CN112795793A - Comprehensive utilization method of niobite - Google Patents
Comprehensive utilization method of niobite Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
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- C21B11/00—Making pig-iron other than in blast furnaces
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- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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Abstract
The invention provides a comprehensive utilization method of niobite. The comprehensive utilization method of the niobite comprises the following steps: step S1, carrying out reduction side-blown smelting on the niobite in a side-blown furnace to obtain molten iron, slag and phosphorus-containing flue gas; and step S2, deeply reducing the slag in the electric furnace to obtain ferrocolumbium, rare earth-rich slag and electric furnace flue gas. According to the method, the ferro-phosphorus is separated by firstly carrying out reduction side-blown smelting on the niobite, phosphorus in the obtained molten iron and the slag is low, the problem caused by high phosphorus content in the raw materials in the subsequent niobium and rare earth extraction process is solved, and the reduction side-blown smelting and the deep reduction are low-cost smelting modes, so that the cost of metal recovery in the niobite is effectively controlled. Meanwhile, the waste heat of the side-blown converter can be recycled, and the generated electric energy can be used for deep reduction in a subsequent electric furnace, so that the dependence on external electric energy resources is reduced. And in the deep reduction stage, adding an iron-containing material as an external iron source to realize deep reduction to form the niobium molten iron.
Description
Technical Field
The invention relates to the technical field of smelting, in particular to a comprehensive utilization method of niobite.
Background
At present, minerals associated with various elements such as niobium, iron, phosphorus, rare earth and the like are generally separated and enriched by mineral separation, reduction roasting-magnetic separation, reduction roasting-electric furnace melting separation, blast furnace reduction and the like.
The conventional beneficiation method needs combination of various beneficiation processes, including beneficiation methods such as gravity separation, magnetic separation, flotation and the like, has long beneficiation flow, large water consumption and more equipment, is particularly not suitable for water-deficient areas and areas with high environmental protection requirements for water treatment, and has low recovery rate of common elements. The reducing roasting-magnetic separation process is that the niobium-iron ore is reduced and roasted in pre-reducing equipment such as a rotary kiln, a shaft furnace, a rotary hearth furnace or a fluidized bed, and the like, and the product is crushed and then magnetically separated to obtain materials containing iron and phosphorus and materials containing niobium and rare earth. The reduction roasting-electric furnace melting method is also characterized in that the ferrocolumbium is subjected to reduction roasting in pre-reduction equipment such as a rotary kiln, a shaft furnace, a rotary hearth furnace or a fluidized bed, the product can be put into an electric furnace in a hot state for deep reduction, high-phosphorus ferrocolumbium containing phosphorus, niobium and iron and rare earth-rich slag are separated, the obtained high-phosphorus ferrocolumbium has higher subsequent dephosphorization difficulty, and the niobium recovery process is longer. The blast furnace reduction niobite process is to sinter and agglomerate niobite and reduce the niobite in a blast furnace, and the obtained products are high-phosphorus niobite and rare earth-rich slag, and the problems of high difficulty in subsequent dephosphorization of the niobite and long niobium recovery process are also existed.
Chinese patent application publication No. CN101787450A discloses a method for enriching tantalum and niobium, rare earth elements, iron and phosphorus from rare metal ores, which comprises mixing minerals, flux and reducing agent in proportion, pressing into balls, roasting, magnetically separating the roasted product to enrich iron and phosphorus in magnetic substances, and enriching tantalum, niobium, rare earth and other elements in slag.
Chinese patent application No. CN105154659A discloses a method for synchronously extracting iron and niobium from bayan obo low-grade ore, which comprises pre-reducing and melting niobium-containing mineral, separating molten iron and niobium-containing slag, chlorinating the slag to obtain niobium chloride, and extracting niobium.
The Chinese patent application with the application publication number of CN105907990A discloses a method for producing ferrocolumbium by prereduction of a rotary hearth furnace and melting separation of an electric furnace, but the method does not have dephosphorization effect, the content of the obtained ferrocolumbium and phosphorus is higher, and only raw materials with lower phosphorus content can be processed.
Therefore, the existing beneficiation method has long process flow, large water consumption and more equipment, is particularly not suitable for water-deficient areas and areas with high requirements on water treatment environmental protection, and has lower recovery rate of common elements. The modes of reduction roasting-magnetic separation, reduction roasting-electric furnace melting separation, blast furnace reduction and the like all have the problem of incomplete separation of elements such as phosphorus, iron, niobium, rare earth and the like, particularly, phosphorus is difficult to separate out, so that the dephosphorization difficulty of a subsequent treatment process is high, and the obtained niobium-iron product has low value. The processes of reduction roasting-magnetic separation, reduction roasting-electric furnace melting separation, blast furnace reduction and the like also have the problems of long pretreatment process, need of pelletizing or sintering process and large consumption of coke in the blast furnace reduction method. The reduction roasting-electric furnace melting process needs additional consumption of electric energy, has high energy consumption cost and is particularly not suitable for areas with electricity shortage or higher electricity consumption cost.
Disclosure of Invention
The invention mainly aims to provide a comprehensive utilization method of niobite, and aims to solve the problems that in the prior art, the niobite is high in recovery cost and the ferro-phosphorus is difficult to separate.
