CN113234920B - Method for converting niobium minerals in niobium rough concentrate into sodium niobium minerals and producing niobium concentrate - Google Patents
Method for converting niobium minerals in niobium rough concentrate into sodium niobium minerals and producing niobium concentrate Download PDFInfo
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- CN113234920B CN113234920B CN202110481042.1A CN202110481042A CN113234920B CN 113234920 B CN113234920 B CN 113234920B CN 202110481042 A CN202110481042 A CN 202110481042A CN 113234920 B CN113234920 B CN 113234920B
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention discloses a method for converting niobium minerals in niobium rough concentrate into sodium niobium minerals and producing niobium concentrate, which comprises the following steps: obtaining a mixture comprising a niobium rough concentrate, wherein the alkalinity of the niobium rough concentrate is regulated to about 1.0 to about 2.0, Na 2 CO 3 Content control is from about 0.5% to about 5%; and (3) roasting the mixture in an inert protective gas at a temperature of between about 900 and about 1050 ℃, so that the iron element in the niobium rough concentrate is reduced into metallic iron in a weak reducing atmosphere, and at least a part of the niobium-containing minerals in the niobium rough concentrate are converted into the sodium niobium minerals. The method has strong adaptability to the niobium rough concentrate, is also suitable for the alkaline or acid niobium rough concentrate, and can be used for controlling various niobium minerals in the niobium rough concentrate into the sodium niobium ore by controlling the alkalinity, the roasting atmosphere and the roasting temperature, the gangue minerals have small change, the tight combination of the niobium minerals and the gangue minerals is avoided, and powerful conditions are provided for obtaining the high-quality niobium concentrate containing the sodium niobium ore by subsequent separation.
Description
Technical Field
The invention belongs to the technical field of metallurgy and mineral separation, and particularly relates to a method for converting niobium minerals in niobium rough concentrate into sodium niobium minerals and producing niobium concentrate.
Background
Niobium is an important strategic metal and is widely applied to the fields of steel, aerospace, electronic information and the like. The Bayan obo iron-niobium-rare earth multi-metal ore is taken as the largest niobium resource base in China, but because the ore contains niobiumThe conventional mineral separation process can only obtain Nb with a high content of Nb, Fe, Nb, rutile, pyrochlore, fine particle size, mostly smaller than 20 μm, and can be closely symbiotic with other minerals 2 O 5 The grade of the coarse niobium concentrate is lower than 5 percent, and the high grade (Nb) similar to Brazil cannot be directly obtained 2 O 5 50% -60%) niobium concentrate.
For example, chinese patent ZL96111328.6 discloses a process for producing medium-grade ferrocolumbium by smelting low-grade niobium rough concentrate in a "two-step" electric furnace, in which 1% -8% grade niobium concentrate, coke powder and organic binder are made into internally-carbon-added pellets, the pellets are first smelted in an electric furnace at 1350-1480 ℃ to separate niobium from iron, and then semi-steel and niobium-rich slag are obtained, and in the second step, the niobium-rich slag is aluminothermic reduced in an electric furnace at a temperature higher than 1550 ℃ to obtain medium-grade ferrocolumbium containing 30.8% niobium, which cannot meet the standard of the medium-grade ferrocolumbium in the state.
Chinese patent ZL201710206924.0 discloses a method for preparing titanium niobium iron ore concentrate powder, carbonaceous reducing agent and CaCO 3 The additive and the binder are used as raw materials, niobium-iron separation is realized through the working procedures of material preparation, uniform mixing, pelletizing, direct reduction, melt separation and the like, the temperature of the melt separation working procedure is 1350-1400 ℃, and the pellets are completely melted, so crystal growth of niobium minerals can be realized only by slow cooling crystallization to be beneficial to subsequent flotation, the size of the niobium minerals can reach 20-50 mu m, pig iron and niobium-rich slag with the grade of 5-12% are obtained after magnetic separation, and the niobium-rich slag is subjected to fine grinding flotation to obtain Nb 2 O 5 The content of the niobium-rich slag concentrate is 15 to 40 percent. But the slag after slow crystallization contains calcium, titanium, iron and niobium and is formed in the niobium/iron ore phase dispersed perovskite, and the theory of coexisting ore phase Nb 2 O 5 The content is low, and qualified niobium concentrate cannot be obtained. Secondly, the crystal size of the niobium mineral is difficult to control, the niobium-rich slag needs to be ground to be less than 30 mu m, the niobium mineral and the gangue mineral are tightly combined after recrystallization, and a large amount of gangue mineral is introduced in the separation process, so the grade of the niobium concentrate is improved limitedly. And the energy consumption of the pellet complete melting process is high, which is not beneficial to industrial application.
