CN112322890B - Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections - Google Patents

Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections Download PDF

Info

Publication number
CN112322890B
CN112322890B CN202011166802.1A CN202011166802A CN112322890B CN 112322890 B CN112322890 B CN 112322890B CN 202011166802 A CN202011166802 A CN 202011166802A CN 112322890 B CN112322890 B CN 112322890B
Authority
CN
China
Prior art keywords
niobium
concentrate
furnace
grade
slag
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011166802.1A
Other languages
Chinese (zh)
Other versions
CN112322890A (en
Inventor
陈雯
任国兴
肖松文
李家林
彭泽友
周瑜林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changsha Research Institute of Mining and Metallurgy Co Ltd
Original Assignee
Changsha Research Institute of Mining and Metallurgy Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changsha Research Institute of Mining and Metallurgy Co Ltd filed Critical Changsha Research Institute of Mining and Metallurgy Co Ltd
Priority to CN202011166802.1A priority Critical patent/CN112322890B/en
Publication of CN112322890A publication Critical patent/CN112322890A/en
Application granted granted Critical
Publication of CN112322890B publication Critical patent/CN112322890B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/006—Starting from ores containing non ferrous metallic oxides
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections, which comprises the following steps: mixing and batching niobium rough concentrate, a slagging agent, a reducing agent and a binder according to a mass ratio to prepare carbon-containing pellets, and drying the carbon-containing pellets for later use; the carbon-containing pellets are distributed on the bottom of a smelting furnace, carbon powder is laid on the carbon-containing pellets to adjust the atmosphere in the furnace and promote the generation of metallic iron, and the carbon-containing pellets are preheated, reduced and melted at high temperature in the furnace; the oxygen potential and CaO/SiO in the furnace are adjusted by controlling the ingredient composition and the oxygen potential in the furnace and monitoring the components of the smelting products and the metallization rate of the pellets2The mass ratio is in a proper range; CaO/SiO of slag2The mass ratio is controlled to be 0.3-0.7; discharging the molten slag-iron out of the furnace by using a discharger, cooling, grinding and then entering a flotation process to obtain high-grade niobium concentrate. The method has the advantages of simple process, easy operation and low cost, and can produce high-grade niobium concentrate by utilizing the niobium rough concentrate.

