WO2024046244A1 - 一种低冰镍生产高冰镍的方法和装置 - Google Patents

一种低冰镍生产高冰镍的方法和装置 Download PDF

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Publication number
WO2024046244A1
WO2024046244A1 PCT/CN2023/115145 CN2023115145W WO2024046244A1 WO 2024046244 A1 WO2024046244 A1 WO 2024046244A1 CN 2023115145 W CN2023115145 W CN 2023115145W WO 2024046244 A1 WO2024046244 A1 WO 2024046244A1
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Prior art keywords
blowing
oxygen
furnace
slag
nickel
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PCT/CN2023/115145
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English (en)
French (fr)
Inventor
陶吴
刘燕庭
訚硕
冯德茂
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中伟新材料股份有限公司
长沙卓瑞冶金环境技术开发有限公司
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Publication of WO2024046244A1 publication Critical patent/WO2024046244A1/zh

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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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation processes
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • C22B9/106—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents the refining being obtained by intimately mixing the molten metal with a molten salt or slag
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/14—Refining in the solid state
    • 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
    • Y02P10/20—Recycling

Definitions

  • the present disclosure relates to the technical field of nickel smelting, and specifically to a method and device for producing high nickel matte from low nickel matte.
  • Nickel ores mainly include nickel sulfide ore and nickel oxide ore.
  • the smelting processes of nickel mainly include fire process and wet process.
  • the pyrotechnic process is generally used for nickel sulfide ore.
  • the nickel sulfide ore is oxidized and smelted to produce low nickel matte, and the low nickel matte is then blown to produce high nickel matte.
  • nickel oxide ore there are mainly wet leaching process and pyro-smelting process.
  • the intermediate products of pyro-smelting process are divided into nickel-iron alloy and low matte nickel.
  • the low nickel matte intermediates produced from sulfide ores and oxidized ores need to be further refined to produce high nickel matte.
  • low matte nickel blowing adopts the traditional converter blowing process.
  • the main defects of the converter blowing process include at least the following: the flue gas is not conducive to the subsequent acid production process.
  • the purpose of the present disclosure is to at least overcome the aforementioned defects in the low nickel matte blowing process in the prior art.
  • the embodiments of the present disclosure provide a process for producing high nickel matte from low nickel matte.
  • a first aspect of the present disclosure provides a method for producing high nickel matte from low nickel matte, which method includes:
  • the low matte nickel blowing step includes continuously introducing solid low matte nickel and flux I into an oxygen-rich blowing furnace for blowing to produce high matte nickel, blowing slag and blowing flue gas.
  • a second aspect of the present disclosure provides a device for producing high nickel matte from low nickel matte, which device includes:
  • Both the oxygen-enriched converting furnace and the slag-depleting furnace include vertical fixed furnace bodies;
  • the vertical fixed furnace body includes a furnace body in the gas phase area, a furnace roof cover, a furnace body in the molten pool reaction area formed by a water-cooled structure, and a furnace hearth made of refractory materials;
  • the furnace hearth is provided with a slag discharge port and a siphon channel.
  • the furnace hearth shell is composed of a steel frame, a tie rod and a spring component.
  • the spring component is located between the steel frame and the tie rod.
  • the furnace hearth shell is an elastic structure.
  • the process for producing high nickel matte from low nickel matte provided by the present disclosure has the advantages of stable flue gas composition and flue gas volume, and is environmentally friendly.
  • Figure 1 is a process flow diagram for producing high nickel matte from low nickel matte according to the present disclosure
  • Figure 2 is a front view and a side view of an oxygen-enriched blowing furnace in a device for producing high nickel matte from low nickel matte according to the present disclosure
  • Figure 3 is a schematic connection diagram of the device for producing high nickel matte from low nickel matte according to the present disclosure.
  • embodiments of the present disclosure provide a method for producing high nickel matte from low nickel matte, which method includes:
  • the low matte nickel blowing step includes continuously introducing solid low matte nickel and flux I into an oxygen-rich blowing furnace for blowing to produce high matte nickel, blowing slag and blowing flue gas.
  • the continuous oxygen-enriched blowing of low matte nickel can increase SO 2 in the blowing flue gas. concentration, and at the same time reduce the SO 2 concentration fluctuation in the blowing flue gas, so that the blowing flue gas can be directly used in the acid making process.
  • it also includes:
  • the oxygen-enriched and depleted step of blowing slag includes injecting reducing agent, vulcanizing agent, and oxygen-enriched air II into the molten pool reaction of the slag depletion furnace. Zone, and the blowing slag is intermittently introduced from the oxygen-rich blowing furnace to flow into the molten pool reaction zone of the slag depletion furnace through the slag chute, and the reduction sulfurization reaction is performed to produce high cobalt, low matte nickel and depleted slag.
  • Control the oxygen excess coefficient ⁇ of the oxygen-rich air II to the reducing agent to be 0.4-0.5; control the temperature in the slag depletion furnace to be 1250-1400°C; return high cobalt and low matte nickel to the oxygen-rich blowing furnace for blowing.
  • the oxygen excess coefficient ⁇ can be any value between 0.4 and 0.5, for example, it can be 0.42, 0.44, 0.46, 0.48, or a value range consisting of any two of the above values, such as the oxygen excess coefficient ⁇ It can be but is not limited to 0.42-0.48.
  • An inappropriate oxygen excess coefficient may result in poor reduction and sulfurization effects in the furnace, and a reduction in the direct yield of nickel and cobalt.
  • the temperature in the slag depletion furnace is any value between 1250 and 1400°C, for example, it can be 1300°C, 1350°C, or a value range consisting of any two of the above values, such as the slag depletion furnace
  • the temperature in may be, but is not limited to, 1300-1350°C.
  • the oxygen excess coefficient ⁇ of the oxygen-enriched air II to the reducing agent the molar amount of oxygen actually provided/the theoretical molar amount of oxygen required for complete reaction of the system.
  • the solid low matte nickel contains 20wt%-25wt% nickel element, 45wt%-55wt% iron element, 0.5wt%-1.5wt% cobalt element, 20wt%-35wt% sulfur element.
  • the blowing slag flows into the molten pool reaction zone of the slag depletion furnace through a slag chute; the flux I is silica; the conditions in the oxygen-rich blowing furnace are controlled and the relationship between the solid low matte nickel and the flux I is controlled.
  • the dosage weight ratio is such that the mass ratio of iron element to silica in the blowing slag is 1.5-2.5:1.
  • it could be 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1 or 2.4:1, or anything between 1.5-2.5:1
  • the mass ratio of iron element to silicon dioxide can be, but is not limited to, 1.6-2.4:1, 1.7-2.3:1.
  • Controlling the proportion of iron elements and silica in the blowing slag can further improve the stability of continuous blowing, reduce the fluctuation of furnace control parameters in the oxygen-rich blowing furnace caused by the shape of the blowing slag, and reduce the impact on continuous blowing. This will further reduce the fluctuation of sulfur dioxide in the blowing flue gas.
  • An unsuitable mass ratio of iron to silica may make continuous blowing impossible or even cause production accidents.
  • the method further includes: injecting oxygen-rich air I into the oxygen-rich blowing furnace.
  • the volume concentration of oxygen in the oxygen-enriched air I is 40% to 70%.
  • the volume concentration of oxygen in the oxygen-enriched air I can be 50%, 55% %, 60%, 65%.
  • the pressure of the injected oxygen-enriched air I is 0.08Mpa ⁇ 0.2Mpa.
  • the pressure of the injected oxygen-enriched air I can be 0.09MPa, 0.1MPa, 0.11MPa, 0.12MPa, 0.13MPa, 0.14MPa, 0.15MPa, 0.16MPa, 0.17MPa, 0.18MPa, 0.19MPa, or any value between 0.08Mpa and 0.2Mpa, or a value range consisting of any two of the above values, for example,
  • the pressure of the oxygen-enriched air I may be, but is not limited to, 0.09-0.19MPa, 0.1MPa-0.18MPa.