Disclosure of Invention
Technical problem
Based on the defects and shortcomings mentioned in the background art, the basic idea of the invention is as follows: and (3) converting a plurality of niobium minerals in the low-grade niobium rough concentrate into one niobium mineral in a centralized manner, or converting at least most of the niobium minerals into one niobium mineral, so that one niobium mineral is mainly used in the converted niobium rough concentrate, and the subsequent flotation and enrichment are facilitated, thereby obtaining the high-grade niobium concentrate.
Therefore, the technical problem to be solved by the invention is to provide a method for converting niobium ore in niobium rough concentrate into a certain niobium ore and producing niobium concentrate from the niobium ore, so as to obtain high-quality niobium concentrate through subsequent separation.
Technical scheme
Through a large amount of experimental observation and theoretical guidance, the niobium ore can be sodium niobium ore through the control of conditions, so that the technical problem can be solved. Therefore, the technical scheme is as follows:
a method of converting niobium minerals in a niobium rough concentrate to sodium niobium minerals, comprising:
obtaining a mixture comprising a niobium rough concentrate, wherein the alkalinity of the niobium rough concentrate is regulated to about 1.0 to about 2.0, Na 2 CO 3 Content control is from about 0.5% to about 5%;
and (3) roasting the mixture in an inert protective gas at the temperature of about 900-1050 ℃, so that the iron element in the niobium rough concentrate is reduced into metallic iron in a weak reducing atmosphere, and at least a part of niobium-containing minerals in the niobium rough concentrate are converted into sodium niobium ores, thereby obtaining the sodium niobium ore niobium rough concentrate.
In some embodiments, the niobium grade in the niobium rough concentrate is 5% or less, and the niobium-containing minerals in the niobium rough concentrate include one or more of niobite, niobite rutile, deliquescent stones, or wairauite.
In some embodiments, the weak reducing atmosphere is achieved by controlling the amount of carbonaceous reducing agent added to the mix or controlling the amount of reducing gas introduced into the firing atmosphere.
In some embodiments, the mass ratio of niobium roughing concentrate to carbonaceous reducing agent is controlled to be 100 (about 5 to about 15).
In some embodiments, the alkalinity is adjusted to be from about 1.2 to about 1.8.
In some embodiments, Na 2 CO 3 The content is regulated to be about 1% to about 3%.
In some embodiments, firing is at a temperature of about 1000 ℃.
In some embodiments, the calcination time is 80 to 100 min.
In some embodiments, greater than 50% of the niobium-containing minerals in the niobium rough concentrate are converted to albite.
The method for producing the niobium concentrate from the niobium rough concentrate also comprises the step of producing the niobium concentrate from the niobium rough concentrate containing sodium niobium concentrate through sorting after converting niobium minerals in the niobium rough concentrate into sodium niobium concentrate.
Advantageous effects
The method has strong adaptability to the niobium rough concentrate, is also suitable for the alkaline or acid niobium rough concentrate, and can be used for controlling various niobium minerals in the niobium rough concentrate into the sodium niobium ore by controlling the alkalinity, the roasting atmosphere and the roasting temperature, the gangue minerals have small change, the tight combination of the niobium minerals and the gangue minerals is avoided, and powerful conditions are provided for obtaining the high-quality niobium concentrate containing the sodium niobium ore by subsequent separation. The invention does not need high-temperature melting, has lower energy consumption and is beneficial to industrial application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram of one embodiment of the present invention;
FIG. 2 is an electron micrograph of the niobium matte concentrate containing sodium niobium ore of example 1;
FIG. 3 is an electron micrograph of the niobium matte concentrate containing sodium niobium ore of example 2;
FIG. 4 is an electron micrograph of the niobium matte concentrate containing sodium niobium ore of example 3;
FIG. 5 is an electron micrograph of the niobium concentrate containing niobite of example 4.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Definition of terms
The "%" as used herein means mass% unless otherwise specified.