In order to achieve the above object, according to an aspect of the present invention, there is provided a niobite comprehensive utilization method including: step S1, carrying out reduction side-blown smelting on the niobite in a side-blown furnace to obtain molten iron, slag and phosphorus-containing flue gas; and step S2, deeply reducing the slag in the electric furnace to obtain ferrocolumbium, rare earth-rich slag and electric furnace flue gas.
Further, the step S1 includes: and carrying out reduction side-blown smelting on the material comprising the first reducing agent and the niobite in a side-blown furnace, forming a slag layer and a metal molten pool in the side-blown furnace, wherein the slag layer is arranged above the metal molten pool, and injecting fuel and oxygen-enriched gas into the side-blown furnace in the reduction side-blown smelting process.
Further, the fuel and the oxygen-enriched gas are injected into the slag layer.
Furthermore, the temperature of the reduction side-blown smelting is 1250-1450 ℃.
Further, the fuel is selected from any one of coal powder, natural gas, coal gas and heavy oil, and the oxygen volume content in the oxygen-enriched gas is 40-99%.
Further, the first reducing agent is any one or more of bituminous coal, anthracite, lignite and coke.
Further, the first reducing agent is a bulk reducing agent or a particulate reducing agent.
Further, the mass ratio of the niobite to the first reducing agent is 100: 0-50.
Further, the ratio of the above is 100: 20-40.
Further, the step S2 includes: and deeply reducing the slag, the iron-containing material, the second reducing agent and the flux in an electric furnace to obtain ferrocolumbium and rare-earth-rich slag.
Further, the temperature of the deep reduction is 1500-1600 ℃.
Further, the slag is a hot slag directly produced from a side-blown converter, and the iron-containing material is preferably any one selected from molten iron, pig iron, steel scrap, iron-containing metallized pellets, iron-containing oxidized pellets, and iron ore.
Further, the second reducing agent is selected from any one or more of bituminous coal, anthracite coal, lignite coal and coke.
Further, the flux is selected from any one of lime, limestone and dolomite.
Further, the weight ratio of the columbite iron ore, the iron-containing material, the second reducing agent and the flux is 1000: 200-400: 5-40: 100 to 300.
Further, at least part of the iron-containing material, at least part of the second reducing agent and at least part of the flux are added in the form of composite pellets, and the main components of the composite pellets comprise iron, carbon and calcium oxide.
Further, the weight ratio of the iron to the calcium oxide to the carbon is 100: 40-110: 2-15, wherein the weight content of iron in the composite pellets is 40-70%, and the weight ratio of the composite pellets to the columbite iron ore is 0-400: 1000.
further, the comprehensive utilization method of the niobite also comprises the following steps: carrying out dust removal treatment on the phosphorus-containing flue gas to obtain phosphorus-containing smoke dust and dust-removing flue gas; optionally, the dedusting flue gas is subjected to purification treatment and evacuation after power generation by a waste heat boiler.
Further, the comprehensive utilization method of the niobite combines the electric furnace flue gas and the phosphorus-containing flue gas and then carries out dust removal treatment.
Further, the electric energy generated by the power generation of the dust-removed flue gas through the waste heat boiler is used as at least part of the electric energy of the electric furnace in the step S2.
Further, the columbite is a rough-separated columbite obtained by performing gravity separation on the columbite ore.
By applying the technical scheme, in the comprehensive utilization method of the niobite, the niobite is subjected to reduction side-blown smelting at first, phosphorus generated in the reduction process is discharged along with flue gas in time by using the side-blown advantage of the reduction side-blown smelting, separation of phosphorus and iron is realized, phosphorus in the obtained molten iron and slag is low, and the problem caused by high phosphorus content in raw materials in the subsequent process of extracting niobium and rare earth is solved; and based on the characteristics of side-blown smelting, the side-blown fuel mode is used for supplying heat, so that the heat supply cost is lower. In addition, the chlorination is carried out without using chlorine gas with higher cost in the process, and the reduction side-blown smelting and the deep reduction are both low-cost smelting modes, so that the cost of metal recovery in the niobium-iron ore is effectively controlled. Meanwhile, the waste heat of the side-blown converter can be recycled, and the generated electric energy can be used for deep reduction in a subsequent electric furnace, so that the dependence on external electric energy resources is reduced. And in the deep reduction stage, adding an iron-containing material as an external iron source to realize deep reduction to form the niobium molten iron. The phosphorus-containing flue gas, molten iron, ferrocolumbium, rare earth slag and the like obtained by the comprehensive utilization method of the ferrocolumbium can be directly sold or made into corresponding products for sale, so that the separation and enrichment of elements such as phosphorus, iron, niobium, rare earth and the like in the ferrocolumbium are realized, and the aim of comprehensively utilizing various valuable elements in the ferrocolumbium is fulfilled.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the present application, in the prior art, the niobite recovery cost is high, and the ferrophosphorus is difficult to separate, and in order to solve the problem, the present application provides a comprehensive niobite utilization method, which includes: step S1, carrying out reduction side-blown smelting on the niobite in a side-blown furnace to obtain molten iron, slag and phosphorus-containing flue gas; and step S2, deeply reducing the slag in the electric furnace to obtain ferrocolumbium, rare earth-rich slag and electric furnace flue gas.