  • further controlling the volume concentration of oxygen is helpful to avoid local overheating of the molten pool during the continuous blowing process, which affects the continuity and safety of production.
  • the method further includes: injecting pulverized coal into the primary tuyere in the oxygen-rich blowing furnace, and the amount of pulverized coal injected is 1wt% ⁇ of the amount of materials entering the furnace.
  • the injection amount of pulverized coal can be 1.5wt%, 2wt%, 2.5wt%, or any value between 1wt% and 3wt%, or a range of any two of the above values, for example , the injection amount of pulverized coal can be, but is not limited to, 1.5wt% ⁇ 2.5wt%, 1.8wt% ⁇ 2.2wt%.
  • the amount of materials entering the furnace is the sum of the amounts of solid low matte nickel and flux I.
  • the blowing temperature in the oxygen-rich blowing furnace is 1250-1350°C.
  • the blowing temperature in the oxygen-rich blowing furnace can be 1260°C or 1270°C. , 1280°C, 1290°C, 1300°C, 1310°C, 1320°C, 1330°C, 1340°C, or any value between 1250 and 1350°C, or a value range consisting of any two of the above values, for example, oxygen-rich
  • the blowing temperature in the blowing furnace can be, but is not limited to, 1290 ⁇ 1350°C, 1300 ⁇ 1350°C. In some embodiments, controlling the temperature within an appropriate range can reduce the formation of a slag layer.
  • the method in the low nickel matte blowing step, also includes: sequentially passing the blowing flue gas through a waste heat boiler to recover waste heat, an electrostatic precipitator for dust removal, and then introducing it into the flue gas acid making system for post-processing .
  • the method further includes: introducing flux II into the slag depletion furnace in the slag oxygen-enriched and depleted molten pool reaction zone; the flux II is limestone.
  • the method further includes: introducing flux II into the slag depletion furnace in the slag oxygen-enriched and depleted molten pool reaction zone; the flux II is calcium oxide and/or or calcium carbonate.
  • the method further includes: introducing flux II into the slag depletion furnace in the slag oxygen-enriched and depleted molten pool reaction zone; the flux II is calcium oxide and/or Or calcium carbonate; the flux II is introduced in an amount such that the weight ratio of CaO/SiO 2 of the slag in the slag depletion furnace is 0.3-0.6:1.
  • the amount of flux II introduced is such that the weight ratio of CaO/SiO2 in the slag depletion furnace can be 0.4:1, 0.5:1, or any value between 0.3-0.6:1, or any two of the above values.
  • the value range of the composition is such that the weight ratio of CaO/SiO2 in the slag depletion furnace can be 0.4:1, 0.5:1, or any value between 0.3-0.6:1, or any two of the above values.
  • the reducing agent in the oxygen-enriched and depleted blowing slag step, is selected from at least one of coke powder, bituminous coal and anthracite coal; the amount of the reducing agent with a particle size of 200 mesh or more is more than 80wt%; the reducing agent is blown
  • the weight ratio of refining slag to reducing agent is 100:5-15.
  • the weight ratio of blowing slag to reducing agent can be 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, or any value between 100:5 and 15, or a value range consisting of any two of the above values.
  • it can be but is not limited to 100: 6 ⁇ 14,100:7 ⁇ 13.
  • the vulcanizing agent in the oxygen-rich and depleted blowing slag step, is sulfur, and the particle size of the vulcanizing agent is 200
  • the amount above mesh is more than 80wt%; the weight ratio of blowing slag and vulcanizing agent is 100:3 ⁇ 5.
  • the weight ratio of blowing slag to vulcanizing agent can be 100:3.5, 100:4, 100:4.5, or any value between 100:3 and 5, or a value range consisting of any two of the above values. , for example, it can be but is not limited to 100:3.5 ⁇ 4.5.
  • the volume concentration of oxygen in the oxygen-enriched air II is 60% to 80%.
  • the volume concentration of oxygen in the oxygen-enriched air II may be 65%. , 70%, 75%, or any value between 60% and 80%, or a value range consisting of any two of the above values, for example, but is not limited to 65%-75%.
  • the pressure of the injected oxygen-enriched air II is 0.2Mpa ⁇ 0.4Mpa.
  • the pressure of the injected oxygen-enriched air II can be 0.25MPa, 0.3MPa, 0.35MPa, or any value between 0.2Mpa ⁇ 0.4Mpa , or a value range composed of any two of the above values, for example, it can be but is not limited to 0.25Mpa ⁇ 0.35Mpa.
  • the reducing agent in the oxygen-enriched and depleted blowing slag step, is sprayed into the slag oxygen-enriched and depleted molten pool reaction zone through compressed air with a pressure of 0.6Mpa to 0.8Mpa, and the vulcanizing agent is sprayed with a pressure of 0.6 Mpa ⁇ 0.8Mpa nitrogen is sprayed into the slag oxygen-rich and depleted molten pool reaction zone.
  • the vulcanizing agent By selecting sulfur as the vulcanizing agent, controlling the particle size of the vulcanizing agent, and combining the feeding method with primary tuyere injection, the vulcanizing agent can be used more efficiently, thereby reducing the introduction of impurities, lowering costs, and improving reaction efficiency.
  • the conditions of the reductive sulfurization reaction are controlled so that the metallization rate of high cobalt and low matte nickel in Me form is 0.20 to 0.4; for example, the Me form can be 0.25, 0.3 , 0.35, or any value between 0.20 and 0.4, or a value range consisting of any two of the above values, for example, it can be but is not limited to 0.25-0.35.
  • Me form (S theory -S actual )/S theory
  • S theory is the theoretical mass content of sulfur element in high cobalt and low matte nickel
  • S actual is the actual mass content of sulfur element in high cobalt and low matte nickel
  • high cobalt The theoretical mass content of sulfur in low matte nickel is the theoretical sulfur content when the iron element, nickel element, and cobalt element in high cobalt low matte nickel are all completely sulfurized. Controlling the metallization rate of high cobalt and low matte nickel within this range will help further ensure the continuity of the oxygen-enriched depletion step of the slag, thereby further improving the stability of the continuous production of high nickel matte from low nickel matte.
  • the time for the blowing slag to participate in the reduction and sulfurization reaction in the slag depletion furnace is 1.5-2.0 h, and the slag discharge time of the blowing slag is 2-3 h, The time interval for discharging depleted slag is 2-3 hours.
  • the following is an optional implementation description of the method for producing high nickel matte from low nickel matte according to the present disclosure in conjunction with Figure 1.
  • the method includes:
  • the solid low nickel matte i.e., the "low nickel matte” shown in Figure 1
  • the flux I i.e., the "silica” shown in Figure 1
  • oxygen-enriched air I is sprayed into the molten pool of the oxygen-rich blowing furnace through the primary tuyere of the furnace body in the molten pool reaction zone
  • pulverized coal is sprayed into the primary tuyer in the oxygen-rich blowing furnace.
  • blowing slag is released from the end slag discharge port every 2-3 hours and flows into the slag depletion furnace in step (2) through the slag chute.
  • the blowing flue gas passes through the waste heat boiler to recover waste heat and the electrostatic precipitator for dust removal. back Introduced into the flue gas acid making system for post-treatment;
  • the control conditions are such that the mass ratio of iron elements to silica in the blowing slag is 1.5-2.5:1; the volume concentration of oxygen in the oxygen-enriched air I is 40% to 70%, and the pressure of the injected oxygen-enriched air I is 0.08Mpa ⁇ 0.2Mpa; the injection amount of pulverized coal is 1wt% ⁇ 3wt% of the material amount entering the furnace; the blowing temperature in the oxygen-rich blowing furnace is 1250 ⁇ 1350°C;
  • Inject flux II (shown as "limestone” in Figure 1), reducing agent, vulcanizing agent, oxygen-enriched air II, and blowing slag into the molten pool reaction zone of the slag depletion furnace to perform the reduction and sulfurization reaction.