Description

Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections
Technical Field
The invention belongs to the field of niobium resource utilization, and particularly relates to a metallurgy method for producing high-grade niobium concentrate from low-grade niobium rough concentrate.
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 reaches 214 ten thousand tons, and the estimation of the prospect reserve exceeds660 million 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 kinds of niobium minerals, up to 20 kinds of niobium minerals, and has complex components, high occupation ratio of low niobium minerals (ferrocolumbium and easy-dissolving stone), low content of high niobium minerals (calcium columbite and pyrochlore), fine embedded granularity, most of niobium minerals being less than 20 mu m, and close symbiosis 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 niobium rough concentrate 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. Furthermore, such aNiobium 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 niobium ore with larger particles and easy flotation separation is obtained through slag slow cooling crystallization, and the niobium grade is further improved through flotation. 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.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provides a method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections.
The technical scheme provided by the invention is a method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections, which comprises the following steps:
(1) mixing the niobium rough concentrate, the slagging agent, the reducing agent and the binder according to the mass ratio of 100 (0-50) to 2-25 to 0-10, preparing carbon-containing pellets and drying for later use; the number of layers of the pellets is preferably 1-5;
(2) the method comprises the following steps of (1) distributing carbon-containing pellets on the bottom of a smelting furnace, paving carbon powder (the thickness is preferably 10-30 mm) to adjust the atmosphere in the furnace and promote the generation of metallic iron, and preheating, reducing and melting the carbon-containing pellets at high temperature in the furnace; the oxygen potential and CaO/SiO in the furnace are adjusted by controlling the ingredient composition and the oxygen potential in the furnace in the step (1) and monitoring the components of the smelted products and the metallization rate of the pellets in the step (2)2The mass ratio is in a proper range; the reduction temperature in the furnace is more than 800 ℃, the reduction time is more than 30min, and the CaO/SiO of the slag2The mass ratio is controlled to be 0.3-0.7;
(3) discharging the molten slag-iron out of the furnace by a discharger, cooling, performing slag-iron separation, grinding the slag (generally to the granularity of less than 200 mu m), and performing flotation to obtain high-grade niobium concentrate.
Preferably, in the method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections, Nb in the niobium rough concentrate is2O51-10% of TiO20.5-12% of the total Fe content, 1-8% of REO content, 5-60% of total Fe content, less than or equal to 30% of CaO content, less than or equal to 20% of MgO content, and SiO2Less than or equal to 50 percent of Al2O3The content is less than or equal to 10 percent; the niobium-containing minerals in the niobium rough concentrate comprise one or more of niobite, niobite rutile, easy-dissolving stones and niobite.
In the above method for producing high-grade niobium concentrate by reducing-melting two sections of niobium rough concentrate, preferably, the reducing agent comprises a solid reducing agent; the solid reducing agent comprises one or more of semi-coke, pulverized coal, coke, petroleum coke, charcoal, anthracite, bituminous coal and coal. 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 method for producing high-grade niobium concentrate by reducing and melting the niobium rough concentrate in two sections, in order to obtain proper slag composition, the slagging agent preferably comprises one or more of quartz stone, river sand, dolomite, limestone, calcite and silica.