According to the comprehensive utilization method of the niobite, the niobite is subjected to reduction side-blown smelting, phosphorus generated in the reduction process is discharged along with flue gas in time by using the side-blown advantage of the reduction side-blown smelting, separation of phosphorus and iron is achieved, phosphorus in the obtained molten iron and slag is low, and the problem caused by high phosphorus content in raw materials in the subsequent process of extracting niobium and rare earth is solved; and based on the characteristics of side-blown smelting, the side-blown fuel mode is used for supplying heat, so that the heat supply cost is lower. In addition, the chlorination is carried out without using chlorine gas with higher cost in the process, and the reduction side-blown smelting and the deep reduction are both low-cost smelting modes, so that the cost of metal recovery in the niobium-iron ore is effectively controlled. Meanwhile, the waste heat of the side-blown converter can be recycled, and the generated electric energy can be used for deep reduction in a subsequent electric furnace, so that the dependence on external electric energy resources is reduced. And in the deep reduction stage, adding an iron-containing material as an external iron source to realize deep reduction to form the niobium molten iron.
Specifically, the above-described side-blown reduction smelting process is, in addition to the conventional carbon combustion reaction, such as:
C+O2↑=CO↑、2C+O2↑=2CO↑、CH4↑+3O2↑=CO2↑+2H2O↑，
reduction of iron also occurs as follows:
C+Fe2O3=2FeO+CO↑、CO↑+Fe2O3=2FeO+CO2↑、C+FeO=Fe+CO↑；
and reductive volatilization of P, such as:
5C+P2O5=2P↑+5CO↑、5C+2P2O5=4P↑+5CO2↑，
the reduced P part enters molten iron, and the other part is volatilized into flue gas in the form of phosphorus simple substance.
In the deep reduction stage in an electric furnace, Nb is contained in the slag2O5Initially reduced and formed into molten iron of niobium, Nb, together with an added iron source and carbon2O5+5C =2Nb +5CO ↓, and CO were not generated due to strong reducibility at this stage2。
The phosphorus-containing flue gas, molten iron, ferrocolumbium, rare earth slag and the like obtained by the comprehensive utilization method of the ferrocolumbium can be directly sold or made into corresponding products for sale, so that the separation and enrichment of elements such as phosphorus, iron, niobium, rare earth and the like in the ferrocolumbium are realized, and the aim of comprehensively utilizing various valuable elements in the ferrocolumbium is fulfilled.
The niobite treated in step S1 described above in this application may be a niobite ore or a roughed niobite obtained by gravity separation of a niobite ore. Even after reselection, most of quartz, namely silicate components with low valuable element content in the ore are removed through the reselection process, so that the process is simple, less in process and less in water consumption compared with the mineral separation process in the prior art, and the loss of various valuable metals is avoided. By adopting the method, the niobite can be directly treated in the side-blown furnace, raw material pretreatment procedures such as dry pelletizing, pre-reduction and the like are not needed, and smelting supporting facilities are reduced.
In some embodiments of the present application, the step S1 includes: and carrying out reduction side-blown smelting on the material comprising the first reducing agent and the niobite in a side-blown furnace, forming a slag layer and a metal molten pool in the side-blown furnace, wherein the slag layer is arranged above the metal molten pool, and injecting fuel and oxygen-enriched gas into the side-blown furnace during the reduction side-blown smelting, preferably injecting the fuel and the oxygen-enriched gas into the slag layer. Preferably, the temperature of the reduction side-blown smelting is 1250-1450 ℃. The fuel and the oxygen-enriched gas which are sprayed into the side-blown furnace are combusted to provide heat energy for reduction side-blown smelting, so that the heat is fully utilized; on the other hand, when fuel and oxygen-enriched gas are sprayed into the slag layer, disturbance of the slag is realized, and volatilization of phosphorus is accelerated.
The fuel and the reducing agent adopted in the reduction side-blown smelting process can be selected by taking the fuel and the reducing agent commonly used in ore smelting side-blown smelting in the prior art as reference, and in order to improve the utilization of heat energy and reduce the introduction of impurities, the fuel is preferably selected from any one of coal powder, natural gas, coal gas and heavy oil, and the volume content of oxygen in the oxygen-enriched gas is 40-99%.
Preferably, the first reducing agent is any one or more of bituminous coal, anthracite coal, lignite coal and coke. Preferably, the first reducing agent is a block reducing agent or a granular reducing agent, so that the first reducing agent is prevented from being carried away by the flue gas and cannot be fully utilized. In the side-blown reduction smelting process, the reduction degree and the flue gas yield can be regulated and controlled by adjusting the ratio of the niobite to the first reducing agent, and in order to realize iron reduction as much as possible and control subsequent flue gas treatment load, the mass ratio of the niobite to the first reducing agent is preferably 100: 0-50, and preferably 100: 20-40.
In the reduction side-blown smelting stage, coal or coke is both fuel and reducing and can be used as a reducing agent, and the coal or coke can be added in two ways, namely, pre-mixed with the niobia (such as pre-mixed through a belt) or sprayed into a molten pool through a side-blown lance, so that when coal powder is used as fuel, the coal powder can be used as fuel to provide heat and can be used as a reducing agent for reducing iron.
In other embodiments of the present application, the step S2 includes: deeply reducing the furnace slag, the iron-containing material, the second reducing agent and the flux in an electric furnace to obtain ferrocolumbium and rare earth-rich slag, wherein the preferable deep reduction temperature is 1500-1600 ℃.