As used herein, "about" preceding a number means that there is a ± 2% float on the number basis. About x, i.e., 0.98x to 1.02 x. About x%, i.e., 0.98 x% to 1.02 x%.
The "niobium-containing raw ore" as used herein refers to a niobium-containing ore in a natural environment, such as bayan obo ore polymetallic ore.
The term "niobium rough concentrate" as used herein refers to a rough concentrate obtained by pre-concentrating niobium-containing raw ore, which is used as a raw material in the present invention. The niobium-containing minerals in the niobium brown concentrate are referred to as "niobium-containing minerals" (or niobium minerals).
The term "niobium rough concentrate containing sodium-niobium ore" as used herein refers to a rough niobium concentrate obtained by converting at least a portion of the niobium minerals in the rough niobium concentrate into sodium-niobium ore by the process of the present invention.
The term "niobium concentrate" as used herein refers to a high-grade niobium ore product of sodium-containing niobium ore obtained by subjecting a niobium rough concentrate or the sodium-containing niobium ore niobium rough concentrate obtained by the present invention to subsequent separation, such as flotation.
FIG. 1 is a process flow diagram of one embodiment of the present invention. The invention firstly obtains a mixture containing the niobium rough concentrate and regulates and controls the alkalinity and Na of the niobium rough concentrate 2 CO 3 And (3) putting the mixture into inert protective gas, roasting at a certain temperature, reducing iron elements in the niobium rough concentrate into metallic iron in a weak reducing atmosphere, and converting at least a part of niobium-containing minerals in the niobium rough concentrate into sodium niobium ores to obtain the sodium niobium ore niobium rough concentrate.
Coarse niobium concentrate
The niobium rough concentrate serving as the raw material of the invention is rough concentrate obtained by pre-selecting complex niobium-containing raw ore. The pre-separation can adopt the conventional ore dressing process, for example, carbonate and partial silicate of raw ore are removed through a table concentrator, pyrite and other sulfide ores are removed through reverse flotation, and finally, the weak magnetic niobium mineral is recovered through strong magnetic separation, so that the niobium rough concentrate is obtained.
In the invention, the niobium grade (Nb) in the niobium rough concentrate 2 O 5 Content) is generally less than 5%, for example from 1 to 5%, for example from 2 to 3.5%, based on the total mass of the niobium rough concentrate. The niobium-containing mineral may comprise one or more of niobite, niobite rutile, delite, wairauite, and the like, and in some embodiments, the niobium-containing minerals may be present. The total iron content is generally between 10 and 20 percent.
In some examples, the niobium rough concentrate from beneficiation of the bayan obo polymetallic ore as the raw material used mainly contains the niobium mineral species niobite (theoretical Nb) 2 O 5 78.69% content, based on the mass of columbite iron ore), ferrocolumbium rutile (theoretical Nb) 2 O 5 Content 17.17%), easy-to-dissolve stone (theoretical Nb) 2 O 5 23.40% -32.88% of niobium-calcium ore (theoretical Nb) 2 O 5 82.60% content), pyrochlore (theoretical Nb) 2 O 5 Content 66%). It has the characteristics of high occupation ratio of low-niobium minerals (ferrocolumbium rutile and easy-dissolving stone), low content of low-iron high-niobium minerals (columbite-calcimine and pyrochlore), fine embedded granularity, mostly less than 20 mu m, close symbiosis with other minerals and the like 。
The main reason that the grade of the niobium rough concentrate produced by Baiyunebo is not high is as follows: the niobium minerals are various and have similar properties, wherein the niobium-iron rutile, the easy-dissolving stone and other low-grade niobium-containing minerals have high occupation ratio and the single high-niobium-grade minerals cannot be sorted; secondly, the iron content in the ore is high, the properties of the niobite are similar to those of other iron-containing minerals, the separation of the niobite is difficult, and the niobium rough concentrate still contains high iron. Therefore, it is necessary to anchor the "internal cause" of ore mineral composition, develop a technology for the iron component reduction to cooperate with the conversion of a plurality of niobium minerals into a single niobium mineral, and obtain qualified niobium concentrate through the "external cause" of ore dressing. The invention provides a method for intensively converting a plurality of niobium minerals in niobium rough concentrate into sodium niobium minerals through solid-phase reaction based on internal cause formed by ore minerals.