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 the method for producing the high-grade niobium concentrate by reducing and melting the niobium rough concentrate in two sections, in order to realize the concentrated conversion of the niobium coexisting in various ore phases to the pyrochlore-type niobium ore, the key point of the method is to control the proper slag composition and the oxygen potential in the furnace in the smelting stage of the step (2). Because the oxygen potential in the furnace is difficult to directly measure, the batch composition in the step (1), namely the proportion of the oxidizing substances (substances which can be reduced by reducing agents, such as iron oxide in niobium concentrate and the like, and oxygen blown into the furnace) and the reducing substances (mainly reducing agents) entering the furnace is controlled, so that the indirect characterization is carried out in the form of the metallization rate of the pellets produced by smelting. More specifically, the reduction temperature in the smelting furnace in the step (2) is controlled to be 800-1150 ℃, the reduction time is 30-60 min, and the metallization rate of the pellets reaches 10-60%; the melting temperature is more than or equal to 1350 ℃, and the melting time is more than or equal to 10 min. Further, the composition of the slag former in the step (1) in the ingredients (namely CaO and SiO in the ingredients) is controlled2Quality) of the slag, and monitoring the CaO/SiO content of the slag produced by the smelting in the step (2)2The mass ratio is adjusted to make the slag system generate the concentrated conversion of niobium to pyrochlore type niobium ore phase. More particularly, the CaO/SiO of the slag2The mass ratio is controlled to be 0.3-0.7, preferably 0.3-0.65. CaO/SiO of slag2The mass ratio is also one of the key factors affecting the niobium-rich ore phase (i.e., niobium-rare earth-titanium mixed ore) and the rare earth ore phase. In order to obtain a pyrochlore phase of larger particle size, which is easily subjected to subsequent beneficiation, separation and recovery operations, even more preferably, the CaO/SiO of the slag2The mass ratio is controlled to be 0.35-0.55.
In the method for producing the high-grade niobium concentrate by reducing and melting the niobium rough concentrate in two sections, preferably, in order to obtain a large-particle artificial pyrochlore phase, the high-grade niobium concentrate can be easily obtained by a subsequent ore dressing method, and the cooling speed of the furnace slag in the step (3) is controlled to be less than or equal to 30 ℃/min; the cooling speed of the slag is preferably controlled to be less than or equal to 15 ℃/min.
Preferably, the high-grade niobium concentrate is pyrochlore-type niobium concentrate, and the Nb content in the high-grade niobium concentrate is zero2O5+REO+TiO2The total content is more than or equal to 30 percent. More preferably, the chemical formula of the main mineral phase pyrochlore in the pyrochlore type niobium concentrate is A2-mB2O6-wY1-n(m is 0 to 1.7, w is 0 to 0.7, and n is 0 to 1), wherein the element at the A position includes Na, Ca, Mn, Ba, REE, Sb, U, Th, Sr, Fe2+At least one of the B-position main constituent elements comprises at least one of Nb, Ti, Ta, Al, Fe (trivalent iron), Zr, Sn and W, and the Y-position mainly has a hole O, F, OH-、H2At least one of O. Based on the theory and the experimental research results, in the forming process of the pyrochlore artificial mineral phase, besides Nb, Rare Earth Elements (REE) and Ti are easy to be enriched into the pyrochlore phase, so that the process not only can solve the problem of recycling niobium in the niobium rough concentrate, but also can synergistically recover the associated rare earth and titanium.
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 difficult dressing of the polymetallic ore niobium minerals in Baiyunebo and the like is the difference of the internal cause of mineral composition/occurrence characteristics, and furthermore, the difficulty degree of subsequent dressing and metallurgy treatment is different due to the difference of the elements of the ore formation and the physicochemical conditions. Based on our latest theoretical and experimental research results, the invention is based on Nb in particular2O5-Na2O-CaO-SiO2-Al2O3-FeOx-TiO2-F-P multicomponent silicateThe slag system is different from a niobium ore carbonate melt system, but the centralized conversion of niobium to a pyrochlore type niobium ore phase can be realized by controlling proper conditions, and then a niobium concentrate product which is easy to concentrate, separate and enrich high grade is obtained.
Compared with the prior art, the process method has the following remarkable advantages:
(1) the process method has strong operability, is economic and reasonable, has simple process steps, can realize the concentrated conversion of various niobium minerals in the iron-niobium rare earth polymetallic ores such as baiyunebo and the like to high-grade and easily-selected pyrochlore ore phases, provides guarantee for obtaining high-grade niobium concentrate, also provides a feasible implementation scheme for the comprehensive utilization of niobium resources in baiyunebo and other places, and really solves the problem of industrial application and development of niobium resources in baiyunebo and other places in China;
(2) the process of the invention also realizes the enrichment of rare earth elements and niobium into rare earth-containing pyrochlore, and realizes the comprehensive recovery of high-value rare earth and niobium;
(3) most of the iron is separated in the form of ferroalloy, so that the comprehensive utilization of the iron in the niobium rough concentrate is realized.
Drawings
FIG. 1 is a microscopic structure view (white particles are pyrochlore phase) of a slag obtained in example 1 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. In the following examples, all the percentages referred to refer to mass percentages unless otherwise specified.
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 producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections comprises the following steps:
(1) coarse niobium concentrate (Nb)2O53.52% of TiO24.29 percent of the total Fe content, 1.50 percent of rare earth oxide REO, 14.03 percent of the total Fe content, 14.03 percent of CaO content 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 slagging agent (limestone in the embodiment), a reducing agent (coke in the embodiment, which contains 84% of C), and a binder are uniformly mixed by a mixer according to the mass ratio of 100:30:5:2, carbon-containing pellets are prepared after uniform mixing by the mixer, and the carbon-containing pellets are dried for later use;
(2) distributing the dried carbon-containing pellets on the furnace bottom of a converter, wherein the number of the pellets is 2, laying a layer of carbon powder with the thickness of 15mm on the furnace bottom in advance to adjust the atmosphere in the furnace and promote the generation of metallic iron, and preheating, reducing and melting the carbon-containing pellets in the furnace at high temperature; the oxygen potential and CaO/SiO in the furnace are adjusted by controlling the ingredient composition and the oxygen potential in the furnace in the step (1) and monitoring the components of the smelted products and the metallization rate of the pellets in the step (2)2The mass ratio is in a proper range; the reduction temperature in the furnace is 900 ℃, the reduction time is 60min, and the metallization rate of the pellets reaches 23.30 percent; the melting temperature is 1500 ℃, the melting time is 30min, and the CaO/SiO of the slag2The mass ratio is controlled to be 0.45;
(3) discharging the molten slag-iron out of the furnace by using a discharger, cooling, performing slag-iron separation, controlling the cooling speed to be 5 ℃/min to obtain the furnace slag shown in the figure 1, grinding the furnace slag by using a ball mill until the granularity is less than 74 mu m, and then entering a flotation process to obtain the high-grade niobium concentrate.
The high-grade pyrochlore-type niobium concentrate obtained in the example was analyzed by conventional testing methods and found to have a chemical formula a for the main mineral phase pyrochlore therein0.94B2O6Y0.15Wherein the elements at the A position mainly comprise Ca, Na and Ba, the rare earth elements La, Ce and Nd, the elements at the B position mainly comprise Nb, Ti and Fe, the elements at the Y position are F,and wherein Nb2O548.91% of content, 26.01% of REO content and TiO2The content is 8.78%.
Example 2:
a method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections comprises the following steps:
(1) coarse niobium concentrate (Nb)2O52.37% of TiO24.13 percent of the content, 3.32 percent of the content of rare earth oxide REO, 16.75 percent of the content of total Fe, 18.94 percent of CaO, and SiO211.23% of MgO, 11.50% of Al2O3The content of niobium is 2.34%, niobium mainly exists in the forms of niobite, niobite rutile, easy-to-dissolve stone and niobite, a slagging agent (limestone and dolomite are selected in the embodiment), a reducing agent (pulverized coal is selected in the embodiment, the carbon content of the pulverized coal is 84%), a binder are uniformly mixed by a mixer according to the mass ratio of 100:20:15:5, carbon-containing pellets are prepared after the uniform mixing by the mixer, and the pellets are dried for later use;
