CN112281002A - Method for enriching and recovering niobium, rare earth and titanium from multi-metal ore containing iron, niobium and rare earth - Google Patents
Method for enriching and recovering niobium, rare earth and titanium from multi-metal ore containing iron, niobium and rare earth Download PDFInfo
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- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
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Abstract
The invention discloses a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth, which comprises the following steps: the iron, niobium and rare earth containing multi-metal ore, slag former and reducer are mixed according to the ratio of 100 (2-100): (0-3)0) Mixing and batching according to the mass ratio of the components; putting the ingredients into a smelting furnace for smelting to produce slag and flue gas; the oxygen potential and CaO/SiO in the furnace are adjusted by controlling the composition in the ingredients and the oxygen potential in the furnace and monitoring the components of the smelted products and the recovery rate of iron2CaO/SiO in a mass ratio within a suitable range2The mass ratio is 2.5-6.0; discharging the produced slag into a slag ladle, and cooling and crystallizing; crushing the obtained furnace slag, and finely grinding to obtain slag powder; and (3) treating the obtained slag powder by adopting a mineral separation process to obtain high-grade composite concentrate containing niobium, rare earth and titanium. The method has simple steps, convenient operation and good economic benefit, and can obtain the composite concentrate for comprehensively recovering various valuable metals.
Description
Technical Field
The invention belongs to the field of niobium resource utilization, and particularly relates to a method for comprehensively recovering niobium, rare earth and titanium from low-grade niobium-containing polymetallic ores.
Background
Niobium is an important strategic metal, is widely applied to the fields of steel, aerospace, electronic information and the like, and is an important strategic resource for national economy and national defense construction. Since 2005, China has become the world's largest niobium consumer, but the demand for niobium in China is extremely dependent on import, and the degree of dependence on the outside is over 97%. However, in China, niobium resources are not in shortage, wherein Baotoyun Obo iron-niobium-rare earth (Fe-Nb-REE) polymetallic ores are used as the largest niobium resource base in China, which has proved that Nb is the most important2O5The reserve amount reaches 214 ten thousand tons, and the prospect reserve amount is estimated to exceed 660 ten thousand tons. Therefore, the realization of the economic utilization of niobium resources in the polymetallic ores has very important significance for relieving the contradiction between supply and demand of niobium in China.
The iron-niobium-rare earth multi-metal ore contains more valuable metal types, Fe, Nb, La, Ce, Nd and Ti, more niobium-containing minerals and up to 20 types, has complex components, high occupation ratio of low niobium-containing minerals (ferrocolumbium and pyrochlore), low content of high niobium-containing minerals (waibium-calcium ore and pyrochlore), fine embedding granularity and most of the low niobium-rare earth multi-metal ore is less than 20 mu m, and is closely coexisted with other minerals. This results in that the conventional beneficiation process can only obtain low grade niobium concentrate, which is Nb2O5The grade is hardly over 10 percent and is far lower than the high grade (Nb) for producing ferrocolumbium2O550% -60%) of niobium concentrate. The niobium content of the ferrocolumbium alloy produced by adopting one-step smelting of the medium/low-grade niobium concentrate is far lower than the national medium ferroniobium standard requirement; the niobium content of the niobium-iron alloy is obviously improved but still lower than the national standard (Nb is more than 50%) by adopting the two-step smelting method.
Through the exploration of years, people recognize that the grade of niobium in the niobium concentrate is closely related to the quality of ferrocolumbium, and the high-grade niobium concentrate is an important guarantee for producing qualified high-grade ferrocolumbium. Therefore, the production of high-grade niobium concentrate from multi-metal ore containing iron, niobium and rare earth has become the focus of research in recent years, and the related specific methods can be divided into the following two types:
(1) the process of magnetizing roasting/reducing roasting-magnetic separation to eliminate iron and to enrich niobium includes the following steps: the refractory iron minerals are converted into the minerals easy for magnetic separation through magnetization roasting or reduction roasting, and the niobium grade in the magnetic separation tailings can be improved through magnetic separation and iron removal. For example, Chinese patent CN104498737A discloses a method for enriching niobium by high-temperature roasting-low intensity magnetic separation, which is used for enriching niobium containing 43.5% of TFe and Nb2O5Selectively reducing 5.75% niobium rough concentrate, destroying the mineral structure of niobium-iron rutile in the original mineral by reducing iron oxide, performing low intensity magnetic separation after ball milling the reduced ore to obtain metal iron powder and the ore containing 7.8% TFe and Nb2O512.76% niobium rich material (also known as niobium concentrate). However, the niobium-rich material Nb produced by the process2O5The grade is still lower than 15 percent, and the requirement of high-grade ferrocolumbium production still cannot be met. In addition, the niobium concentrate product Nb obtained by the method2O5The grade is closely and positively correlated with the grade of niobium in the raw material, and the grade is directly correlated with the grade of low-grade niobium rough concentrate (Nb)2O51.77% -2.76%) can only be improved to 5.01% -6.91% after treatment.