Mixture material
Besides the niobium-containing rough concentrate, the mixture optionally contains a reducing agent, and the alkalinity and Na of the niobium rough concentrate need to be regulated and controlled 2 CO 3 The content is in a certain range.
(reducing agent)
The reducing agent is mainly used for reducing the iron element in the niobium rough concentrate into metallic iron, and any reducing agent capable of achieving the purpose is applicable. In some embodiments, the mixture comprises a niobium matte and a solid carbonaceous reductant. The reducing agent may be a gaseous reducing gas, and may be introduced during the calcination. Non-limiting examples of reducing agents include one or more of petroleum coke, coal fines, coke, heavy oil, natural gas, water gas, carbon monoxide, and hydrogen.
In some embodiments, the mass ratio of niobium matte to carbonaceous reducing agent is 100 (about 5 to about 15), preferably 100 (about 5 to about 10), and more preferably 100 (about 5 to about 8). In this range, the iron element in the niobium rough concentrate can be sufficiently reduced to metallic iron.
(control of basicity)
The basicity in the present invention is defined as CaO/SiO 2 The mass ratio of (a). The basicity of the niobium rough concentrate is controlled to be about 1 to about 2, preferably about 1.2 to about 1.8, and more preferably about 1.5. The alkalinity is controlled to convert into sodium niobium oreIt is important that the basicity is too low or too high and the melting point of the reaction system is high, resulting in incomplete reaction. The invention mainly controls the alkalinity and Na 2 CO 3 The contents, the roasting atmosphere and the roasting temperature of the plurality of niobium minerals in the niobium rough concentrate are intensively regulated and controlled into sodium niobium minerals.
In some embodiments, modulating the basicity of the niobium rough concentrate may be achieved by adding a reagent called a modifier (or modulating agent) to the niobium rough concentrate. The addition amount of the modifier is determined according to the original alkalinity of different niobium rough concentrates, and in some embodiments, the mass ratio of the niobium rough concentrate to the modifier is 100 (5-30), and is further 100 (5-10). Of course, if the basicity of the individual niobium rough concentrate is within the claimed range of the invention, no modifier is added.
In some embodiments, the modifier comprises a calcareous reagent and/or a siliceous reagent, both of which are not necessarily added, one of which may be added depending on the basicity of the niobium rough concentrate. Non-limiting examples of calcareous agents include limestone, fluorite, quicklime, dolomite, and the like. Non-limiting examples of siliceous agents include quartz sand, water glass, feldspar, fly ash, mine tailings, waste glass, and the like.
(Na 2 CO 3 Control of content)
Na 2 CO 3 The content is regulated to be about 0.5% to about 5%, preferably about 1% to about 3%, and more preferably about 2%, based on the total mass of the niobium rough concentrate. Na (Na) 2 CO 3 The content is controlled within the above range, and is also converted into the albite to a greater extent. Na (Na) 2 CO 3 If the content is too low, the reaction for converting the niobium ore into the sodium niobium ore is insufficient; when the content is too high, the melting point of other minerals is reduced, the reaction of other minerals is promoted, and the product impurities are increased.
In some embodiments, the sodium reagent (e.g., Na) can be added by adding it 2 CO 3 、NaHCO 3 Etc.) regulating Na 2 CO 3 And (4) content. The addition amount of the Na depends on different niobium rough concentrates 2 CO 3 According to the content, in some embodiments, the mass ratio of the niobium rough concentrate to the sodium reagent is 100 (1-5), and is further, for example, 100 (2-4). Of course, if individual niobium roughnesses are usedNa of ore 2 CO 3 The content is in the range required by the invention, so that no sodium reagent is required to be added.
Step of mixing
The niobium rough concentrate and the reducing agent, and optionally the modifier and the sodium reagent are uniformly mixed, and any mixing equipment and mixing method can be adopted, for example, mixing by ball milling, a powder mill and the like.