  • the slag is depleted and high-temperature flue gas is produced at the same time; the reducing agent is injected through compressed air, and the vulcanizing agent is injected through nitrogen;
  • Control the oxygen excess coefficient ⁇ of the oxygen-enriched air II to the reducing agent to be 0.4 ⁇ 0.5; control the temperature in the slag depletion furnace in the slag oxygen-enriched and depleted molten pool reaction zone to be 1250 ⁇ 1400°C; the pressure of the compressed air is 0.6Mpa ⁇ 0.8Mpa; the pressure of nitrogen is 0.6Mpa ⁇ 0.8Mpa; the amount of flux II introduced is such that the weight ratio of CaO/SiO 2 in the slag depletion furnace is 0.3:1 to 0.6:1; the ratio of blowing slag to reducing agent
  • the dosage weight ratio is 100:5 ⁇ 15; the dosage weight ratio of blowing slag and vulcanizing agent is 100:3 ⁇ 5; the volume concentration of oxygen in oxygen-enriched air II is 60% ⁇ 80%, and the pressure of oxygen-enriched air II It is 0.2Mpa ⁇ 0.4Mpa.
  • low matte nickel is blown and oxidized in an oxygen-rich blowing furnace to produce high matte nickel and blowing slag.
  • the blowing slag enters the slag depletion furnace for reduction and sulfurization, and the obtained low matte nickel is Nickel can be returned to the oxygen-rich converting furnace to continue converting.
  • nickel sulfide and ferrous sulfide need to be converted into elemental nickel, nickel disulfide, iron oxide and sulfur dioxide in the oxygen-rich blowing furnace, and impurities such as iron and sulfur are removed through oxidation, so More oxygen is required, and a flux needs to be added to separate impurities such as iron oxides in the melt.
  • the slag depletion furnace needs to reduce and sulfurize the nickel oxide in the blowing slag into nickel sulfide for enrichment. If the oxygen content is too high, the reduction will not be enough, resulting in poor nickel enrichment effect.
  • the present disclosure controls different oxygen concentrations, pressures, temperatures, proportions of other raw materials, feeding methods, etc. of the oxygen-rich air injected into the oxygen-rich blowing furnace and the slag depletion furnace respectively. Control the degree of redox.
  • the second aspect of the embodiment of the present disclosure provides a device for producing high nickel matte from low nickel matte.
  • the device includes:
  • Both the oxygen-enriched converting furnace and the slag-depleting furnace include vertical fixed furnace bodies;
  • the vertical fixed furnace body includes a furnace body in the gas phase area, a furnace roof cover, a furnace body in the molten pool reaction area formed by a water-cooled structure, and a furnace hearth made of refractory materials;
  • the furnace hearth is provided with a slag discharge port and a siphon channel.
  • the furnace hearth shell is composed of a steel frame, a tie rod and a spring component.
  • the spring component is located between the steel frame and the tie rod.
  • the furnace hearth shell is an elastic structure.
  • the vertical fixed furnace body further includes a flue.
  • the water-cooling structure in the furnace body of the molten pool reaction zone, is composed of multiple layers of water-cooling components.
  • the water-cooling component is a copper water jacket or a steel water jacket; the water-cooling component located at the bottom of the furnace body is a layer of water-cooling components.
  • the upper part of the first-layer water-cooling component is a second-layer water-cooling component.
  • the first-layer water-cooling component is equipped with no less than two primary air outlets; the angle of the air outlets is -5 degrees to 5 degrees in the horizontal direction;
  • the primary tuyere of the oxygen-enriched blowing furnace is used to inject oxygen-enriched air I
  • the primary tuyere of the slag depletion furnace is used to inject oxygen-enriched air II, reducing agent and vulcanizing agent
  • the feeding hole of the slag depletion furnace is used to add flux II.
  • the furnace body in the gas phase zone is formed by alternating refractory masonry and water-cooling water jacket structures, and the thickness of the refractory masonry between the water-cooling water jacket structures is independently 200 mm to 400 mm.
  • the furnace top cover adopts a water-cooling structure.
  • the water-cooling structure is composed of multiple layers of water-cooling components.
  • the water-cooling components are copper water jackets or steel water jackets.
  • the furnace top cover is provided with no less than one feeding hole.
  • a slag discharge port is provided at one end of the furnace body in the molten pool reaction zone higher than the tuyere.
  • the water jacket of the molten pool reaction zone of the oxygen-enriched blowing furnace and the slag depletion furnace is connected to the steel frame through tie rods.
  • the device includes:
  • Oxygen-enriched blowing furnace a
  • Both the oxygen-enriched converting furnace a and the slag depleting furnace c include vertical fixed furnace bodies;
  • the vertical fixed furnace body includes a gas phase zone furnace body, a furnace roof cover 10, a melt pool reaction zone furnace body formed by a water-cooling structure, and a furnace hearth 1 made of refractory materials;
  • the furnace 1 is provided with a slag discharge port 13 and a siphon channel.
  • the casing of the furnace 1 is composed of a steel frame 16, a tie rod 17 and a spring component.
  • the spring component is located between the steel frame and the tie rod.
  • the casing of the furnace 1 is an elastic structure. .
  • the furnace 1 is provided with a nickel matte discharge port 15 to discharge high cobalt and low nickel matte.
  • the upper surface of the furnace hearth 1 is provided with a flat water jacket 2 .
  • the water-cooling structure in the furnace body of the molten pool reaction zone, is composed of multiple layers of water-cooling components, and the water-cooling component is a copper water jacket or a steel water jacket; the water-cooling component located at the bottom of the furnace body is a layer of water-cooling component 3 , the upper part of the first-layer water-cooling component 3 is a second-layer water-cooling component 4, wherein the first-layer water-cooling component 3 is provided with no less than two primary air outlets 14; the angle of the primary air outlet is -5 degrees to 5 degrees in the horizontal direction.
  • the second-layer water-cooling component 4 is provided with no less than two secondary air outlets 12 .
  • the angle of each secondary air outlet independently ranges from 0° to 30° downward in the horizontal direction.
  • the cross-sectional area ratio of the primary tuyere of the oxygen-rich blowing furnace a and the primary tuyere of the slag-depleted furnace c is 1.1 to 1.25:1.
  • the oxygen-enriched converting furnace is positioned higher than the slag-depleting furnace.
  • the furnace body in the gas phase zone is formed by alternating structures of refractory masonry 5 and water-cooling water jacket 6.
  • the thickness of the refractory masonry between the water-cooling water jacket structures is independently 200 mm to 400 mm.
  • tertiary tuyeres 11 are provided on both sides of the furnace body in the gas phase zone for injecting air or oxygen-enriched air into the furnace.
  • the angles of each tertiary tuyere are independently 0° to 30° downward in the horizontal direction. .
  • the furnace top cover 10 is provided with a smoke exhaust flue 7 and a flue water jacket 8 .
  • the furnace top cover 10 adopts a water-cooling structure.
  • the water-cooling structure is composed of multiple layers of water-cooling components.
  • the water-cooling components are copper water jackets or steel water jackets.
  • the furnace top cover 10 is provided with no less than one feeding hole 9 .
  • the water jacket of the molten pool reaction zone of the oxygen-rich blowing furnace and the slag depletion furnace is connected to the steel frame 16 through a tie rod 17 .
  • a slag discharge port 13 is provided at one end of the furnace body in the molten pool reaction zone higher than the tuyere.
  • the solution provided by the present disclosure has the characteristics of short process flow, low energy consumption, good environmental protection effect, and high degree of automation.
  • one or more embodiments of the present disclosure have the following advantages:
  • This disclosure uses continuous feeding, continuous oxygen-enriched blowing, and a slight excess of vulcanizing agent to make the sulfur dioxide concentration in the flue gas high and stable, which is conducive to flue gas acid production and solves the current low sulfur dioxide concentration in the flue gas of nickel matte converter blowing. Problems with large fluctuations and low-altitude pollution;
  • the special blowing and slag depletion device used in this disclosure reduces the temperature, and the tuyere area adopts a water-cooling structure of a copper water jacket or a steel water jacket.
  • the furnace body has a longer life and solves the current converter blowing furnace body problem.