(2) Reduction and melting separation, slag phase slow cooling crystallization, fine grinding and flotation. On one hand, the process preferentially removes almost all iron through reduction and melting, thereby realizing the primary enrichment of niobium grade in a slag phase; on the other hand, the slag is slowly cooled and crystallized to obtain larger particlesAnd floating the separated niobium ore to further improve the niobium grade. For example, the Chinese patent with publication number CN106987673B discloses a method for producing a titanium niobium iron ore concentrate powder3The additive and the binder are used as raw materials, and the niobium and iron are separated through the working procedures of material preparation, uniform mixing, agglomeration, reduction melting and the like to prepare pig iron and Nb2O55-12% of niobium-rich slag, wherein the niobium-rich slag is subjected to slag phase quenching and tempering and slow cooling crystallization to realize aggregation and growth of niobium minerals, the size of the niobium-rich slag can reach 20-50 mu m, and Nb is obtained by fine grinding and flotation2O5And (3) the content of the niobium-rich slag concentrate is 15-40%. Compared with the process of magnetizing roasting/reducing roasting-magnetic separation for removing iron and niobium, the niobium flotation concentrate obtained by the method has obviously improved niobium grade, but the niobium grade of the produced niobium-rich slag concentrate (also called niobium concentrate) can not meet the production standard of high-grade ferrocolumbium, and the reason is that the concentrated conversion of niobium in slag to a single high-grade niobium ore phase can not be realized only by a slag slow cooling crystallization mode. The relevant literature shows that: the slag after slow crystallization still has various niobium ore phases including easy-dissolving stones, niobite, waibanite, and chrysolite, and the dispersed and coexisting niobium ore phases are difficult to be efficiently enriched by flotation, so that high-grade niobium concentrate for ferrocolumbium cannot be obtained.
More importantly, many low-grade niobium concentrates (such as bayan obo iron-niobium-rare earth multi-metal ores) are rich in a certain amount of rare earth and titanium elements, and how to realize the comprehensive utilization of niobium, rare earth and titanium is also a technical problem to be solved.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provides a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth.
The technical scheme provided by the invention is a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth, which comprises the following steps:
a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth comprises the following steps:
(1) mixing and batching the multi-metal ore containing iron, niobium and rare earth, the slag former and the reducing agent according to the mass ratio of 100 (2-100) to 0-30;
(2) putting the ingredients obtained in the step (1) into a smelting furnace for smelting to produce slag and flue gas; controlling the smelting temperature to be more than or equal to 1350 ℃ and the smelting time to be more than or equal to 10 min; by controlling the composition of the ingredients in the step (1) and the oxygen potential in the furnace, and monitoring the components (such as whether iron-containing alloy is produced) of the smelting product in the step (2), the recovery rate of iron and the CaO/SiO of the slag2CaO/SiO of the slag to a suitable range2The mass ratio is 2.5-6.0;
(3) discharging the slag produced in the step (2) into a slag ladle, and cooling and crystallizing;
(4) crushing the furnace slag obtained in the step (3) and then finely grinding to obtain slag powder;
(5) and (4) treating the slag powder obtained in the step (4) by adopting a mineral separation process to obtain high-grade composite concentrate containing niobium, rare earth and titanium.