The low-phosphorus and low-iron slag obtained by side-blown reduction smelting is deeply reduced with the iron-containing material, the second reducing agent and the flux, and in the deep reduction stage, the addition of the iron-containing material has the function of increasing an iron source and the reducing agent, so that the introduction of impurities in the deep reduction stage is reduced, the deep reduction efficiency and the reduction effect are improved, the reduction of power consumption is facilitated, and the product quality is improved. The obtained niobium-iron-containing water is increased, the niobium trapping by metal is promoted, the niobium yield is improved, and the phosphorus content in the niobium-iron is low.
In order to improve the energy efficiency, it is preferable that the slag is hot slag directly produced from a side-blown furnace.
The iron-containing material can be selected from iron-containing materials commonly used in the industry at present, and in order to reduce cost and facilitate utilization, the iron-containing material is preferably selected from any one of molten iron, pig iron, steel scrap, iron-containing metallized pellets, iron-containing oxidized pellets and iron ore. The second reducing agent used for the deep reduction may be any one or more of those commonly used for deep reduction, and in order to reduce costs, it is preferable that the second reducing agent is selected from any one or more of bituminous coal, anthracite coal, lignite coal and coke. The flux can promote the melting of solid materials such as iron-containing materials, and is preferably selected from any one of lime, limestone and dolomite in order to reduce cost.
Through experimental exploration, the weight ratio of the columbite iron ore, the iron-containing material, the second reducing agent and the flux is preferably 1000: 200-400: 5-40: 100-300 to improve the reduction efficiency of iron in the slag.
In some embodiments, at least part of the iron-containing material, at least part of the second reducing agent and at least part of the flux are added in a composite pellet mode, so that the material adding mode is simplified, and the accuracy of the proportioning of each main element is improved. Preferably, the main components of the composite pellet comprise iron, carbon and calcium oxide, and the weight ratio of the iron to the calcium oxide to the carbon is preferably 100: 40-110: 2-15, wherein the weight content of iron in the composite pellet is 40-70%. The weight ratio of the composite pellets to the columbite iron ore is 0-400: 1000 to improve the reduction efficiency of iron in the slag. The iron-containing material, the second reducing agent and the flux can be partially or completely added in a composite pellet mode, so that the using amount of the composite pellets can be in a range from 0 to 400: 1000, provided that the weight ratio of niobite, iron-containing material, second reducing agent and flux is 1000: 200-400: 5-40: 100 to 300 times.
In some embodiments, the comprehensive utilization method of niobite further includes: carrying out dust removal treatment on the phosphorus-containing flue gas to obtain phosphorus-containing smoke dust and dust-removing flue gas; optionally, the dedusting flue gas is subjected to purification treatment and evacuation after power generation by a waste heat boiler. Carrying out dust removal treatment on the phosphorus-containing flue gas, and collecting phosphorus in smoke dust; the dedusting flue gas can then be used for power generation through a waste heat boiler so as to utilize waste heat in the dedusting flue gas. The flue gas discharged by the waste heat boiler can be emptied by conventional purification treatment. Through the process, the heat and resources of the flue gas generated by the reduction side-blown smelting are effectively recycled, and the comprehensive benefits of the method are improved.
The flue gas generated by the deep reduction of the electric furnace is less, and in order to reduce equipment investment, the comprehensive utilization method of the niobite is preferably used for combining the flue gas of the electric furnace and the flue gas containing phosphorus and then carrying out dust removal treatment.
Further, in order to realize comprehensive utilization of energy, it is preferable that the electric energy generated by the exhaust-heat boiler through the dust-removed flue gas is used as at least part of the electric energy of the electric furnace in step S2. When the method is implemented, the reduction degree of reduction side-blown smelting and the type of materials prepared in the deep reduction stage can be adjusted, the smoke waste heat generating capacity and the power consumption of the deep reduction stage can be flexibly adjusted, the balance of power generation and sales in a plant area can be realized, the external electric energy is not depended on, the electric energy is not surplus, the plant can be independently built without depending on the external social infrastructure conditions, the method is particularly suitable for the underdeveloped areas of the power system infrastructure, the requirement on the process plant building conditions is low, and the site selection is flexible.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
The following examples used the following niobia ore compositions in weight percent, where niobia ore one was the niobia ore raw and niobia ore two was the ore after rough beneficiation.
TABLE 1
Example 1
And directly feeding the first columbite into a charging hole of a side-blown furnace through a belt conveyor, and putting into the furnace (the pre-mixed coal amount is 0).
The first niobium-iron ore is put into a side-blown furnace molten pool for reduction side-blown smelting, the pulverized coal and the oxygen-enriched gas are sprayed into the molten pool by a side-blown spray gun, the oxygen-enriched gas is formed by mixing oxygen and air, and when each ton of niobium-iron ore is treated, the main technical parameters of a side-blown furnace injection system are as follows: 292kg of coal powder and 290Nm of oxygen3Air 131Nm3The oxygen-enriched concentration is 75.07 percent, the temperature of a side-blown converter molten pool is 1450-1500 ℃, and the furnace slag 673kg, the phosphorus-containing molten iron 106kg, the smoke 78kg and the high-temperature smoke 784Nm can be produced3. Wherein, the slag components are as follows: 3.22% FeO, 0.47% P2O5、0.99%Nb2O51.21% REO; the phosphorus-containing molten iron comprises the following components: 0.1% C, 3.89% P, 0.03% Nb; the smoke dust contains 27.99 percent of phosphorus.