(2) distributing the dried carbon-containing pellets on the bottom of a converter, wherein the number of the pellets is 3, laying a layer of carbon powder with the thickness of 20mm on the bottom of the converter in advance to adjust the atmosphere in the converter and promote the generation of metallic iron, and preheating, reducing and melting the carbon-containing pellets in the converter at high temperature; the oxygen potential and CaO/SiO in the furnace are adjusted by controlling the ingredient composition and the oxygen potential in the furnace in the step (1) and monitoring the components of the smelted products and the metallization rate of the pellets in the step (2)2The mass ratio is in a proper range; the reduction temperature in the furnace is 1000 ℃, the reduction time is 40min, and the metallization rate of the pellets reaches 28.29 percent; the melting temperature is 1400 ℃, the melting time is 60min, and the CaO/SiO of the slag2The mass ratio is controlled to be 0.58;
(3) discharging the molten slag-iron out of the furnace by using a discharger, cooling, performing slag-iron separation, controlling the cooling speed to be 1 ℃/min to obtain furnace slag, grinding the furnace slag by using a ball mill until the granularity is less than 50 mu m, and then entering a flotation process to obtain high-grade niobium concentrate.
The high-grade pyrochlore-type niobium concentrate obtained in the example was analyzed by conventional testing methods and found to have a chemical formula a for the main mineral phase pyrochlore therein1.5B2O5.38Y0.2WhereinThe A site elements include Na, Ca, Mn, Ba and REE, the B site main constituent elements are Nb and Ti, and the Y site F is Nb2O522.05% of content, 9.01% of REO content and TiO2The content is 6.93 percent.
Example 3:
a method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections comprises the following steps:
(1) coarse niobium concentrate (Nb)2O5Content of 6.31%, TiO23.61 percent of the content, 2.5 percent of the content of rare earth oxide REO, 24.03 percent of the content of total Fe, 4.03 percent of CaO, and SiO221.87% of MgO, 1.05% of Al2O30.26 percent of niobium, which mainly exists in the forms of niobite, niobium rutile and easy-to-dissolve stones, a slagging agent (river sand is selected in the embodiment), a reducing agent (anthracite and petroleum coke are selected in the embodiment, the average carbon content of the anthracite and the petroleum coke is 90 percent), a binder, and the binder are uniformly mixed by a mixer according to the mass ratio of 100:5:20:1, and are prepared into carbon-containing pellets after being uniformly mixed by the mixer, and the carbon-containing pellets are dried for later use;
(2) distributing the dried carbon-containing pellets on the bottom of a converter, wherein the number of the pellets is 1, laying a layer of 10mm thick carbon powder on the bottom of the converter in advance to adjust the atmosphere in the converter and promote the generation of metallic iron, and preheating, reducing and melting the carbon-containing pellets at high temperature in the converter; the oxygen potential and CaO/SiO in the furnace are adjusted by controlling the ingredient composition and the oxygen potential in the furnace in the step (1) and monitoring the components of the smelted products and the metallization rate of the pellets in the step (2)2The mass ratio is in a proper range; the reduction temperature in the furnace is 1100 ℃, the reduction time is 30min, and the metallization rate of the pellets reaches 25.9 percent; the melting temperature is 1550 ℃, the melting time is 15min, and the CaO/SiO of the slag2The mass ratio is controlled to be 0.38;
(3) discharging the molten slag-iron out of the furnace by using a discharger, cooling, performing slag-iron separation, controlling the cooling speed to be 10 ℃/min to obtain furnace slag, grinding the furnace slag by using a ball mill until the granularity is less than 25 mu m, and then entering a flotation process to obtain high-grade niobium concentrate.
The high-grade pyrochlore-type niobium concentrate obtained in this example was analyzed by conventional testing methods and found to have a predominant mineral phase pyrochlore thereinHas a chemical formula of A2B2O6Y0.13Wherein the elements at the A position comprise Na, Ca, Mn, Ba and REE, the main constituent elements at the B position comprise Nb, Ti and Fe, the Y position comprises F, and Nb2O547.67% of content, 22.19% of REO content and TiO2The content is 7.98 percent.