  • Refractory masonry, especially refractory masonry in the tuyere area, has a short service life due to excessive temperature;
  • the hot blowing slag flows into the slag depletion furnace through the slag chute, and the reduction and sulfurization reaction is carried out in the slag depletion furnace.
  • the nickel and cobalt are fully recovered, and high cobalt and low matte nickel can be produced.
  • the reduction and enrichment obtain Low matte nickel solves the problem of low nickel and cobalt recovery rate;
  • the oxygen-enriched blowing furnace of the present disclosure has three tuyeres, which increases the amount of enriched oxygen.
  • the separation effect of slag and high matte nickel is better, thereby improving the purity of high matte nickel.
  • composition of solid low ice nickel is, in terms of elements, 22.5wt% nickel, 49.09wt% Fe, 0.81wt% cobalt, and 27.6wt% sulfur.
  • the following nickel recovery rate [(sum of the mass of the nickel element in the product high-cobalt matte nickel and the product high-cobalt low matte nickel)/the mass of the nickel element in the raw material solid low matte nickel] ⁇ 100%;
  • (1) Solid low matte nickel and silica are batched through the metering belt and then continuously introduced into the oxygen-enriched blowing furnace through the feeding hole for blowing.
  • Oxygen-rich air I is injected into the molten pool, and pulverized coal is injected into the primary tuyer in the oxygen-rich blowing furnace to produce high nickel matte, blowing slag and blowing flue gas; the high nickel matte is intermittently released into water to quench; the blowing slag is The slag discharge port at the end is discharged every 2 hours through the slag chute and flows into the slag depletion furnace in step (2).
  • the blowing flue gas is sequentially passed through the waste heat boiler to recover waste heat and the electric precipitator for dust removal before being introduced into the flue gas system. Post-treatment in acid system;
  • the control conditions are such that the mass ratio of iron elements to silica in the blowing slag is 2.0:1; the volume concentration of oxygen in the oxygen-enriched air I is 50%, and the oxygen-enriched air pressure is 0.2Mpa; the injection amount of pulverized coal is 1wt% of the amount of materials entering the furnace; the blowing temperature in the oxygen-rich blowing furnace is 1250°C;
  • blowing flue gas is sequentially passed through a waste heat boiler to recover waste heat, an electric precipitator for dust removal, and then introduced into the flue gas acid making system for post-processing.
  • High matte nickel based on the mass content of elements, Ni is 73.94%, Co is 1.82%, Fe is 1.8%, and S is 21.77%.
  • High cobalt and low matte nickel based on the mass content of elements, Ni is 20.50%, Co is 4.60%, Fe is 45.44%, and S is 28.20%.
  • the nickel recovery rate is 99.5% and the cobalt recovery rate is 86.3%.
  • the injection amount of pulverized coal is 2wt% of the material amount entering the furnace; the blowing temperature in the oxygen-rich blowing furnace is 1300°C;
  • High nickel matte based on the mass content of elements, Ni is 74.52%, Co is 1.92%, Fe is 1.25%, and S is 21.86%.
  • High cobalt and low matte nickel based on the mass content of elements, Ni is 22.60%, Co is 4.77%, Fe is 50.35%, and S is 29.16%.
  • the nickel recovery rate is 99.41% and the cobalt recovery rate is 85.32%.
  • the injection amount of pulverized coal is 3% of the material amount entering the furnace