The slag is put into an electric furnace for deep reduction smelting, 8.47kg of anthracite, 228kg of lime, 202kg of pig iron blocks, 339KWh of power consumption and 1500-1550 ℃ of an electric furnace molten pool are required to be added for treating each ton of ferrocolumbium in the deep reduction stage of the electric furnace, and 861kg of slag and 220kg of ferrocolumbium can be produced. Wherein, the slag components are as follows: 0.32% FeO, 0.04% Nb2O50.95% REO; niobium-iron component: 3.8% of C, 0.08% of P and 2.0% of Nb.
The side-blown converter and the electric furnace high-temperature flue gas are converged and then used for generating power by using a waste heat boiler, the generated energy of the waste heat boiler for treating each ton of the niobium-iron ore is 695KWh, and the electric furnace is powered.
Example 2
The niobium-iron-ore anthracite is directly fed into a charging hole of a side-blown furnace by using belt ingredients (100 kg of anthracite is added to each ton of ore) according to the mass ratio of 100:10, and then the materials are put into the furnace.
The first columbite and anthracite are put into a side-blown furnace molten pool for reduction side-blown smelting, the coal powder and oxygen-enriched gas are sprayed into the molten pool by a side-blown spray gun, the oxygen-enriched gas is formed by mixing oxygen and air, and when each ton of columbite is treated, the main technical parameters of a side-blown furnace injection system are as follows: 160kg of coal powder and 268Nm of oxygen3Air 37Nm3The oxygen-enriched concentration is 89.98 percent, the temperature of a side-blown converter molten pool is 1350-1400 ℃, and 668kg of slag, 109kg of phosphorus-containing molten iron, 75kg of smoke dust and 650Nm of high-temperature smoke gas can be produced3. Wherein, the slag components are as follows: 2.57% FeO, 0.94% P2O5、1.00%Nb2O51.22% REO; the phosphorus-containing molten iron comprises the following components: 0.13% C, 3.77% P, 0.03% Nb; the smoke dust contains 27.57 percent of phosphorus.
The slag is put into an electric furnace for deep reduction smelting, 9.5kg of anthracite, 248kg of lime, 334kg of molten iron, 332KWh of power consumption and 1500-1550 ℃ of an electric furnace molten pool are required to be added for treating each ton of niobium-iron ore in the deep reduction stage of the electric furnace, and 877kg of slag and 348kg of niobium-iron can be produced. Wherein, the slag components are as follows: 0.26% FeO, 0.03% Nb2O50.93% REO; niobium-iron component: 4.0% C, 0.09% P, 1.29% Nb.
The side-blown converter and the electric furnace high-temperature flue gas are converged and then used for generating power by using a waste heat boiler, the generated energy of the waste heat boiler for treating each ton of the niobite is 590KWh, and the electric furnace is powered.
Example 3
And directly feeding the niobium-iron ore II and the anthracite into a charging hole of a side-blown furnace by using belt ingredients (400 kg of anthracite is added to each ton of ore) according to the mass ratio of 100:40, and putting into the furnace.
The second columbite and anthracite are put into a side-blown furnace molten pool for reduction side-blown smelting, natural gas and oxygen-enriched gas are sprayed into the molten pool by a side-blown spray gun, the oxygen-enriched gas is formed by mixing oxygen and air, and when each ton of columbite is treated, the main technical parameters of a side-blown furnace injection system are as follows: natural gas 30Nm3278Nm of oxygen3Air 722Nm3The oxygen-enriched concentration is 42.83 percent, the temperature of a side-blown converter molten pool is 1350-1400 ℃, and 605kg of slag, 172kg of phosphorus-containing molten iron, 91kg of smoke dust and 1410Nm of high-temperature smoke gas can be produced3. Wherein, the slag components are as follows: 3.22% FeO, 0.63% P2O5、1.74%Nb2O52.12% REO; the phosphorus-containing molten iron comprises the following components: 0.11% C, 2.91% P, 0.03% Nb; the smoke dust contains 29.16 percent of phosphorus.
Furnace slag is put into an electric furnace for deep reduction smelting, and 388kg of composite pellets (Fe in the pellets: CaO:c = 100: 57: 15) 371KWh power consumption, 1550-1600 ℃ electric furnace molten pool temperature, 676kg slag and 194kg ferroniobium can be produced. Wherein, the slag components are as follows: 0.32% FeO, 0.08% Nb2O51.88% REO; niobium-iron component: 4.3% of C, 0.1% of P and 3.55% of Nb.
The side-blown converter and the electric furnace high-temperature flue gas are converged and then used for generating power by using a waste heat boiler, the generated energy of the waste heat boiler for treating each ton of the niobite is 1183KWh, and the electric furnace is powered.
Example 4
And directly feeding the niobium-iron ore II into a charging hole of a side-blown converter, and putting into the furnace.
And the second columbite is put into a side-blown furnace molten pool for reduction side-blown smelting, the pulverized coal, natural gas and oxygen-enriched gas are sprayed into the molten pool by a side-blown spray gun, the oxygen-enriched gas is formed by mixing oxygen and air, and when each ton of columbite is treated, the main technical parameters of a side-blown furnace injection system are as follows: 300kg of pulverized coal and 30Nm of natural gas are injected3304Nm of oxygen3The oxygen concentration is 99 percent, the side-blown converter molten pool temperature is 1400-1450 ℃, 594kg of slag, 172kg of phosphorus-containing molten iron, 91kg of smoke and 658Nm of high-temperature smoke are produced3. Wherein, the slag components are as follows: 3.52% FeO, 0.64% P2O5、1.77%Nb2O52.16% REO; the phosphorus-containing molten iron comprises the following components: 0.13% C, 2.9% P, 0.04% Nb; the soot dust contains 29.24% of phosphorus.