In some embodiments, the binder is added to the uniformly mixed ingredients, which are then shaped to obtain a green mixture. In some embodiments, the binder may be added in an amount of 1% to 5% based on the total mass of the mix. The binder may be any solution of those known in the art, including, but not limited to, solutions of one or more of PVA, water glass, clay, and the like. The shaping can be carried out by conventional methods using existing equipment (including presses, dies, ball presses, etc.), for example, by briquetting or pelletizing. The pressure for molding is not particularly limited, and the molding can be carried out at a pressure of 2 to 20MPa or higher or lower. After the forming, the contact area of the niobium mineral and the reactant is increased, and the solid-phase reaction is promoted to be carried out.
Step of calcination
And (3) placing the mixture or the mixture blank in inert protective gas, roasting at a certain temperature, and obtaining the sodium-containing niobium ore niobium rough concentrate by adopting a solid-phase reaction (different from melting smelting).
The firing temperature is desirably from about 900 to about 1050 deg.C, preferably about 1000 deg.C. When the temperature is too high, the sodium niobium ore and other minerals continue to react, and a large amount of impurities are introduced; the temperature is too low to facilitate the reaction, such as the reaction temperature of the major niobite is close to 950 ℃. In some embodiments, the roasting heat preservation time is more than or equal to 30min, such as 30-120 min, preferably 80-100 min. Firing may be carried out in a known firing apparatus, such as a tube furnace or the like, as long as the firing apparatus has a cavity for accommodating the mix or the mixed compact and is capable of introducing a desired atmosphere into the cavity.
The roasting atmosphere is required to be a weak reducing atmosphere, so that the iron component in the system can be directly reduced into the metallic iron, but the niobium is not reduced, and if the reducing property of the reaction system is too strong, part of niobium minerals are reduced into niobium carbide and attached to the periphery of the metallic iron. In some embodiments, a weakly reducing atmosphere may be achieved by: inert protective gas (such as nitrogen and the like) is introduced into the system, and because the existence of the reducing agent is required for conversion, if the reducing agent adopts reducing gases such as natural gas, water gas, carbon monoxide, hydrogen and the like, the reducing gases are introduced into the reaction system and mixed with the inert protective gas to form a weak reducing atmosphere. If the reducing agent is carbonaceous reducing agents such as petroleum coke, coal powder, coke, heavy oil and the like, the carbonaceous reducing agents react with partial materials at the roasting temperature to generate reducing gases such as CO and the like, and the reducing gases are mixed in inert protective gas to form weak reducing atmosphere.
Here, the weakly reducing atmosphere, in some embodiments, if the reductant is a gaseous reductant, is controlled by controlling the gaseous reductant to inert gas volume ratio, e.g., controlling CO to CO 2 The volume ratio is (4-5): 5, preferably 1: 1. If the reducing agent is a carbonaceous reducing agent, it is sufficient to control the reducing agent in the proportions mentioned in the preceding paragraph. The reducing atmosphere must not be too strong, i.e. the amount of reducing agent added must not be too high.
Experiments prove that the reducing agent is added into the niobium rough concentrate, and the alkalinity and Na are regulated and controlled 2 CO 3 After the content is increased, roasting is carried out in a weak reducing atmosphere, so that not only are iron-containing components such as hematite/goethite/pyrite/columbite rutile in the rough concentrate directly reduced into metallic iron, but also niobium minerals such as low-niobium-grade columbite rutile and resolvable stones can be converted into high-grade sodium niobium minerals, the niobium minerals such as weak-magnetic columbite and columbite rutile are converted into non-magnetic sodium niobium minerals, the magnetic difference between the niobium minerals and the metallic iron is enlarged, the subsequent columbite separation is facilitated, and powerful conditions are provided for the subsequent separation work of the rough niobium concentrate containing the sodium niobium minerals.
Niobium rough concentrate containing sodium niobium ore
After the roasting treatment and cooling, most of the niobium-containing minerals in the niobium rough concentrate are converted into sodium niobium ore (NaNbO) 3 ). Of which "most", for exampleThis is 50% or more, or 60% or more, or 75% or more, and may even be up to 90% or more, based on the total mass of the niobium-containing minerals in the niobium rough concentrate. In some embodiments, the Nacolumbite is intercalated with small amounts of Ca, and in other embodiments, with small amounts of K, Ca, Fe.