  • Control the oxygen excess coefficient ⁇ of the oxygen-enriched air II to the reducing agent to be 0.5; the weight ratio of the blowing slag to the reducing agent (pulverized coal) is 100:15; the weight ratio of the blowing slag to the vulcanizing agent (sulfur) The ratio is 100:5.
  • High matte nickel based on the mass content of elements, Ni is 75.52%, Co is 1.72%, Fe is 1.05%, and S is 22.13%.
  • High cobalt and low matte nickel based on the mass content of elements, Ni is 25.10%, Co is 5.32%, Fe is 39.92%, and S is 29.20%.
  • the nickel recovery rate is 99.6% and the cobalt recovery rate is 88.32%.
  • the introduction amount of flux II (calcium oxide) is such that the weight ratio of CaO/SiO 2 in the slag depletion furnace is 0.4:1; the volume concentration of oxygen in oxygen-enriched air II is 80%, and the oxygen-enriched air II
  • the pressure is 0.4Mpa; the temperature in the slag depletion furnace in the slag oxygen-rich and oxygen-depleted molten pool reaction zone is controlled to 1350°C.
  • High nickel matte based on the mass content of elements, Ni is 74.38%, Co is 1.45%, Fe is 1.65%, and S is 21.23%.
  • High cobalt and low matte nickel based on the mass content of elements, Ni is 25.20%, Co is 6.37%, Fe is 39.62%, and S is 27.50%.
  • the nickel recovery rate is 99.52% and the cobalt recovery rate is 89.32%.

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Abstract

本公开涉及镍冶炼技术领域，公开了一种低冰镍生产高冰镍的方法和装置，该方法包括：将固态低冰镍、二氧化硅连续引入至富氧吹炼炉中进行吹炼，产出高冰镍、吹炼渣以及吹炼烟气。本公开提供的低冰镍生产高冰镍的工艺具有烟气成分及烟气量稳定的优点。

Description

一种低冰镍生产高冰镍的方法和装置
相关申请的交叉引用
本公开要求于2022年8月30日提交的申请号为CN202211059047.6、发明名称为“一种低冰镍生产高冰镍的方法和装置”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及镍冶炼技术领域，具体涉及一种低冰镍生产高冰镍的方法和装置。
背景技术
镍矿主要有硫化镍矿和氧化镍矿。
镍的冶炼工艺主要有火法工艺和湿法工艺。
对于硫化镍矿一般均采用火法工艺，硫化镍矿经过氧化熔炼产出低冰镍，低冰镍进而经吹炼产出高冰镍。
对于氧化镍矿主要有湿法浸出工艺和火法冶炼工艺，火法工艺中间品分为镍铁合金和低冰镍。
硫化矿和氧化矿产出的低冰镍中间品均需要进一步经过吹炼产出高冰镍。
目前，低冰镍吹炼均采用传统的转炉吹炼工艺。转炉吹炼工艺主要存在的缺陷至少包括：烟气不利于后续制酸工艺。
发明内容
本公开的目的是为了至少克服现有技术中低冰镍吹炼过程存在的前述缺陷，本公开实施方式提供一种低冰镍生产高冰镍的工艺。
为了实现上述目的，本公开的第一方面提供一种低冰镍生产高冰镍的方法，该方法包括：
低冰镍吹炼步骤，包括将固态低冰镍、熔剂I连续引入至富氧吹炼炉中进行吹炼，产出高冰镍、吹炼渣以及吹炼烟气。
本公开的第二方面提供一种低冰镍生产高冰镍的装置，该装置中包括：
富氧吹炼炉；
渣贫化炉；
渣溜槽，连接富氧吹炼炉和渣贫化炉；
富氧吹炼炉和渣贫化炉均包括立式固定式炉体；
立式固定式炉体中包括气相区炉身、炉顶盖、采用水冷结构形成的熔池反应区炉身、由耐火材料砌筑而成的炉缸；
炉缸上设有放渣口、虹吸道，炉缸的壳体由钢架、拉杆及弹簧部件组成，弹簧部件位于钢架和拉杆之间，炉缸的壳体为弹性结构。
本公开提供的低冰镍生产高冰镍的工艺具有烟气成分及烟气量稳定、对环境友好的优点。
附图说明
图1是本公开的低冰镍生产高冰镍的工艺流程图；
图2是本公开低冰镍生产高冰镍的装置中的富氧吹炼炉的主视图和侧视图；
图3是本公开低冰镍生产高冰镍的装置连接示意图。
附图标记说明
a、富氧吹炼炉；b、渣溜槽；c、渣贫化炉
1、炉缸；2、平板水套；3、一层水冷件；4、二层水冷件；5、耐火材料砌体；6、水
冷水套；7、排烟烟道；8、烟道水套；9、加料孔；10、炉顶盖；11、三次风口；12、二次风口；13、放渣口；14、一次风口；15、冰镍放出口；16、钢架；17、拉杆
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
如前所述，本公开实施方式提供了一种低冰镍生产高冰镍的方法，该方法包括：
低冰镍吹炼步骤，包括将固态低冰镍、熔剂I连续引入至富氧吹炼炉中进行吹炼，产出高冰镍、吹炼渣以及吹炼烟气。
通过选择固态低冰镍作为原料，配合使用富氧吹炼炉进行吹炼，可实现连续、定量添加低冰镍原料，低冰镍的连续富氧吹炼，可提高吹炼烟气中SO2浓度、同时减小吹炼烟气中SO2浓度波动，从而使吹炼烟气可以直接用于制酸工艺。
在一些实施方式中，还包括：
吹炼渣富氧贫化步骤，包括将还原剂、硫化剂、富氧空气II喷入渣贫化炉的熔池反应 区中，以及将吹炼渣间断地从富氧吹炼炉中引出以通过渣溜槽流入渣贫化炉的熔池反应区中，进行还原硫化反应以产出高钴低冰镍和贫化渣；控制富氧空气II对还原剂的氧气过剩系数α为0.4～0.5；控制渣贫化炉中的温度为1250～1400℃；高钴低冰镍返回所述富氧吹炼炉吹炼。
可以理解的是，氧气过剩系数α可以为0.4～0.5之间的任一值，例如，可以是0.42、0.44、0.46、0.48，或上述任意两个数值组成的取值范围，例如氧气过剩系数α可以但不限于为0.42-0.48。不合适的氧气过剩系数，可能造成炉内炉内还原、硫化效果差，镍、钴直收率降低。
可以理解的是渣贫化炉中的温度为1250～1400℃之间的任一值，例如，可以是1300℃、1350℃，或上述任意两个数值组成的取值范围，例如渣贫化炉中的温度可以但不限于为1300-1350℃。
在本公开中，富氧空气II对还原剂的氧气过剩系数α＝实际提供的氧气摩尔量/系统完全反应需要的理论氧气摩尔量。
在一些实施方式中，在低冰镍吹炼步骤中，固态低冰镍中含有20wt％-25wt％的镍元素、45wt％-55wt％的铁元素、0.5wt％-1.5wt％的钴元素、20wt％-35wt％的硫元素。