The slag is put into an electric furnace for deep reduction smelting, 356kg of steel scraps, 35kg of coke, 144kg of lime and 378KWh of electricity are consumed for treating each ton of ferrocolumbium in the deep reduction stage of the electric furnace, the temperature of a molten pool of the electric furnace is 1550-1600 ℃, and 646kg of slag and 384kg of ferrocolumbium can be produced. Wherein, the slag components are as follows: 0.19% FeO, 0.05% Nb2O51.98% REO; niobium-iron component: 2.5% of C, 0.04% of P and 1.81% of Nb.
The side-blown converter and the electric furnace high-temperature flue gas are converged and then used for generating power by using a waste heat boiler, the generated energy of the waste heat boiler for treating each ton of the niobite is 1532KWh, and the electric furnace is supplied with power.
Example 5
And directly feeding the niobium-iron ore II into a charging hole of a side-blown converter, and putting into the furnace.
The niobium-iron ore II is put into a side-blown furnace molten pool for reduction side-blown smelting, and coalThe powder, the natural gas and the oxygen-enriched gas are sprayed into the molten pool by a side-blowing spray gun, the oxygen-enriched gas is formed by mixing oxygen and air, and when each ton of columbite is treated, the main technical parameters of a side-blowing furnace spraying system are as follows: 300kg of pulverized coal and 30Nm of natural gas are injected3304Nm of oxygen3The oxygen concentration is 99 percent, the side-blown converter molten pool temperature is 1400-1450 ℃, 594kg of slag, 172kg of phosphorus-containing molten iron, 91kg of smoke and 658Nm of high-temperature smoke are produced3. Wherein, the slag components are as follows: 3.52% FeO, 0.64% P2O5、1.77%Nb2O52.16% REO; the phosphorus-containing molten iron comprises the following components: 0.13% C, 2.9% P, 0.04% Nb; the soot dust contains 29.24% of phosphorus.
The slag enters an electric furnace for deep reduction smelting, 398kg of steel scraps, 50kg of coke, 97kg of lime and 340KWh of power are consumed for treating each ton of ferrocolumbium in the deep reduction stage of the electric furnace, the temperature of a molten pool of the electric furnace is 1550-1600 ℃, and 618kg of slag and 436kg of ferrocolumbium can be produced. Wherein, the slag components are as follows: 0.19% FeO, 0.03% Nb2O52.07% REO; niobium-iron component: 4.5% of C, 0.03% of P and 1.64% of Nb.
The side-blown converter and the electric furnace high-temperature flue gas are converged and then used for generating power by using a waste heat boiler, the generated energy of the waste heat boiler for treating each ton of the niobite is 1202KWh, and the electric furnace is powered.
Example 6
In contrast to example 5, in the deep reduction stage of the electric furnace, when less iron source is added, i.e. niobite: the mass ratio of steel scraps is 1000:100, and Nb in the obtained slag at the moment2O5The content of 0.17% higher than 0.03% in example 5 indicates that the niobium trapping is facilitated when the iron-containing material is appropriately added in the deep reduction stage.
Comparative example 1
Compared with example 5, in the deep reduction stage of the electric furnace, the deep reduction can not be carried out without adding steel scraps, and the recovery of niobium can not be realized by obtaining a metal phase.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
1) the columbite iron ore raw material is simply reselected or directly enters a storage bin without mineral separation, and is used as a raw material, so that the mineral separation process is simplified or omitted;
2) after the niobite and the reducing agent are mixed by the belt conveyor, the mixture is directly put into a side-blown converter, and a plurality of processes such as temperature rise, melting, reduction and the like are quickly realized in the converter, so that a raw material pretreatment process is omitted, and the treatment process is short;
3) the P, Nb content in the molten iron obtained by side blowing reduction is respectively less than 4 percent and less than 0.05 percent, the phosphorus and niobium content in the molten iron is lower, and the separation of iron is realized.
4) The contents of Fe and P in the slag obtained by side-blown reduction are respectively 1-5% and 0.1-0.5%, the phosphorus content in the slag is low, and the niobium and rare earth elements basically remain in the slag.
5) The smelting is carried out in the side-blown furnace by coal injection, reduction and volatilization, the reduction and volatilization of phosphorus in the raw materials are promoted, the volatilization separation of phosphorus is realized, the phosphorus volatilization rate is more than 60 percent, most of phosphorus enters smoke dust, the smoke dust containing phosphorus can be obtained, the phosphorus content of the smoke dust is more than 20 percent, and the smoke dust can be used as the raw material for extracting phosphorus.
6) The high-temperature flue gas of the side-blown converter is generated by recovering waste heat by using a waste heat boiler, the dust removal of the flue gas can reach the standard and be discharged, the recovered electric energy is used for the deep reduction of a subsequent electric furnace, and other surplus electric energy is used for daily power utilization or external transmission in a plant area.