The niobium content of the rough concentrate is low and cannot be verified by XRD (X-ray diffraction), and only SEM-EDS (scanning Electron microscope) -EDS (electronic data System) tests prove that the niobium element distribution can be known through SEM surface scanning, and then the niobium mineral is subjected to energy spectrum analysis, so that the niobium mineral component is sodium niobium mineral (NaNbO) 3 ) And the sodium niobium ore proportion data is obtained by calculating the proportion of the particle niobium ore in the electron microscope picture.
Because of the large number of species of niobium ore in the niobium rough concentrate, if it is difficult to convert a plurality of niobium ore species into single sodium niobium ore, it is necessary to not only cooperatively control the chemical composition and thermodynamic conditions (such as roasting temperature) of the roasted mixed ore, but also adjust the kinetic process (such as roasting time control) thereof to control the crystal growth thereof. By adopting the control conditions of the invention, in some embodiments, the grain size of the obtained NaNb ore is 30-120 μm, or 30-110 μm, or 30-80 μm, the 30 μm niobium ore is few, and the majority is more than 50 μm, so that the NaNb ore can be dissociated only by grinding to 40 μm for further separation.
Because most of the niobium-containing minerals are converted into single sodium niobium ore, the subsequent separation (such as flotation) enrichment is facilitated to obtain high-grade niobium concentrate. By adopting the method, the change of the gangue minerals is small, and the tight combination of the niobium minerals and the gangue minerals is avoided. The niobium concentrate of the sodium-containing niobium ore can be used as a main raw material for producing niobium pentoxide by hydrometallurgy.
Examples
(example 1)
Niobium rough concentrate with the niobium grade of 2.24 percent, which is obtained by pre-selecting raw niobium-containing ores in Baiyunebo, is used as a main raw material, and the chemical composition is shown in table 1. The niobium-containing mineral species include columbite, ferrocolumbium, and waironite. The alkalinity of the present example was controlled to 1.5, Na 2 CO 3 The content is regulated to 0.5%.
TABLE 1 raw materials chemical composition/wt%
Taking 20g of niobium rough concentrate, adding 1.2g of petroleum coke as a reducing agent, fully mixing the niobium rough concentrate with a powder making machine, adding 2mL of 5% PVA solution, molding the mixed material by using a press machine and a mold to obtain a cylinder with the diameter of phi 30mm, drying the cylinder in an oven for 8 hours, placing the cylinder in a tubular furnace, and introducing N 2 Roasting at 1000 ℃ for 60min under the condition of protective gas, cooling along with the furnace, and then finding by an electron microscope that 50% of niobium ore is converted into granular sodium niobium ore doped with a small amount of K, Ca and Fe, wherein the grain size is 30-80 mu m, as shown by an energy spectrum point 2-3, the central part is unreacted niobium iron ore (because the roasting time is short), as shown by an energy spectrum point 1, and specifically as shown in figure 2.
(example 2)
The niobium rough concentrate with the niobium grade of 2.24 percent obtained by pre-selecting the niobium-containing raw ore is taken as a main raw material, and the chemical composition is shown in table 1. The niobium-containing mineral species include columbite, ferrocolumbium, and waironite. The alkalinity of the present example was controlled to 1.5, Na 2 CO 3 The content is regulated to be 2 percent.
Taking 20g of niobium rough concentrate, adding 1.2g of petroleum coke, fully mixing the niobium rough concentrate with a powder making machine, adding 2mL of 5% PVA solution, forming the mixed material by utilizing a press and a mould to obtain a cylinder with the diameter of phi 30mm, drying the cylinder in an oven for 8 hours, placing the cylinder in a tubular furnace, and introducing N 2 Roasting at 1000 ℃ for 90min under the condition of protective gas, cooling along with the furnace, and then finding through an electron microscope that 90% of niobium ore is converted into granular sodium niobium ore doped with a small amount of Ca, wherein the grain size is 30-110 mu m, as shown in energy spectrum points 1 and 4-7, and specifically as shown in figure 3, the mineral phase theory Nb is Nb 2 O 5 The content was 57.22%.