在一些实施方式中，吹炼渣通过渣溜槽流入渣贫化炉的熔池反应区中；熔剂I为二氧化硅；控制富氧吹炼炉中的条件以及控制固态低冰镍与熔剂I的用量重量比，使得吹炼渣中的铁元素与二氧化硅的质量比为1.5-2.5：1。例如，可以为1.6：1、1.7：1、1.8：1、1.9：1、2.0：1、2.1：1、2.2：1、2.3：1或2.4：1，或1.5-2.5：1之间的任一值，或上述任意两个数值组成的取值范围，例如，铁元素与二氧化硅的质量比可以但不限于为1.6-2.4：1，1.7-2.3：1。
控制吹炼渣中铁元素和二氧化硅的比例可以进一步提高连续吹炼的稳定性，减少因为吹炼渣的形态带来的富氧吹炼炉中炉控参数的波动，减小对吹炼连续性的不利影响，从而进一步减小吹炼烟气中二氧化硫的波动。不适合的铁元素与二氧化硅的质量比可能造成连续吹炼无法实现，甚至造成生产事故。
在一些实施方式中，在低冰镍吹炼步骤中，该方法还包括：向富氧吹炼炉中喷入富氧空气I。
在一些实施方式中，在低冰镍吹炼步骤中，富氧空气I中的氧气的体积浓度为40％～70％，例如，富氧空气I中的氧气的体积浓度可以为50％、55％、60％、65％。喷入的富氧空气I的压力为0.08Mpa～0.2Mpa，例如，喷入的富氧空气I的压力可以为0.09MPa、0.1MPa、0.11MPa、0.12MPa、0.13MPa、0.14MPa、0.15MPa、0.16MPa、0.17MPa、0.18MPa、0.19MPa，或0.08Mpa～0.2Mpa之间的任一值，或上述任意两个数值组成的取值范围，例如， 富氧空气I的压力可以但不限于为0.09-0.19MPa，0.1MPa-0.18MPa。在一些实施方式中，进一步控制氧气的体积浓度有利于避免连续吹炼过程中熔池局部过热，影响生产的连续性和安全性。
在一些实施方式中，在低冰镍吹炼步骤中，该方法还包括：向富氧吹炼炉中的一次风口喷入粉煤，粉煤的喷入量为入炉物料量的1wt％～3wt％，例如，粉煤的喷入量可以为1.5wt％、2wt％、2.5wt％，或1wt％～3wt％之间的任一值，或上述任意两个数值组成的取值范围，例如，粉煤的喷入量可以但不限于为1.5wt％～2.5wt％，1.8wt％～2.2wt％。且入炉物料量为固态低冰镍和熔剂I的用量之和。
在一些实施方式中，在低冰镍吹炼步骤中，富氧吹炼炉中的吹炼温度为1250～1350℃，例如，富氧吹炼炉中的吹炼温度可以为1260℃、1270℃、1280℃、1290℃、1300℃、1310℃、1320℃、1330℃、1340℃，或1250～1350℃之间的任一值，或上述任意两个数值组成的取值范围，例如，富氧吹炼炉中的吹炼温度可以但不限于为1290～1350℃，1300～1350℃。在一些实施方式中，控制温度在合适的范围内可以减少粘渣层的形成，粘渣层的存在会对高冰镍与炉渣的分离带来不利影响。不合适的温度还可能造成炉渣含镍、钴等有价元素偏高，影响吹炼直接收率，且还可能导致连续生产无法进行。
在一些实施方式中，在低冰镍吹炼步骤中，该方法还包括：将吹炼烟气依次经过余热锅炉以回收余热、电除尘器进行除尘后引入至烟气制酸系统中进行后处理。
在一些实施方式中，在吹炼渣富氧贫化步骤中，该方法还包括：向渣富氧贫化熔池反应区中的渣贫化炉中引入熔剂II；熔剂II为石灰石。
在一些实施方式中，在吹炼渣富氧贫化步骤中，该方法还包括：向渣富氧贫化熔池反应区中的渣贫化炉中引入熔剂II；熔剂II为氧化钙和/或碳酸钙。
在一些实施方式中，在吹炼渣富氧贫化步骤中，该方法还包括：向渣富氧贫化熔池反应区中的渣贫化炉中引入熔剂II；熔剂II为氧化钙和/或碳酸钙；熔剂II的引入量使得渣贫化炉中渣的CaO/SiO2的重量比为0.3-0.6：1。例如，熔剂II的引入量使得渣贫化炉中渣的CaO/SiO2的重量比可以为0.4：1、0.5：1，或0.3-0.6：1之间的任一值，或上述任意两个数值组成的取值范围。
在一些实施方式中，在吹炼渣富氧贫化步骤中，还原剂选自焦粉、烟煤和无烟煤中的至少一种；还原剂中的粒度为200目以上的量为80wt％以上；吹炼渣与还原剂的用量重量比为100：5～15，例如，吹炼渣与还原剂的用量重量比可以为100：6、100：7、100：8、100：9、100：10、100：11、100：12、100：13、100：14，或100：5～15之间的任一值，或上述任意两个数值组成的取值范围，例如，可以但不限于为100：6～14，100：7～13。
在一些实施方式中，在吹炼渣富氧贫化步骤中，硫化剂为硫磺，硫化剂中的粒度为200 目以上的量为80wt％以上；吹炼渣与硫化剂的用量重量比为100：3～5。例如，吹炼渣与硫化剂的用量重量比可以为100：3.5、100：4、100：4.5，或100：3～5之间的任一值，或上述任意两个数值组成的取值范围，例如，可以但不限于为100：3.5～4.5。
在一些实施方式中，在吹炼渣富氧贫化步骤中，富氧空气II中的氧气的体积浓度为60％～80％，例如，富氧空气II中的氧气的体积浓度可以为65％、70％、75％，或60％～80％之间的任一值，或上述任意两个数值组成的取值范围，例如，可以但不限于为65％-75％。喷入的富氧空气II的压力为0.2Mpa～0.4Mpa，例如，喷入的富氧空气II的压力可以为0.25MPa、0.3MPa、0.35MPa，或0.2Mpa～0.4Mpa之间的任一值，或上述任意两个数值组成的取值范围，例如，可以但不限于为0.25Mpa～0.35Mpa。
在一些实施方式中，在吹炼渣富氧贫化步骤中，还原剂通过压力为0.6Mpa～0.8Mpa的压缩空气喷入渣富氧贫化熔池反应区中，以及硫化剂通过压力为0.6Mpa～0.8Mpa的氮气喷入渣富氧贫化熔池反应区中。
通过选择硫磺作为硫化剂，控制硫化剂的粒径，配合通过一次风口喷吹的加料方式，使硫化剂的使用效率更高，达到减少杂质引入、降低成本、提高反应效率的效果。
在一些实施方式中，在吹炼渣富氧贫化步骤中，控制还原硫化反应的条件，使得高钴低冰镍的金属化率Me形式为0.20～0.4；例如，Me形式可以为0.25、0.3、0.35，或0.20～0.4之间的任一值，或上述任意两个数值组成的取值范围，例如，可以但不限于为0.25-0.35。其中，Me形式＝(S理论-S实际)/S理论，S理论为高钴低冰镍中硫元素的理论质量含量，S实际为高钴低冰镍中硫元素的实际质量含量，高钴低冰镍中硫元素的理论质量含量为高钴低冰镍中的铁元素、镍元素、钴元素均被完全硫化时的理论含硫量。控制高钴低冰镍的金属化率在此范围内，利于进一步保障渣富氧贫化步骤的连续性，从而进一步提高低冰镍连续生产高冰镍的稳定性。
在一些实施方式中，在吹炼渣富氧贫化步骤中，吹炼渣在渣贫化炉中参与还原硫化反应的时间为1.5-2.0h，吹炼渣的放渣时间为2-3h，贫化渣的放渣时间间隔为2-3h。
以下结合图1对本公开的低冰镍生产高冰镍的方法提供一种可选的实施方式进行说明，该方法包括：
(1)将固态低冰镍(即为图1中所示的“低冰镍”)、熔剂I(即为图1中所示的“二氧化硅”)通过计量皮带配料后连续引入至富氧吹炼炉中进行吹炼，通过熔池反应区炉身的一次风口向富氧吹炼炉的熔池中喷入富氧空气I，向富氧吹炼炉中的一次风口喷入粉煤(即为图1中所示的“煤”)，同时向富氧吹炼炉中引入二次风，产出高冰镍、吹炼渣以及吹炼烟气；将间断地放出的高冰镍水淬；将吹炼渣从端部放渣口每隔2-3小时放出并通过渣溜槽流入步骤(2)中的渣贫化炉，将吹炼烟气依次经过余热锅炉以回收余热、电除尘器进行除尘后 引入至烟气制酸系统中进行后处理；
控制条件使得吹炼渣中的铁元素与二氧化硅的质量比为1.5-2.5：1；富氧空气I中氧气的体积浓度为40％～70％，喷入的富氧空气I的压力为0.08Mpa～0.2Mpa；粉煤的喷入量为入炉物料量的1wt％～3wt％；富氧吹炼炉中的吹炼温度为1250～1350℃；
(2)将熔剂II(图1中示出为“石灰石”)、还原剂、硫化剂、富氧空气II、吹炼渣喷入渣贫化炉的熔池反应区中进行还原硫化反应，同时向渣富氧贫化熔池反应区中引入二次富氧气体，控制还原硫化反应的条件，使得高钴低冰镍的金属化率Me形式为0.20～0.4，产出高钴低冰镍、贫化渣，同时产出高温烟气；还原剂通过压缩空气喷入，硫化剂通过氮气喷入；
控制富氧空气II对还原剂的氧气过剩系数α为0.4～0.5；控制渣富氧贫化熔池反应区中的渣贫化炉中的温度为1250～1400℃；压缩空气的压力为0.6Mpa～0.8Mpa；氮气的压力为0.6Mpa～0.8Mpa；熔剂II的引入量使得渣贫化炉中渣的CaO/SiO2的重量比为0.3：1至0.6：1；吹炼渣与还原剂的用量重量比为100：5～15；吹炼渣与硫化剂的用量重量比为100：3～5；富氧空气II中的氧气的体积浓度为60％～80％，富氧空气II的压力为0.2Mpa～0.4Mpa。