In the above method for enriching and recovering niobium, rare earth and titanium from the iron, niobium and rare earth-containing polymetallic ore, preferably, Nb is contained in the iron, niobium and rare earth-containing polymetallic ore2O51-10% of TiO20.5 to 12 percent of the total Fe content, 0.5 to 8 percent of the REO content, 5 to 60 percent of the total Fe content, less than or equal to 30 percent of the CaO content, less than or equal to 20 percent of the MgO content, and SiO22-50% of Al2O3The content is less than or equal to 10 percent; the iron, niobium and rare earth containing polymetallic ore comprises one or more of low-grade niobium concentrate, iron-niobium rare earth concentrate, high-titanium niobium-rich slag, niobium-containing iron ore powder, niobium-iron paragenic ore, niobium-iron concentrate and flotation rare earth tailings.
In the above method for recovering niobium, rare earth and titanium from polymetallic ores containing iron, niobium and rare earth, preferably, the reducing agent comprises a solid reducing agent and/or a gaseous reducing agent; the solid reducing agent comprises one or more of semi-coke, pulverized coal, coke, petroleum coke, charcoal, anthracite, bituminous coal and coal; the gas reducing agent comprises one or more of natural gas, water gas, carbon monoxide and hydrogen. In order to avoid introducing excessive impurity elements into the solid reducing agent, it is further preferable that the content of C in the solid reducing agent is not less than 75%.
In the above method for enriching and recovering niobium, rare earth and titanium from the polymetallic ore containing iron, niobium and rare earth, preferably, the slagging agent comprises one or more of dolomite, limestone and calcite.
In the above method for recovering niobium, rare earth and titanium from polymetallic ores containing iron, niobium and rare earth, in order to reduce the yield of smelting smoke dust, preferably, the ingredients in the step (1) are pelletized, granulated and/or sintered into blocks, and then put into the smelting furnace for smelting, and air, pure oxygen or oxygen-enriched air can be preferably introduced during smelting, but the common electric furnace does not need.
Preferably, the smelting furnace comprises one or more of a shaft furnace, a blast furnace, an open hearth furnace, an electric furnace, a converter, a side blown furnace, a bottom blown furnace, a top blown furnace and a reverberatory furnace.
In order to enrich niobium, rare earth and titanium in the same mineral phase in the complex material, the method for enriching and recovering niobium, rare earth and titanium from the polymetallic ores containing iron, niobium and rare earth finds that the key point is to control the proper slag composition (specifically, slag CaO/SiO) in the smelting stage of the step (2)2Value) and furnace oxygen potential. Since the oxygen potential in the furnace is difficult to measure directly, it is preferable to indirectly characterize the oxygen potential level in the furnace by controlling the composition of the ingredients in step (1), i.e., the ratio of the oxidizing substance (a substance reducible by a reducing agent, such as iron oxide in the ore, or oxygen blown into the furnace) and the reducing substance (mainly, a reducing agent) so that an index of recovery of Fe in the iron-containing alloy produced by melting in step (2) (the oxygen potential can also be controlled by controlling the recovery of iron to 0 without producing the iron-containing alloy). More preferably, the smelting process also produces iron-containing alloy, the oxygen potential in the furnace is adjusted to a proper range by controlling the composition of the ingredients in the step (1) and monitoring the recovery rate of Fe in the iron-containing alloy produced by smelting in the step (2), and the recovery rate of Fe in the iron-containing alloy produced by smelting is controlled below 80%. Further, the composition of the slag former in the step (1) in the ingredients (namely CaO and SiO in the ingredients) is controlled2Quality) and monitorControlling CaO/SiO of the slag produced by smelting in the step (2)2The mass ratio is adjusted to adjust the slag system. A large number of experimental researches show that in order to enrich niobium, rare earth and titanium in a complex material in the same mineral phase, CaO/SiO of the slag is controlled2The mass ratio is 2.6-5.5.
Preferably, in the method for enriching and recovering the niobium, the rare earth and the titanium from the polymetallic ores containing the iron, the niobium and the rare earth, in order to ensure the separation effect between the iron alloy melt and the slag, the smelting temperature in the step (2) is controlled to be 1400-1550 ℃, and the smelting time is more than or equal to 30 min.
In order to obtain large-particle mixed ore phase containing niobium, rare earth and titanium and facilitate a subsequent ore dressing method to obtain high-grade niobium-rare earth-titanium composite concentrate, the method for enriching and recovering niobium, rare earth and titanium from the polymetallic ore containing iron, niobium and rare earth is preferably used, wherein the cooling speed of the slag in the step (3) is less than or equal to 30 ℃/min; particularly preferably ≦ 15 ℃/min.