7) The side-blown slag enters an electric furnace for deep reduction, and iron-containing materials, reducing agents and fusing agents or composite pellets are added in the deep reduction stage, so that the quality of a metal phase is improved, and the capturing effect of the metal on niobium in the slag can be enhanced. For example, the molten iron and the pig iron blocks contain carbon, so that the iron can be supplemented, the reduction performance is high, and the addition of the molten iron and the pig iron also has the effects of reducing the addition of a reducing agent and reducing the heat consumption of the electric furnace.
8) The contents of C, Nb and P in the niobium molten iron obtained by the electric furnace deep reduction are respectively 2.0-4.5%, 0.5-4% and less than 0.1%, the phosphorus content is low, and the subsequent dephosphorization cost is low.
9) The contents of Fe, Nb and RE in the rare earth-rich slag obtained by the deep reduction of the electric furnace are respectively less than 0.5 percent, less than 0.1 percent and more than 0.5 percent, the extraction of niobium is more thorough, the rare earth enrichment effect is good, and the separation effect of niobium and rare earth is enhanced.
10) The flue gas produced by the electric furnace is merged into the side-blown furnace flue gas treatment system, the used electric energy is generated by the waste heat of the high-temperature flue gas of the side-blown furnace, the distribution of the material inflow energy flow is reasonable, the reduction degree of the side-blown furnace can be dynamically adjusted according to the reduction degree, the deep reduction electric energy consumption is further adjusted, and the reasonable distribution of the plant energy and the material can be conveniently controlled.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (22)
1. A comprehensive utilization method of niobite is characterized by comprising the following steps:
step S1, carrying out reduction side-blown smelting on the niobite in a side-blown furnace to obtain molten iron, slag and phosphorus-containing flue gas;
and step S2, deeply reducing the slag in an electric furnace to obtain ferrocolumbium, rare earth-rich slag and electric furnace flue gas.
2. The integrated niobium-iron ore utilization method according to claim 1, wherein the step S1 includes:
and carrying out reduction side-blown smelting on the material comprising the first reducing agent and the niobite in a side-blown furnace, forming a slag layer and a metal molten pool in the side-blown furnace, wherein the slag layer is arranged above the metal molten pool, and injecting fuel and oxygen-enriched gas into the side-blown furnace in the reduction side-blown smelting process.
3. The integrated columbite and siderite utilization method as claimed in claim 2, wherein said fuel and said oxygen-rich gas are injected into said slag layer.
4. The niobite comprehensive utilization method according to any one of claims 1 to 3, characterized in that the temperature of the reduction side-blown smelting is 1250 to 1450 ℃.
5. The method for comprehensively utilizing the niobite according to claim 2, wherein the fuel is selected from any one of pulverized coal, natural gas, coal gas and heavy oil, and the oxygen-enriched gas contains 40-99% of oxygen by volume.
6. The method for comprehensively utilizing niobite according to claim 2, wherein the first reducing agent is any one or more of bituminous coal, anthracite coal, lignite coal, and coke.
7. The integrated niobium-iron ore utilization method according to claim 2 or 6, wherein the first reducing agent is a lump reducing agent or a granular reducing agent.
8. The method for comprehensively utilizing the niobite according to claim 2 or 6, characterized in that the mass ratio of the niobite to the first reducing agent is 100: 0-50.
9. The method for comprehensively utilizing the niobite according to claim 8, characterized in that the mass ratio of the niobite to the first reducing agent is 100: 20-40.
10. The integrated niobium-iron ore utilization method according to claim 1, wherein the step S2 includes:
and deeply reducing the slag, the iron-containing material, the second reducing agent and the flux in the electric furnace to obtain ferrocolumbium and rare-earth-rich slag.
11. The method for comprehensively utilizing the niobite according to claim 1 or 10, characterized in that the deep reduction temperature is 1500-1600 ℃.
12. The integrated columbite utilization method as claimed in claim 10, wherein said slag is a hot slag directly produced from said side-blown furnace.
13. The method for comprehensively utilizing niobite according to claim 10, wherein the iron-containing material is any one selected from molten iron, pig iron, steel scrap, iron-containing metallized pellets, iron-containing oxidized pellets, and iron ore.
14. The integrated columbite utilization method as claimed in claim 10, wherein said second reducing agent is selected from any one or more of bituminous coal, anthracite coal, lignite coal and coke.
15. The integrated columbite and pyrite utilization method of claim 10, wherein said flux is selected from any one of lime, limestone and dolomite.
16. The integrated columbite utilization method as claimed in any one of claims 10 and 12 to 15, wherein the weight ratio of the columbite, the iron-containing material, the second reducing agent and the flux is 1000: 200-400: 5-40: 100 to 300.
17. The integrated niobium-iron ore utilization method as claimed in claim 10, wherein at least a part of the iron-containing material, at least a part of the second reducing agent and at least a part of the flux are added in the form of composite pellets, and main components of the composite pellets include iron, carbon and calcium oxide.
18. The integrated columbite utilization method as claimed in claim 17, wherein the weight ratio of said iron, said calcium oxide and said carbon is 100: 40-110: 2-15, wherein the weight content of iron in the composite pellet is 40-70%, and the weight ratio of the composite pellet to the columbite iron ore is 0-400: 1000.