本公开的上述可选的实施方式中，低冰镍在富氧吹炼炉中进行吹炼氧化，产出高冰镍和吹炼渣，吹炼渣进入渣贫化炉进行还原硫化，得到的低冰镍可返回富氧吹炼炉继续吹炼。在低冰镍吹炼步骤中，富氧吹炼炉中需要将镍硫化物、硫化亚铁转化为镍单质、二硫化三镍、铁氧化物和二氧化硫，通过氧化除去铁、硫等杂质，所以需要更多的氧气，同时需要加入熔剂分离熔体中的铁氧化物等杂质。在吹炼渣富氧贫化步骤中，渣贫化炉需要将吹炼渣中的氧化镍还原硫化为硫化镍进行富集，如果氧含量太高，还原不够，导致镍富集效果较差。为了得到更高的镍收率，本公开通过分别控制向富氧吹炼炉、渣贫化炉喷入的富氧空气不同的氧气浓度和压力、温度、其他原料的比例、加料方法等，来控制氧化还原程度。
如前所述，本公开实施方式的第二方面提供了一种低冰镍生产高冰镍的装置，该装置中包括：
富氧吹炼炉；
渣贫化炉；
渣溜槽，连接富氧吹炼炉和渣贫化炉；
富氧吹炼炉和渣贫化炉均包括立式固定式炉体；
立式固定式炉体中包括气相区炉身、炉顶盖、采用水冷结构形成的熔池反应区炉身、由耐火材料砌筑而成的炉缸；
炉缸上设有放渣口、虹吸道，炉缸的壳体由钢架、拉杆及弹簧部件组成，弹簧部件位于钢架和拉杆之间，炉缸的壳体为弹性结构。
在一些实施方式中，立式固定式炉体中还包括烟道。
在一些实施方式中，在熔池反应区炉身中，水冷结构由多层水冷件组合而成，水冷件为铜水套或钢水套；位于炉身最下部的水冷件为一层水冷件，一层水冷件上部为二层水冷件，其中，一层水冷件设有不少于两个一次风口；风口角度为水平方向上-5度～5度；
富氧吹炼炉的一次风口用于喷入富氧空气I，渣贫化炉的一次风口用于喷入富氧空气II、还原剂以及硫化剂；渣贫化炉的加料孔用于加入熔剂II。
在一些实施方式中，气相区炉身采用耐火材料砌体与水冷水套结构形式交替形成，水冷水套结构之间的耐火材料砌体的厚度各自独立地为200mm～400mm。
在一些实施方式中，炉顶盖采用水冷结构，水冷结构由多层水冷件组合而成，水冷件为铜水套或钢水套，炉顶盖上设有不少于1个加料孔。
在一些实施方式中，熔池反应区炉身的一端高于风口处设有放渣口。
在一些实施方式中，富氧吹炼炉和渣贫化炉的熔池反应区水套通过拉杆与钢架连接。
以下结合图2和图3对本公开的低冰镍生产高冰镍的装置的可选的实施方式进行说明，该装置中包括：
富氧吹炼炉a；
渣贫化炉c；
渣溜槽b，连接富氧吹炼炉a和渣贫化炉c；
富氧吹炼炉a和渣贫化炉c均包括立式固定式炉体；
立式固定式炉体中包括气相区炉身、炉顶盖10、采用水冷结构形成的熔池反应区炉身、由耐火材料砌筑而成的炉缸1；
炉缸1上设有放渣口13、虹吸道，炉缸1的壳体由钢架16、拉杆17及弹簧部件组成，弹簧部件位于钢架和拉杆之间，炉缸的壳体为弹性结构。
可选地，炉缸1上设有冰镍放出口15以放出高钴低冰镍。
在一些实施方式中，炉缸1的上表面设有平板水套2。
在一些实施方式中，在熔池反应区炉身中，水冷结构由多层水冷件组合而成，水冷件为铜水套或钢水套；位于炉身最下部的水冷件为一层水冷件3，一层水冷件3上部为二层水冷件4，其中，一层水冷件3设有不少于两个一次风口14；一次风口的角度为水平方向上-5度～5度。
在一些实施方式中，二层水冷件4设有不少于两个二次风口12。
在一些实施方式中，各个二次风口的角度各自独立地为沿水平方向向下0°～30°。
在一些实施方式中，富氧吹炼炉a的一次风口和渣贫化炉c的一次风口的横截面面积比为1.1～1.25：1。
在一些实施方式中，富氧吹炼炉设置得比渣贫化炉高。
在一些实施方式中，气相区炉身采用耐火材料砌体5与水冷水套6结构交替形式形成，水冷水套结构之间的耐火材料砌体的厚度各自独立地为200mm～400mm。
在一些实施方式中，气相区炉身两侧设有三次风口11，用于向炉内喷入空气或富氧空气，各个三次风口的角度各自独立地为沿水平方向向下0°～30°。
在一些实施方式中，炉顶盖10设有排烟烟道7、烟道水套8。
在一些实施方式中，炉顶盖10采用水冷结构，水冷结构由多层水冷件组合而成，水冷件为铜水套或钢水套，炉顶盖10上设有不少于1个加料孔9。
在一些实施方式中，富氧吹炼炉和渣贫化炉的熔池反应区水套通过拉杆17与钢架16连接。
在一些实施方式中，熔池反应区炉身的一端高于风口处设有放渣口13。
本公开提供的方案具有工艺流程短、能耗低、环保效果好、自动化程度高等特点，可选地，本公开的一个或多个实施方式具有如下优势：
(1)本公开采用连续加料，连续富氧吹炼，且硫化剂稍微过量，使烟气二氧化硫浓度高且稳定，有利于烟气制酸，解决了目前低冰镍转炉吹炼烟气二氧化硫浓度波动大以及低空污染的问题；
(2)本公开采用冷料吹炼，吹炼系统可以脱离熔炼独立运行，解决了目前转炉热料吹炼必须与熔炼配置在一起，吹炼难以冷料单独运行的难题，同时连续吹炼克服了传统吹炼烟气浓度波动的问题；
(3)本公开采用的专用的吹炼及渣贫化装置，降低了温度，且风口区采用了铜水套或钢水套的水冷结构，炉体寿命更长，解决了目前转炉吹炼炉体耐火材料砌体尤其是风口区耐火材料砌体因温度过高导致使用周期短的问题；
(4)本公开采用热态吹炼渣通过渣溜槽流入渣贫化炉，在渣贫化炉内进行还原硫化反应，镍钴得到充分回收，能够产出高钴低冰镍，还原富集得到的低冰镍，解决了镍钴回收率低的问题；
(5)本公开的富氧吹炼炉上有三次风口，提高了富氧的通入量，并通过控制原料的配比，使渣与高冰镍分离效果更好，从而提高了高冰镍的纯度。
以下将通过实例对本公开进行详细描述。以下实例中，在没有特别说明的情况下，使用的原料均为普通市售品。
在没有特别说明的情况下，以下实例均采用图1所示的工艺流程进行。
固态低冰镍的组成为，以元素计，22.5wt％的镍、49.09wt％的Fe、0.81wt％的钴、27.6wt％的硫。
以下镍回收率＝[(产品高冰镍与产品高钴低冰镍中的镍元素的质量之和)/原料固态低冰镍中的镍元素的质量]×100％；
以下钴回收率＝[(产品高冰镍与产品高钴低冰镍中的钴元素的质量之和)/原料低冰镍中的钴元素的质量]×100％。
实施例1
(1)将固态低冰镍、二氧化硅通过计量皮带配料后通过加料孔连续引入至富氧吹炼炉中进行吹炼，通过熔池反应区炉身的一次风口向富氧吹炼炉的熔池中喷入富氧空气I，向富氧吹炼炉中的一次风口喷入粉煤，产出高冰镍、吹炼渣以及吹炼烟气；将高冰镍间断地放出水淬；将吹炼渣从端部放渣口每隔2小时放出通过渣溜槽流入步骤(2)中的渣贫化炉，将吹炼烟气依次经过余热锅炉以回收余热、电除尘器进行除尘后引入至烟气制酸系统中进行后处理；
控制条件使得吹炼渣中的铁元素与二氧化硅的质量比为2.0：1；富氧空气I中氧气的体积浓度为50％，富氧空气压力为0.2Mpa；粉煤的喷入量为入炉物料量的1wt％；富氧吹炼炉中的吹炼温度为1250℃；
(2)吹炼渣通过渣溜槽流入渣贫化炉后，将石灰石通过加料孔加入，将还原剂、硫化剂、富氧空气II通过一次风口喷入渣贫化炉的熔池反应区中进行还原硫化反应，控制还原硫化反应的条件，使得高钴低冰镍的金属化率Me形式为0.20，产出高钴低冰镍和贫化渣；还原剂通过压缩空气喷入，硫化剂通过氮气喷入；
控制富氧空气II对还原剂的氧气过剩系数α为0.4；控制渣富氧贫化熔池反应区中的渣贫化炉中的温度为1250℃；压缩空气的压力为0.6Mpa；氮气的压力为0.6Mpa；熔剂II(氧化钙)的用量使得渣贫化炉中渣的CaO/SiO2的重量比为0.3：1；吹炼渣与还原剂(无烟煤)的用量重量比为100：5；吹炼渣与硫化剂(硫磺)的用量重量比为100：3；富氧空气II中的氧气的体积浓度为80％，富氧空气II的压力为0.3Mpa。
将吹炼烟气依次经过余热锅炉以回收余热、电除尘器进行除尘后引入至烟气制酸系统中进行后处理。
结果：
高冰镍：以元素的质量含量计，Ni为73.94％，Co为1.82％，Fe为1.8％，S为21.77％。
高钴低冰镍：以元素的质量含量计，Ni为20.50％，Co为4.60％，Fe为45.44％，S为28.20％。
镍回收率为99.5％，钴回收率为86.3％。
实施例2
本实施例采用与实施例1相似的工艺进行，所不同的是，本实施例中：
(1)粉煤的喷入量为入炉物料量的2wt％；富氧吹炼炉中的吹炼温度为1300℃；
