气高炉冶炼高比例钒钛铁矿的方法，其特征在于：所述热煤气为煤气加热炉加热后的气体，所述煤气加热炉中气体来源包括焦炉煤气、水蒸气以及净化煤气，其中送入煤气加热炉的焦炉煤气流量为20Nm3/t-200Nm3/t，送入加热炉的水蒸气与焦炉煤气物质的量之比为0.10-0.30：1。
  3. 如权利要求1所述的一种氧气高炉冶炼高比例钒钛铁矿的方法，其特征在于：高炉冶炼过程中，
    当高炉炉渣中TiO2的质量分数＞15％且≤18％时，铁水中[Si]和[Ti]的质量分数之和≥0.4％且≤0.8％；
    当高炉炉渣中TiO2的质量分数＞18％且≤20％时，铁水中[Si]和[Ti]的质量分数之和≥0.3％且≤0.7％；
    当高炉炉渣中TiO2的质量分数＞20％且≤25％时，铁水中[Si]和[Ti]的质量分数之和≥0.10％且≤0.6％；
    当高炉炉渣中TiO2的质量分数＞25％时，铁水中[Si]和[Ti]的质量分数之和≥0.05％且≤0.55％。
  4. 如权利要求1所述的一种氧气高炉冶炼高比例钒钛铁矿的方法，其特征在于：所述高炉铁料与焦炭的质量比为5.5-7.5:1，所述高炉铁料与煤粉的质量比为15-40:1；高炉冶炼中高炉燃料比＜400kg/t，焦比＜300kg/t。
  5. 如权利要求1所述的一种氧气高炉冶炼高比例钒钛铁矿的方法，其特征在于：高炉冶炼过程中钒元素在铁水和炉渣中的分配系数[V]/(V2O5)＞1.1。
  6. 如权利要求1所述的一种氧气高炉冶炼高比例钒钛铁矿的方法，其特征在于：所述喷入热煤气的流量为700Nm3/t-1280Nm3/t，所述喷入纯氧的流量为145Nm3/t-245Nm3/t。
  7. 如权利要求1所述的一种氧气高炉冶炼高比例钒钛铁矿的方法，其特征在于，所述铁料和焦炭的装料方法为：在高炉料面高度，取水平方向的高炉截面，将截面所在圆等分成11个等面积的圆环，从内环到外环依次进行编号，布料制度为：60％-80％的焦炭分布于9环-11环和1环-5环，20％-40％的焦炭分布于6环-8环，70％-90％的铁料分布于4环-10环，10％-30％的铁料分布于1环-3环和11环。
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