(example 3)
The niobium rough concentrate with the niobium grade of 2.24 percent obtained by pre-selecting the niobium-containing raw ore is taken as a main raw material, and the chemical composition is shown in table 1. The niobium-containing mineral species include columbite, ferrocolumbium, and waironite. The alkalinity of the present example was controlled to 1.5, Na 2 CO 3 The content is regulated to 5%.
Taking 20g of niobium rough concentrate, adding 1.2g of petroleum coke, fully mixing the niobium rough concentrate with a powder making machine, adding 2mL of 5% PVA solution, forming the mixed material by utilizing a press and a mould to obtain a cylinder with the diameter of phi 30mm, drying the cylinder in an oven for 8 hours, placing the cylinder in a tubular furnace, and introducing N 2 Roasting at 1000 ℃ for 90min under the condition of protective gas, cooling along with the furnace, and then finding through an electron microscope that 90% of niobium ore is converted into granular sodium niobium ore mixed with Ca, the grain size of the sodium niobium ore is 30-120 mu m, as shown by an energy spectrum point 1-7, the aggregation effect of the sodium niobium ore is more obvious, but the niobium content of the sodium niobium ore is reduced, as shown in figure 4.
(example 4)
The calcination temperature in this example was 950 ℃ and the other conditions were the same as in example 1. After furnace cooling, the niobium ore edge was converted by electron microscopy to sodiobium with a small amount of K, Ca incorporated, as shown at spectral point 4, and the central portion of the niobium ore body was unreacted niobite, as shown at spectral point 3, and in particular in fig. 5.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (9)
1. A method for converting niobium minerals in a niobium rough concentrate to sodium niobium minerals, comprising:
obtaining a mixture containing niobium rough concentrate, wherein the alkalinity of the niobium rough concentrate is regulated to 1.0-2.0, Na 2 CO 3 The content regulation is 2% -5%;
placing the mixture in an inert protective gas, roasting at the temperature of 900-1050 ℃, reducing iron elements in the niobium rough concentrate into metallic iron in a weak reducing atmosphere, and converting at least a part of niobium-containing minerals in the niobium rough concentrate into sodium niobium ores to obtain the sodium niobium ore niobium rough concentrate; the weak reducing atmosphere is achieved by controlling the amount of carbonaceous reducing agent added to the mix or controlling the amount of reducing gas introduced into the firing atmosphere.
2. The method of claim 1, wherein the niobium concentrate comprises niobium ore having a niobium grade of 5% or less, and wherein the niobium-containing minerals comprise one or more of niobite, niobite rutile, deliquesite, or wairauite.
3. The method for converting niobium minerals in niobium rough concentrate into sodium niobium minerals as claimed in claim 1, wherein the mass ratio of the niobium rough concentrate to the carbonaceous reducing agent is controlled to be 100 (5-15).
4. The method for converting niobium minerals in niobium rough concentrate into sodium niobium minerals according to claim 1 or 2, wherein the alkalinity is controlled to be 1.2-1.8.
5. The process for converting niobium minerals in niobium roughing concentrates to sodiumbillite according to claim 1 or 2 characterized by that Na 2 CO 3 The content is regulated and controlled to be 2% -3%.
6. The process for converting niobium minerals in niobium concentrates to sodiumbinite according to claim 1 or 2, characterized by firing at a temperature of 1000 ℃.
7. The method for converting niobium minerals in niobium rough concentrate into sodium niobium minerals as claimed in claim 1 or 2, wherein the roasting time is 80-100 min.
8. The method of converting niobium minerals in niobium roughing concentrate to sodiobiute as claimed in claim 1 or 2 wherein more than 50% of the niobium containing minerals in niobium roughing concentrate are converted to sodiobiute.
9. A method for producing niobium concentrate from niobium rough concentrate, characterized in that, after the niobium minerals in the niobium rough concentrate are converted into sodium niobium minerals by the method of any one of claims 1 to 8, the method further comprises the step of producing niobium concentrate from the sodium niobium minerals by sorting.
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