19. the integrated columbite utilization method as claimed in claim 1, further comprising:
carrying out dust removal treatment on the phosphorus-containing flue gas to obtain phosphorus-containing smoke dust and dust removal flue gas;
optionally, the dedusting flue gas is subjected to purification treatment and evacuation after power generation by a waste heat boiler.
20. The integrated niobium-iron ore utilization method according to claim 19, wherein the dust removal treatment is performed after the electric furnace flue gas and the phosphorus-containing flue gas are combined.
21. The integrated niobium-iron ore utilization method as claimed in claim 19, wherein the electric energy generated by the dust-removed flue gas passing through the waste heat boiler is used as at least part of the electric energy of the electric furnace in the step S2.
22. The method for comprehensively utilizing the niobite according to claim 1, characterized in that the niobite is a coarsely-selected niobite obtained by reselecting a niobite ore.
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| CN114959157A (en) * | 2022-04-22 | 2022-08-30 | 中国恩菲工程技术有限公司 | Method and device for producing low-phosphorus molten iron by high-phosphorus reduced iron |
| WO2022194285A1 (en) * | 2021-03-19 | 2022-09-22 | 中国恩菲工程技术有限公司 | Comprehensive utilization method for columbite |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU676916A1 (en) * | 1977-11-09 | 1979-07-30 | Институт Минеральных Ресурсов Министерства Геологии Украинской Сср | Method of determining minerals of tantalite-columbite group |
| US4454013A (en) * | 1982-05-28 | 1984-06-12 | Skf Steel Engineering Ab | Method of separating iron and its alloy metals from fine-grained crude oxidic products |
| CN106987673A (en) * | 2017-03-31 | 2017-07-28 | 北京科技大学 | A kind of method that selecting smelting combination is enriched with niobium from titaniferous ferro-niobium concentrate |
| CN111235389A (en) * | 2020-03-30 | 2020-06-05 | 中国恩菲工程技术有限公司 | Smelting method and device of vanadium titano-magnetite |
| CN111705225A (en) * | 2020-07-24 | 2020-09-25 | 中国恩菲工程技术有限公司 | Method and device for preparing nickel matte |
| CN211947176U (en) * | 2020-03-30 | 2020-11-17 | 中国恩菲工程技术有限公司 | Smelting device of vanadium titano-magnetite |
| CN112410586A (en) * | 2020-10-27 | 2021-02-26 | 长沙矿冶研究院有限责任公司 | Method for comprehensively recovering niobium, rare earth and titanium from multi-metal ore containing iron, niobium and rare earth |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092242C (en) * | 1996-07-25 | 2002-10-09 | 冶金工业部长沙矿冶研究院 | Method for smelting ferrocolumbium by two-step electric furnace reduction |
| CN202770196U (en) * | 2012-06-15 | 2013-03-06 | 成都昊地科技有限责任公司 | Oxygen side blowing bath smelting system for non-ferrous metal smelting |
| CN106755651A (en) * | 2016-12-10 | 2017-05-31 | 东北大学 | A kind of method reclaimed containing rare earth and/or niobium slag metallurgy one-step method |
| CN211451836U (en) * | 2019-12-13 | 2020-09-08 | 洛南环亚源铜业有限公司 | Oxygen-enriched side-blown converter |
| CN112795793B (en) * | 2021-03-19 | 2021-08-03 | 中国恩菲工程技术有限公司 | Comprehensive utilization method of niobite |
-
2021
- 2021-03-19 CN CN202110298156.2A patent/CN112795793B/en active Active
-
2022
- 2022-03-18 WO PCT/CN2022/081742 patent/WO2022194285A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU676916A1 (en) * | 1977-11-09 | 1979-07-30 | Институт Минеральных Ресурсов Министерства Геологии Украинской Сср | Method of determining minerals of tantalite-columbite group |
| US4454013A (en) * | 1982-05-28 | 1984-06-12 | Skf Steel Engineering Ab | Method of separating iron and its alloy metals from fine-grained crude oxidic products |
| CN106987673A (en) * | 2017-03-31 | 2017-07-28 | 北京科技大学 | A kind of method that selecting smelting combination is enriched with niobium from titaniferous ferro-niobium concentrate |
| CN111235389A (en) * | 2020-03-30 | 2020-06-05 | 中国恩菲工程技术有限公司 | Smelting method and device of vanadium titano-magnetite |
| CN211947176U (en) * | 2020-03-30 | 2020-11-17 | 中国恩菲工程技术有限公司 | Smelting device of vanadium titano-magnetite |
| CN111705225A (en) * | 2020-07-24 | 2020-09-25 | 中国恩菲工程技术有限公司 | Method and device for preparing nickel matte |
| CN112410586A (en) * | 2020-10-27 | 2021-02-26 | 长沙矿冶研究院有限责任公司 | Method for comprehensively recovering niobium, rare earth and titanium from multi-metal ore containing iron, niobium and rare earth |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022194285A1 (en) * | 2021-03-19 | 2022-09-22 | 中国恩菲工程技术有限公司 | Comprehensive utilization method for columbite |
| CN114959157A (en) * | 2022-04-22 | 2022-08-30 | 中国恩菲工程技术有限公司 | Method and device for producing low-phosphorus molten iron by high-phosphorus reduced iron |
| CN114959157B (en) * | 2022-04-22 | 2024-04-09 | 中国恩菲工程技术有限公司 | Method and device for producing low-phosphorus molten iron from high-phosphorus reduced iron |
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