(2)控制富氧空气II对还原剂的氧气过剩系数α为0.5；控制渣富氧贫化熔池反应区中的渣贫化炉中的温度为1300℃；吹炼渣与还原剂(粉煤)的用量重量比为100：10；吹炼渣与硫化剂(硫磺)的用量重量比为100：4。
结果：
高冰镍：以元素的质量含量计，Ni为74.52％，Co为1.92％，Fe为1.25％，S为21.86％。
高钴低冰镍：以元素的质量含量计，Ni为22.60％，Co为4.77％，Fe为50.35％，S为29.16％。
镍回收率为99.41％，钴回收率为85.32％。
实施例3
本实施例采用与实施例1相似的工艺进行，所不同的是，本实施例中：
(1)粉煤的喷入量为入炉物料量的3％；
(2)控制富氧空气II对还原剂的氧气过剩系数α为0.5；吹炼渣与还原剂(粉煤)的用量重量比为100：15；吹炼渣与硫化剂(硫磺)的用量重量比为100：5。
结果：
高冰镍：以元素的质量含量计，Ni为75.52％，Co为1.72％，Fe为1.05％，S为22.13％。
高钴低冰镍：以元素的质量含量计，Ni为25.10％，Co为5.32％，Fe为39.92％，S为29.20％。
镍回收率为99.6％，钴回收率为88.32％。
实施例4
本实施例采用与实施例1相似的工艺进行，所不同的是，本实施例中：
(1)控制条件使得吹炼渣中的铁元素与二氧化硅的质量比为1.8：1；富氧空气I中氧气的体积浓度为60％，富氧空气压力为0.2Mpa；富氧吹炼炉中的吹炼温度为1350℃；
(2)熔剂II(氧化钙)的引入量使得渣贫化炉中渣的CaO/SiO2的重量比为0.4：1；富氧空气II中的氧气的体积浓度为80％，富氧空气II的压力为0.4Mpa；控制渣富氧贫化熔池反应区中的渣贫化炉中的温度为1350℃。
高冰镍：以元素的质量含量计，Ni为74.38％，Co为1.45％，Fe为1.65％，S为21.23％。
高钴低冰镍：以元素的质量含量计，Ni为25.20％，Co为6.37％，Fe为39.62％，S为27.50％。
镍回收率为99.52％，钴回收率为89.32％。
以上详细描述了本公开的可选实施方式，但是，本公开并不限于此。在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，包括各个技术特征以任何其它的合 适方式进行组合，这些简单变型和组合同样应当视为本公开所公开的内容，均属于本公开的保护范围。

Claims (20)

  1. 一种低冰镍生产高冰镍的方法，其特征在于，该方法包括：
    低冰镍吹炼步骤，包括将固态低冰镍、熔剂I连续引入至富氧吹炼炉中进行吹炼，产出高冰镍、吹炼渣以及吹炼烟气。
  2. 根据权利要求1所述的方法，其中，在低冰镍吹炼步骤中，所述吹炼渣通过渣溜槽流入所述渣贫化炉的熔池反应区中；所述熔剂I为二氧化硅；控制所述富氧吹炼炉中的条件，使得所述吹炼渣中的铁元素与所述二氧化硅的质量比为1.5-2.5：1。
  3. 根据权利要求1所述的方法，其中，在低冰镍吹炼步骤中，该方法还包括：向所述富氧吹炼炉中喷入富氧空气I。
  4. 根据权利要求3所述的方法，其中，在低冰镍吹炼步骤中，所述富氧空气I中的氧气的体积浓度为40％～70％，喷入的所述富氧空气I的压力为0.08Mpa～0.2Mpa。
  5. 根据权利要求1所述的方法，其中，在低冰镍吹炼步骤中，该方法还包括：向所述富氧吹炼炉中的一次风口喷入粉煤，所述粉煤的喷入量为入炉物料量的1wt％～3wt％，且所述入炉物料量为所述固态低冰镍和所述熔剂I的用量之和。
  6. 根据权利要求1所述的方法，其中，在低冰镍吹炼步骤中，所述富氧吹炼炉中的吹炼温度为1250～1350℃。
  7. 根据权利要求1所述的方法，其中，在低冰镍吹炼步骤中，该方法还包括：将所述吹炼烟气依次经过余热锅炉以回收余热、电除尘器进行除尘后引入至烟气制酸系统中进行后处理。
  8. 根据权利要求1所述的方法，其中，还包括：
    吹炼渣富氧贫化步骤，包括将还原剂、硫化剂、富氧空气II喷入渣贫化炉的熔池反应区中，以及将所述吹炼渣间断地从所述富氧吹炼炉中引入所述渣贫化炉的熔池反应区中，进行还原硫化反应以产出高钴低冰镍和贫化渣；控制所述富氧空气II对还原剂的氧气过剩系数α为0.4～0.5；控制所述渣贫化炉中的温度为1250～1400℃；所述高钴低冰镍返回所述富氧吹炼炉吹炼。
  9. 根据权利要求1-8中任意一项所述的方法，其中，在吹炼渣富氧贫化步骤中，该方法还包括：向所述渣贫化炉中加入熔剂II；所述熔剂II为石灰石。
  10. 根据权利要求1-8中任意一项所述的方法，其中，在吹炼渣富氧贫化步骤中，所述还原剂选自焦粉、烟煤和无烟煤中的至少一种；所述还原剂中的粒度为200目以上的量为80wt％以上；所述吹炼渣与所述还原剂的用量重量比为100：5～15。
  11. 根据权利要求1-8中任意一项所述的方法，其中，在吹炼渣富氧贫化步骤中，所述硫化剂为硫磺，所述硫化剂中的粒度为200目以上的量为80wt％以上；所述吹炼渣与所述硫化剂的用量重量比为100：3～5。
  12. 根据权利要求1-8中任意一项所述的方法，其中，在吹炼渣富氧贫化步骤中，所述富氧空气II中的氧气的体积浓度为60％～80％，喷入的所述富氧空气II的压力为0.2Mpa～0.4Mpa。
  13. 根据权利要求1-8中任意一项所述的方法，其中，在吹炼渣富氧贫化步骤中，所述还原剂通过压力为0.6Mpa～0.8Mpa的压缩空气喷入所述渣富氧贫化熔池反应区中，以及所述硫化剂通过压力为0.6Mpa～0.8Mpa的氮气喷入所述渣富氧贫化熔池反应区中。
  14. 根据权利要求1-8中任意一项所述的方法，其中，在吹炼渣富氧贫化步骤中，控制所述还原硫化反应的条件，使得所述高钴低冰镍的金属化率Me形式为0.20～0.4；其中，Me形式＝(S理论-S实际)/S理论，S理论为所述高钴低冰镍中硫元素的理论质量含量，S实际为所述高钴低冰镍中硫元素的实际质量含量，所述高钴低冰镍中硫元素的理论质量含量为所述高钴低冰镍中的铁元素、镍元素、钴元素均被完全硫化时的理论含硫量。
  15. 根据权利要求1-8中任意一项所述的方法，其中，在吹炼渣富氧贫化步骤中，所述吹炼渣在所述渣贫化炉中参与所述还原硫化反应的时间为1.5-2.0h，所述吹炼渣的放渣时间为2-3h，所述贫化渣的放渣时间间隔为2-3h。
  16. 一种低冰镍生产高冰镍的装置，其特征在于，该装置中包括：
    富氧吹炼炉；
    渣贫化炉；
    渣溜槽，连接所述富氧吹炼炉和所述渣贫化炉；
    所述富氧吹炼炉和所述渣贫化炉均包括立式固定式炉体；
    所述立式固定式炉体中包括气相区炉身、炉顶盖、采用水冷结构形成的熔池反应区炉身、由耐火材料砌筑而成的炉缸；
    所述炉缸上设有放渣口、虹吸道，所述炉缸的壳体由钢架、拉杆及弹簧部件组成，所述弹簧部件位于所述钢架和所述拉杆之间，所述炉缸的壳体为弹性结构。
  17. 根据权利要求16所述的装置，其中，在所述熔池反应区炉身中，所述水冷结构由多层水冷件组合而成，所述水冷件为铜水套或钢水套；位于所述炉身最下部的水冷件为一层水冷件，所述一层水冷件上部为二层水冷件，其中，所述一层水冷件设有不少于两个一次风口；所述一次风口的角度为水平方向上-5度～5度；
    所述富氧吹炼炉的一次风口用于喷入富氧空气I，所述渣贫化炉的一次风口用于喷入富氧空气II、还原剂以及硫化剂；所述渣贫化炉的加料孔用于加入熔剂II。
  18. 根据权利要求16所述的装置，其中，所述气相区炉身采用耐火材料砌体与水冷水套结构形式交替形成，所述水冷水套结构之间的所述耐火材料砌体的厚度各自独立地为200mm～400mm。
  19. 根据权利要求16所述的装置，其中，所述炉顶盖采用水冷结构，所述水冷结构由多层水冷件组合而成，所述水冷件为铜水套或钢水套；所述炉顶盖上设有不少于1个加料孔。
  20. 根据权利要求16所述的装置，其中，所述熔池反应区炉身的一端高于风口处设有放渣口。
PCT/CN2023/115145 2022-08-30 2023-08-28 一种低冰镍生产高冰镍的方法和装置 WO2024046244A1 (zh)

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