In the above method for recovering niobium, rare earth and titanium from polymetallic ores containing iron, niobium and rare earth, preferably, the beneficiation process treatment in the step (5) includes one or more of gravity separation, flotation and electric separation.
In the above method for enriching and recovering niobium, rare earth and titanium from the polymetallic ore containing iron, niobium and rare earth, preferably, Nb is contained in the composite concentrate containing niobium, rare earth and titanium2O5+REO+TiO2The total content is more than or equal to 25 percent, preferably more than or equal to 30 percent.
The core technical idea of the invention is as follows: the occurrence characteristics of the minerals are the 'internal factors' which determine the good and bad dressing and smelting performance of the ore raw materials. For multi-metal complex ores, a better idea is to perform artificial ore phase transformation on raw material minerals by starting from internal causes to drive target metal/element enrichment to be transformed into easily-selected enriched ore phases, and then the easily-selected enriched ore phases can be treated by adopting a simple dressing and smelting process. In fact, our research finds that the root cause of the refractory selection of the polymetallic complex minerals lies in the difference of the internal factors of mineral composition/occurrence characteristics, and furthermore, the difficulty of the subsequent selection and metallurgy treatment is different due to the difference of the elements of the formed minerals and the physicochemical conditions. Based on usThe present invention is based in particular on Nb2O5-REO-CaO-MgO-“FeO”-TiO2-SiO2-Al2O3On the basis of research on a multi-component melt crystallization rule and a regulation and control principle and method of niobium/rare earth directional mineralization, niobium, titanium and rare earth elements which are dispersed in a low-grade niobium-containing rare earth titanium complex material and difficult to enrich and recover are directionally regulated and enriched in the same artificial ore phase by controlling proper conditions, Fe is enriched in an iron-aluminum-magnesium spinel phase in iron alloy or slag, and a high-grade niobium rare earth titanium composite concentrate can be obtained by a further beneficiation method, so that the comprehensive recovery of the niobium, the rare earth and the titanium elements can be realized.
Compared with the prior art, the process method has the following remarkable advantages:
(1) the invention creatively provides the method for directionally regulating and controlling the niobium rare earth titanium in the low-grade niobium rare earth titanium complex material and enriching the niobium rare earth titanium in the same mineral phase in the slag, provides possibility for obtaining high-grade niobium-rare earth-titanium composite concentrate through a beneficiation method in the follow-up process, and further solves the problem of comprehensive recycling of niobium, rare earth and titanium in the low-grade niobium rare earth titanium complex material;
(2) the process of the invention also realizes the comprehensive recycling of high-value rare earth, niobium and titanium;
(3) the key point of the process method is two stages of material preparation and smelting, and the process has the advantages of strong operability, economy, reasonability, simple process steps and the like, and is suitable for industrial application and popularization.
Drawings
FIG. 1 is a microstructure view of slag obtained after step 3 of example 1 of the present invention.
FIG. 2 is a microstructure view of slag obtained after step 3 of example 2 of the present invention.
FIG. 3 is a microstructure view of slag obtained after step 3 of example 3 of the present invention.
FIG. 4 is a microstructure view of slag obtained after step 3 of example 4 of the present invention.
FIG. 5 is a microstructure view of slag obtained after step 3 of example 5 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention is described more fully and in detail below, but the scope of the invention is not limited to the following specific examples.
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.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth comprises the following steps:
(1) mixing complex ore material (such as low-grade niobium concentrate obtained by primary ore dressing, Nb thereof)2O52.37% of TiO24.13 percent of the content, 16.75 percent of Fe, 3.32 percent of rare earth oxide REO, 14.03 percent of CaO, and SiO212.75% of MgO 10.05% of Al2O31.87% of niobium, which is mainly in the form of niobite, niobite rutile or easy-to-dissolve stone, a slag former (limestone in the embodiment), a reducing agent (coke in the embodiment, with a content of 84% of C) based on 100: 20: 4, mixing and batching;
(2) putting the ingredients obtained in the step (1) into an electric furnace for smelting to produce slag and flue gas; controlling the smelting temperature to 1550 ℃ and the smelting time to be 30 min; by controlling the composition and the oxygen potential in the furnace in the burdening in the step (1), the components of the smelting products, the recovery rate of iron and the CaO/SiO of the slag in the step (2) are monitored2The mass ratio is adjusted to adjust a slag system, and the step smelts and controls the alloy containing iron which is not produced (wherein the recovery rate of iron is 0); CaO/SiO of slag produced by smelting2Adjusting the mass ratio of CaO to SiO2The mass ratio is controlled to be 3.06;
(3) discharging the slag produced in the step (2) into a slag ladle, cooling and crystallizing, and controlling the cooling speed to be 5 ℃/min to obtain a slag phase (white particles are niobium-rare earth-titanium-containing mineral phases) shown in figure 1;
(4) crushing the furnace slag obtained in the step (3) and then finely grinding to obtain slag powder;
(5) and (4) treating the slag powder obtained in the step (4) by adopting a mineral separation process to obtain high-grade composite concentrate containing niobium, rare earth and titanium.
The high-grade composite concentrate containing niobium, rare earth and titanium obtained in the embodiment is detected by a conventional method, and the detection shows that Nb in the high-grade composite concentrate2O510.08 percent of content, 12.96 percent of REO content and TiO2The content is 12.65%.
Example 2:
a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth comprises the following steps:
(1) mixing complex mineral material (such as iron-niobium-rare earth concentrate, Nb thereof) containing low-grade niobium/rare earth/titanium2O55.40% of TiO24.29 percent of the total weight of the alloy, 35.09 percent of the total weight of Fe, 4.11 percent of rare earth oxide REO, 3.91 percent of CaO and SiO220.05% of MgO, 1.17% of Al2O30.34 percent of niobium, which mainly exists in the forms of niobite, niobite rutile and easy-to-dissolve stones), and a slagging agent (in the embodiment, the mass ratio of limestone to dolomite is 1: 1), reducing agent (the mass ratio of anthracite to coal particles is 1: 0.5 mixture, total average C content 79%) as 100: 73: 15, mixing and batching;
(2) putting the ingredients obtained in the step (1) into a shaft furnace for smelting to produce iron-containing alloy, slag and flue gas; controlling the smelting temperature to 1550 ℃ and the smelting time to be 30 min; by controlling the composition and the oxygen potential in the furnace in the burdening in the step (1), the components of the smelting products, the recovery rate of iron and the CaO/SiO of the slag in the step (2) are monitored2The mass ratio is adjusted to a slag system, and the recovery rate of iron in the iron-containing alloy in the step is 56.57 percent; CaO/SiO of slag produced by smelting2Adjusting the mass ratio of CaO to SiO2The mass ratio is controlled to be 3.84;
(3) discharging the slag produced in the step (2) into a slag ladle, cooling and crystallizing, and controlling the cooling speed to be 10 ℃/min to obtain a slag phase (white particles are niobium-rare earth-titanium-containing mineral phases) shown in figure 2;
(4) crushing the furnace slag obtained in the step (3) and then finely grinding to obtain slag powder;
(5) and (4) treating the slag powder obtained in the step (4) by adopting a mineral separation process to obtain high-grade composite concentrate containing niobium, rare earth and titanium.
The high-grade composite concentrate containing niobium, rare earth and titanium obtained in the embodiment is detected by a conventional method, and the detection shows that Nb in the high-grade composite concentrate2O512.22% of REO 16.52% of TiO2The content is 16.53 percent.
Example 3:
a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth comprises the following steps:
(1) mixing complex mineral material containing low grade niobium/rare earth/titanium (such as ferrocolumbium concentrate, Nb thereof)2O53.52% of TiO24.29 percent of the total weight of the alloy, 14.03 percent of the total weight of Fe, 1.50 percent of the rare earth oxide REO, 14.03 percent of the total weight of CaO, and SiO212.75% of MgO 10.05% of Al2O31.87% of niobium, which is mainly in the form of niobite, niobite rutile and easy-to-dissolve stones, a slag former (dolomite is selected in the embodiment), and a reducing agent (pulverized coal is selected in the embodiment, and the content of C is 89%), based on 100: 54: 6, mixing and batching;
(2) putting the ingredients obtained in the step (1) into a converter for smelting to produce slag and flue gas; controlling the smelting temperature to 1550 ℃ and the smelting time to be 30 min; by controlling the composition and the oxygen potential in the furnace in the burdening in the step (1), the components of the smelting products, the recovery rate of iron and the CaO/SiO of the slag in the step (2) are monitored2The mass ratio is adjusted to adjust a slag system, and the step does not produce the iron-containing alloy (namely the recovery rate of iron is 0); CaO/SiO of slag produced by smelting2Adjusting the mass ratio of CaO to SiO2The mass ratio is controlled to be 5.41;
(3) discharging the slag produced in the step (2) into a slag ladle, cooling and crystallizing, and controlling the cooling speed to be 5 ℃/min to obtain a slag phase (white particles are niobium-rare earth-titanium-containing mineral phases) shown in figure 3;
(4) crushing the furnace slag obtained in the step (3) and then finely grinding to obtain slag powder;
(5) and (4) treating the slag powder obtained in the step (4) by adopting a mineral separation process to obtain high-grade composite concentrate containing niobium, rare earth and titanium.
The high-grade composite concentrate containing niobium, rare earth and titanium obtained in the embodiment is detected by a conventional method, and the detection shows that Nb in the high-grade composite concentrate2O510.06% of content, 13.32% of REO content and TiO2The content is 13.03%.
Example 4:
a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth comprises the following steps:
(1) mixing low-grade niobium/rare earth/titanium-containing complex ore material (niobium concentrate obtained by primary ore dressing, Nb thereof2O52.37% of TiO24.13 percent of the content, 16.75 percent of Fe, 3.32 percent of rare earth oxide REO, 14.03 percent of CaO, and SiO212.75% of MgO 10.05% of Al2O31.87% of niobium, which is mainly in the form of niobite, niobite rutile or easy-to-dissolve stone, a slag former (limestone in the embodiment), a reducing agent (coke in the embodiment, with a content of 84% of C) based on 100: 15: 10, mixing and batching;
(2) putting the ingredients obtained in the step (1) into an electric furnace for smelting to produce iron-containing alloy, slag and flue gas; controlling the smelting temperature to 1550 ℃ and the smelting time to be 30 min; by controlling the composition and the oxygen potential in the furnace in the burdening in the step (1), the components of the smelting products, the recovery rate of iron and the CaO/SiO of the slag in the step (2) are monitored2The mass ratio is adjusted to adjust a slag system, and the recovery rate of iron in the iron-containing alloy produced in the step is 33.07%; CaO/SiO of slag produced by smelting2Adjusting the mass ratio of CaO to SiO2The mass ratio is controlled to be 2.66;
(3) discharging the slag produced in the step (2) into a slag ladle, cooling and crystallizing, and controlling the cooling speed to be 5 ℃/min to obtain a slag phase (white particles are niobium-rare earth-titanium-containing mineral phases) shown in figure 4;
(4) crushing the furnace slag obtained in the step (3) and then finely grinding to obtain slag powder;
(5) and (4) treating the slag powder obtained in the step (4) by adopting a mineral separation process to obtain high-grade composite concentrate containing niobium, rare earth and titanium.
The high-grade composite concentrate containing niobium, rare earth and titanium obtained in the embodiment is detected by a conventional method, and the detection shows that Nb in the high-grade composite concentrate2O513.85% of content, 18.90% of REO content and TiO2The content is 12.19%.
Example 5:
a method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth comprises the following steps:
(1) mixing low-grade niobium/rare earth/titanium-containing complex ore material (niobium concentrate obtained by primary ore dressing, Nb thereof2O52.37% of TiO24.13 percent of the content, 16.75 percent of Fe, 3.32 percent of rare earth oxide REO, 14.03 percent of CaO, and SiO212.75% of MgO 10.05% of Al2O31.87% of niobium, which is mainly in the form of niobite, niobite rutile or easy-to-dissolve stone), a slag former (calcite is selected in the embodiment), a reducing agent (coke is selected in the embodiment, and the content of C is 84%), based on 100: 50: 25, mixing and batching;
(2) putting the ingredients obtained in the step (1) into an electric furnace for smelting to produce iron-containing alloy, slag and flue gas; controlling the smelting temperature to 1550 ℃ and the smelting time to be 30 min; by controlling the composition and the oxygen potential in the furnace in the burdening in the step (1), the components of the smelting products, the recovery rate of iron and the CaO/SiO of the slag in the step (2) are monitored2The mass ratio is adjusted to a slag system, and the recovery rate of the control iron in the iron-containing alloy produced in the step is 75.7 percent; CaO/SiO of slag produced by smelting2Adjusting the mass ratio of CaO to SiO2The mass ratio is controlled to be 3.84;
(3) discharging the slag produced in the step (2) into a slag ladle, cooling and crystallizing, and controlling the cooling speed to be 5 ℃/min to obtain a slag phase (white particles are niobium-rare earth-titanium-containing mineral phases) shown in figure 5;
(4) crushing the furnace slag obtained in the step (3) and then finely grinding to obtain slag powder;
(5) and (4) treating the slag powder obtained in the step (4) by adopting a mineral separation process to obtain high-grade composite concentrate containing niobium, rare earth and titanium.
The high-grade composite concentrate containing niobium, rare earth and titanium obtained in the embodiment is detected by a conventional method, and the detection shows that Nb in the high-grade composite concentrate2O511.84 percent of content, 15.68 percent of REO content and TiO2The content is 15.33%.
Claims (10)
1. A method for enriching and recovering niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth is characterized by comprising the following steps:
(1) mixing and batching the iron-containing, niobium-containing and rare earth multi-metal ore, a slagging agent and a reducing agent according to the mass ratio of 100 (2-100) to 0-30;
(2) putting the ingredients obtained in the step (1) into a smelting furnace for smelting to produce slag and flue gas; controlling the smelting temperature to be more than or equal to 1350 ℃ and the smelting time to be more than or equal to 10 min; the oxygen potential and the CaO/SiO in the furnace are adjusted by controlling the composition in the ingredients in the step (1) and the oxygen potential in the furnace and monitoring the components of the smelting products and the recovery rate of iron in the step (2)2CaO/SiO of the slag to a suitable range2The mass ratio is 2.5-6.0;
(3) discharging the slag produced in the step (2) into a slag ladle, and cooling and crystallizing;
(4) crushing the furnace slag obtained in the step (3) and then finely grinding to obtain slag powder;
(5) and (4) treating the slag powder obtained in the step (4) by adopting a mineral separation process to obtain high-grade composite concentrate containing niobium, rare earth and titanium.
2. The method for the enrichment recovery of niobium, rare earth and titanium from the iron, niobium and rare earth containing polymetallic ores according to claim 1, wherein the Nb in the iron, niobium and rare earth containing polymetallic ores is2O51-10% of TiO20.5 to 12 percent of the total Fe content, 0.5 to 8 percent of the REO content, 5 to 60 percent of the total Fe content, less than or equal to 30 percent of the CaO content, less than or equal to 20 percent of the MgO content, and SiO22-50% of Al2O3The content is less than or equal to 10 percent; the iron, niobium and rare earth containing polymetallic ore comprises one or more of low-grade niobium concentrate, iron-niobium rare earth concentrate, high-titanium niobium-rich slag, niobium-containing iron ore powder, niobium-iron paragenic ore, niobium-iron concentrate and flotation rare earth tailings.
3. The method for the enrichment recovery of niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth according to claim 1, wherein the reducing agent comprises a solid reducing agent and/or a gaseous reducing agent; the solid reducing agent comprises one or more of semi-coke, pulverized coal, coke, petroleum coke, charcoal, anthracite, bituminous coal and coal; the gas reducing agent comprises one or more of natural gas, water gas, carbon monoxide and hydrogen.
4. The method for recovering niobium, rare earth and titanium from the polymetallic ore containing iron, niobium and rare earth in an enriching way according to claim 1, wherein the slagging agent comprises one or more of dolomite, limestone and calcite.
5. The method for enriching and recovering the niobium, the rare earth and the titanium from the polymetallic ore containing the iron, the niobium and the rare earth according to the claim 1, wherein the ingredients in the step (1) are put into the smelting furnace for smelting after being pelletized, granulated and/or sintered into blocks; the smelting furnace comprises one or more than one of a shaft furnace, a blast furnace, an open hearth furnace, an electric furnace, a converter, a side-blown furnace, a bottom-blown furnace, a top-blown furnace and a reverberatory furnace, and air, pure oxygen or oxygen-enriched air is introduced during smelting.
6. The method for the enrichment recovery of niobium, rare earth and titanium from iron, niobium and rare earth-containing polymetallic ores according to any one of claims 1 to 5, wherein the smelting process also produces iron-containing alloy, the oxygen potential in the furnace is adjusted to a proper range by controlling the composition of ingredients in the step (1) and monitoring the recovery rate of Fe in the iron-containing alloy produced by smelting in the step (2), and the recovery rate of Fe in the iron-containing alloy produced by smelting is controlled to be below 80%.
7. The method for the enrichment recovery of niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth according to claim 6, characterized in that CaO/SiO of the slag2The mass ratio is controlled to be 2.6-5.5.
8. The method for enriching and recovering the niobium, the rare earth and the titanium from the polymetallic ore containing the iron, the niobium and the rare earth as recited in any one of claims 1 to 5, wherein the smelting temperature in the step (2) is controlled to be 1400 ℃ to 1550 ℃ and the smelting time is more than or equal to 30 min.
9. The method for the enrichment recovery of niobium, rare earth and titanium from the polymetallic ore containing iron, niobium and rare earth according to any one of claims 1 to 5, characterized in that the cooling speed of the slag in the step (3) is less than or equal to 30 ℃/min; particularly preferably ≦ 15 ℃/min.
10. The method for the enrichment recovery of niobium, rare earth and titanium from multi-metal ores containing iron, niobium and rare earth according to any one of claims 1 to 5, wherein the Nb is contained in the composite concentrate containing niobium, rare earth and titanium2O5+REO+TiO2The total content is more than or equal to 25 percent, preferably more than or equal to 30 percent.
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| WO2022237607A1 (en) * | 2021-05-08 | 2022-11-17 | 包头稀土研究院 | Method for enriching niobium-titanium in iron-containing niobium-titanium ore and use of nickel-containing substance |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446116A (en) * | 1981-04-02 | 1984-05-01 | Hermann C. Starck Bertin | Process for recovering niobium and/or tantalum compounds from such ores further containing complexes of uranium, thorium, titanium and/or rare earth metals |
| CN105803231A (en) * | 2014-12-30 | 2016-07-27 | 包钢集团矿山研究院（有限责任公司） | Preparation method of low-grade niobium-titanium ferroalloy |
| CN106048107A (en) * | 2016-07-18 | 2016-10-26 | 东北大学 | Smelting reduction production and thermal refining method for titanium-containing slag mixture |
| WO2017015435A1 (en) * | 2015-07-21 | 2017-01-26 | Hazen Research, Inc. | Recovery of rare earths from concentrates containing fluorine |
| CN111041332A (en) * | 2019-12-23 | 2020-04-21 | 包头稀土研究院 | Rare earth niobium-titanium-iron alloy and production method and use method thereof |
-
2020
- 2020-10-27 CN CN202011164943.XA patent/CN112281002B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446116A (en) * | 1981-04-02 | 1984-05-01 | Hermann C. Starck Bertin | Process for recovering niobium and/or tantalum compounds from such ores further containing complexes of uranium, thorium, titanium and/or rare earth metals |
| CN105803231A (en) * | 2014-12-30 | 2016-07-27 | 包钢集团矿山研究院（有限责任公司） | Preparation method of low-grade niobium-titanium ferroalloy |
| WO2017015435A1 (en) * | 2015-07-21 | 2017-01-26 | Hazen Research, Inc. | Recovery of rare earths from concentrates containing fluorine |
| CN106048107A (en) * | 2016-07-18 | 2016-10-26 | 东北大学 | Smelting reduction production and thermal refining method for titanium-containing slag mixture |
| CN111041332A (en) * | 2019-12-23 | 2020-04-21 | 包头稀土研究院 | Rare earth niobium-titanium-iron alloy and production method and use method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022237607A1 (en) * | 2021-05-08 | 2022-11-17 | 包头稀土研究院 | Method for enriching niobium-titanium in iron-containing niobium-titanium ore and use of nickel-containing substance |
| EP4190923A4 (en) * | 2021-05-08 | 2024-03-13 | Baotou Research Institute of Rare Earths | Method for enriching niobium-titanium in iron-containing niobium-titanium ore and use of nickel-containing substance |
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