Claims (10)

1. A method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections is characterized by comprising the following steps:
(1) mixing the niobium rough concentrate, the slagging agent, the reducing agent and the binder according to the mass ratio of 100 (0-50) to 2-25 to 0-10, preparing carbon-containing pellets and drying for later use;
(2) the carbon-containing pellets are distributed on the bottom of a smelting furnace, carbon powder is laid on the carbon-containing pellets to adjust the atmosphere in the furnace and promote the generation of metallic iron, and the carbon-containing pellets are preheated, reduced and melted at high temperature in the furnace; the oxygen potential in the furnace and the CaO/SiO of the slag are adjusted by controlling the ingredient composition and the oxygen potential in the furnace in the step (1) and monitoring the components of the smelting products and the metallization rate of the pellets in the step (2)2The mass ratio is in a proper range; the reduction temperature in the furnace is 800-1150 ℃, the reduction time is 30-60 min, and the CaO/SiO of the slag2The mass ratio is controlled to be 0.3-0.7; the metallization rate of the pellets reaches 10-60%; the melting temperature is more than or equal to 1350 ℃, and the melting time is more than or equal to 10 min;
(3) discharging the molten slag-iron out of the furnace by using a discharger, cooling, performing slag-iron separation, grinding the slag, and performing flotation to obtain high-grade niobium concentrate.
2. The method for producing the high-grade niobium concentrate through the two-stage reduction-melting of the niobium rough concentrate as claimed in claim 1, wherein the niobium rough concentrate contains 1-10% of Nb2O5, 0.5-12% of TiO2, 1-8% of REO, 5-60% of total Fe, 30% or less of CaO, 20% or less of MgO, and 20% or less of SiO2Less than or equal to 50 percent of Al2O3The content is less than or equal to 10 percent; the niobium-containing minerals in the niobium rough concentrate comprise one or more of niobite, niobite rutile, easy-dissolving stones and niobite.
3. The method for producing high grade niobium concentrate in two stages by reduction-melting of niobium rougher concentrate according to claim 1, wherein the reducing agent comprises a solid reducing agent; the solid reducing agent comprises one or more of semi-coke, petroleum coke, charcoal and coal; the content of C in the solid reducing agent is more than or equal to 75 percent.
4. The method for producing high-grade niobium concentrate through two-stage reduction-melting of niobium rough concentrate according to claim 1, wherein the slagging agent comprises one or more of quartz stone, river sand, dolomite, limestone and silica.
5. The method for producing high-grade niobium concentrate in two stages by reduction-melting of niobium rough concentrate according to claim 1, wherein 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.
6. The method for producing high-grade niobium concentrate through two-stage reduction-melting of niobium rough concentrate according to any one of claims 1-5, characterized in that the composition of the slag former in the ingredients in the step (1) is controlled, and the CaO/SiO content of the slag produced by melting in the step (2) is monitored2The mass ratio is adjusted to ensure that the slag system generates concentrated conversion of niobium to pyrochlore type columbite phase, and the CaO/SiO of the slag2The mass ratio is controlled to be 0.3-0.65.
7. The method for producing high grade niobium concentrate in two stages by reduction-melting of niobium rough concentrate according to claim 6, characterized in that CaO/SiO of the slag is CaO/SiO2The mass ratio is controlled to be 0.35-0.55.
8. The method for producing high-grade niobium concentrate in two stages by reduction-melting of niobium rough concentrate according to any of claims 1-5, characterized in that the cooling rate of the slag in step (3) is less than or equal to 30 ℃/min.
9. The method for producing high-grade niobium concentrate in two stages by reduction-melting of niobium rough concentrate according to any of claims 1-5, characterized in that the high-grade niobium concentrate is a pyrochlore-type niobium concentrate, and wherein Nb is present in the concentrate2O5+REO+TiO2The total content is more than or equal to 30 percent.
10. The method for producing high-grade niobium concentrate according to claim 9, wherein the chemical formula of the main ore phase pyrochlore in the pyrochlore type niobium concentrate is A2-mB2O6-wY1-nM = 0-1.7, w = 0-0.7, n = 0-1, wherein the A site element includes Na, Ca, Mn, Ba, REE, Sb, U, Th, Sr, Fe2+At least one of the main constituent elements in the B position includes at least one of Nb, Ti, Ta, Al, Fe, Zr, Sn and W, and the Y position mainly has a hole O, F, OH-、H2At least one of O.
CN202011166802.1A 2020-10-27 2020-10-27 Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections Active CN112322890B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011166802.1A CN112322890B (en) 2020-10-27 2020-10-27 Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011166802.1A CN112322890B (en) 2020-10-27 2020-10-27 Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections

Publications (2)

Publication Number Publication Date
CN112322890A CN112322890A (en) 2021-02-05
CN112322890B true CN112322890B (en) 2021-08-31

Family

ID=74296901

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011166802.1A Active CN112322890B (en) 2020-10-27 2020-10-27 Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections

Country Status (1)

Country Link
CN (1) CN112322890B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1172170A (en) * 1996-07-25 1998-02-04 冶金工业部长沙矿冶研究院 Method for smelting ferrocolumbium by two-step electric furnace reduction
CN103993162A (en) * 2014-05-21 2014-08-20 包头稀土研究院 Method for removing iron and phosphorus of high phosphorus ferroniobium concentrate
RU2014152467A (en) * 2014-12-24 2016-07-20 Федеральное государственное бюджетное учреждение науки Объединенный институт высоких температур Российской академии наук (ОИВТ РАН) METHOD FOR THERMOCHEMICAL PROCESSING OF RARE METAL RAW MATERIALS
CN105907990A (en) * 2016-05-26 2016-08-31 江苏省冶金设计院有限公司 Method of producing ferrocolumbium
CN106755653A (en) * 2016-12-10 2017-05-31 东北大学 A kind of method containing rare earth or the also original production of niobium slag metallurgy melting
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1172170A (en) * 1996-07-25 1998-02-04 冶金工业部长沙矿冶研究院 Method for smelting ferrocolumbium by two-step electric furnace reduction
CN103993162A (en) * 2014-05-21 2014-08-20 包头稀土研究院 Method for removing iron and phosphorus of high phosphorus ferroniobium concentrate
RU2014152467A (en) * 2014-12-24 2016-07-20 Федеральное государственное бюджетное учреждение науки Объединенный институт высоких температур Российской академии наук (ОИВТ РАН) METHOD FOR THERMOCHEMICAL PROCESSING OF RARE METAL RAW MATERIALS
CN105907990A (en) * 2016-05-26 2016-08-31 江苏省冶金设计院有限公司 Method of producing ferrocolumbium
CN106755653A (en) * 2016-12-10 2017-05-31 东北大学 A kind of method containing rare earth or the also original production of niobium slag metallurgy melting
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

Also Published As

Publication number Publication date
CN112322890A (en) 2021-02-05

Similar Documents

Publication Publication Date Title
CN106048107B (en) A kind of method of titaniferous mixing slag melting and reducing production and modifier treatment
CN112301236B (en) Method for producing high-grade niobium concentrate from niobium rough concentrate
CN106191344B (en) A kind of method for mixing the production of slag melting and reducing and modifier treatment
CN101906498B (en) Method for comprehensively smelting sefstromite
CN106048108B (en) A kind of method of titaniferous mixing slag melting and reducing recycling and modifier treatment
CN112410586B (en) Method for comprehensively recovering niobium, rare earth and titanium from multi-metal ore containing iron, niobium and rare earth
CN106987673B (en) A kind of method that selecting smelting combination is enriched with niobium from titaniferous ferro-niobium concentrate
CN106755651A (en) A kind of method reclaimed containing rare earth and/or niobium slag metallurgy one-step method
WO2019071790A1 (en) Method for recovering valuable components from mixed slag containing zinc and iron
CN102399998A (en) Method for reducing and smelting titania slag by utilizing vanadium-titanium-iron ore concentrates in molten state
CN110592303B (en) Method for smelting vanadium-containing pig iron from vanadium-containing titanomagnetite
CN106755652A (en) A kind of method that titanium-containing slag metallurgy one-step method is reclaimed
CN109880999B (en) Method for recovering iron in copper slag after modification of composite additive and application
CN101643806B (en) Method for producing molten iron with high-phosphorus and low-iron refractory iron ore
CN104446021A (en) Steel and iron slag micro-powder and production method thereof
CN106119447A (en) A kind of produce and the method for modifier treatment containing rare earth and niobium mixing slag melting and reducing
CN112662896A (en) Method for preparing titanium-rich material from titanium ore
CN106755653A (en) A kind of method containing rare earth or the also original production of niobium slag metallurgy melting
CN106755658A (en) A kind of method of the metallurgical also original production of titanium-containing slag
CN106755655A (en) A kind of recovery method for mixing the reduction of slag metallurgy melting
CN106755657A (en) A kind of method that titaniferous mixing slag metallurgy melting reduction is reclaimed
CN112281002B (en) Method for enriching and recovering niobium, rare earth and titanium from multi-metal ore containing iron, niobium and rare earth
CN112322890B (en) Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections
CN109897934B (en) Method for improving efficient phosphorus enrichment effect in phosphorus-containing steel slag
CN106755659A (en) A kind of method that the slag of mixing containing rare earth metallurgy melting reduction is reclaimed

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant