CN109609759B - Separation and enrichment method of valuable components in titanium-iron-containing mineral - Google Patents
Separation and enrichment method of valuable components in titanium-iron-containing mineral Download PDFInfo
- Publication number
- CN109609759B CN109609759B CN201910068307.8A CN201910068307A CN109609759B CN 109609759 B CN109609759 B CN 109609759B CN 201910068307 A CN201910068307 A CN 201910068307A CN 109609759 B CN109609759 B CN 109609759B
- Authority
- CN
- China
- Prior art keywords
- titanium
- iron
- vanadium
- ilmenite
- percent
- 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
Links
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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
-
- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—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
- C22B34/1218—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 obtaining titanium or titanium compounds from ores or scrap by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a separation and enrichment method of valuable components in titanium-containing iron minerals, which comprises the steps of blending the titanium-containing iron minerals and ferrosilicon alloy powder serving as a reducing agent, heating and preserving heat in an electric furnace to perform reduction reaction, grinding into fine powder after the reaction is finished, and performing magnetic separation to obtain iron-containing magnetic substances and titanium-containing nonmagnetic substances. The titaniferous iron minerals include, but are not limited to, ilmenite and vanadium titano-magnetite. Compared with the technology for preparing the high-titanium slag by smelting the ilmenite in the electric arc furnace, the method has the advantages that the reaction temperature is lower, the reduction temperature of the ilmenite can be reduced, the energy is saved, the effective separation and enrichment of the valuable components iron and titanium in the ilmenite are realized, and the recovery rates of the iron and the titanium can reach more than 70 percent and 80 percent respectively. Compared with the traditional blast furnace smelting vanadium-titanium magnetite, the method can recover the valuable component titanium, and can improve the recovery rates of vanadium and chromium, wherein the recovery rates of iron, titanium, vanadium and chromium can respectively reach more than 70%, 80% and 90%.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of mineral resources, and particularly relates to a method for separating and enriching valuable components in titaniferous iron minerals.
Background
Vanadium titano-magnetite is an important iron-containing resource. At present, no mature all vanadium-titanium smelting process exists because the vanadium titano-magnetite has high titanium content (titanium dioxide grade is 7-13%). Vanadium titano-magnetite is usually adopted to be matched with common magnetite or hematite to be smelted in a blast furnace, and in order to ensure the smooth operation of the blast furnace, the content of titanium dioxide in blast furnace slag is controlled to be 22-24 percent at most. The blast furnace slag has low titanium content and low economic value, is mainly stacked at present, occupies land and pollutes the environment. Especially for low-grade vanadium titano-magnetite, because the grade of titanium dioxide in the low-grade vanadium titano-magnetite can reach 20-24%, although blast furnace smelting can be adopted by adding ordinary ore, the total iron grade of blast furnace burden after ore blending can be reduced, so that not only the coke ratio of the blast furnace can be increased, but also valuable component titanium can enter slag, and titanium can not be effectively utilized. If the coal-based reduction-magnetic separation technology of a non-blast furnace method is adopted, although the aim of valuable component extraction can also be achieved, only about 50% of titanium in the vanadium titano-magnetite can be enriched in a non-magnetic substance at most, and the recovery rate of vanadium resources is only 68%. Therefore, the recovery rate of the vanadium-titanium valuable components in the low-grade vanadium-titanium magnetite is low.
Meanwhile, ilmenite has the advantages of abundant reserves, low price and the like, and is often used for producing high-titanium slag and titanium white. In the conventional ferrotitanium separation process, carbon is added into an electric arc furnace to reduce and separate iron and titanium, or ilmenite is directly leached by adopting a sulfuric acid method to obtain titanium white. The preparation of high titanium slag by an electric arc furnace consumes a large amount of energy, the temperature required by reduction is up to 1700-.
Therefore, how to efficiently recycle the valuable components in the minerals containing ferrotitanium, so as to maximally utilize the resources, save energy consumption and reduce a large amount of waste liquid and environmental pollution caused by using sulfuric acid is a topic worthy of discussion and research.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides a method for separating and enriching valuable components in titanium-containing iron ore, which comprises the steps of mixing the titanium-containing iron ore with ferrosilicon alloy powder serving as a reducing agent, heating and preserving heat in an electric furnace to enable the mixture to generate a reduction reaction, and separating iron-containing magnetic substances and titanium-containing nonmagnetic substances generated by the reaction by combining a magnetic separation method, so that the separation and enrichment of the valuable components of iron and titanium in the titanium-containing iron ore are realized, and both the iron-containing magnetic substances and the titanium-containing nonmagnetic substances can be used as raw materials for subsequent production; if the raw material ore is vanadium-titanium magnetite ore, the non-magnetic material obtained by magnetic separation contains valuable components such as titanium, vanadium, chromium and the like.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a process for separating and enriching the valuable components from Ti-Fe ore includes such steps as mixing Ti-Fe ore with ferrosilicon alloy powder as reducer, heating in electric furnace, holding temp for reduction reaction, grinding, magnetic separation to obtain Fe-contained magnetic substance and Ti-contained non-magnetic substance.
Wherein, after the titaniferous iron mineral and the ferrosilicon alloy powder are mixed uniformly, the uniformly mixed mineral powder can be directly used, or the mineral powder is prepared into pellets or blocks and then transferred into an electric furnace for heating reaction.
In a preferred embodiment of the present invention, the ferrosilicon powder contains 69 to 75 wt% of silicon and 25 to 31 wt% of iron.
In a preferred embodiment of the present invention, the titaniferous iron ore is low-grade vanadium titano-magnetite, which comprises the following components: FeO: 17.0-20.0 wt%, CaO: 2.0 to 6.0 wt% of SiO2：6.0～8.0wt％，MgO：0.5～0.9wt％，Al2O3：1.3～2.5wt％，TiO2：20.0～24.0wt％，V2O5：1.6～1.8wt％，Cr2O3: 0.02-0.3 wt%, S is less than or equal to 0.05 wt%, P is less than or equal to 0.01 wt%, and the balance is inevitable impurities; wherein TFe is 42.0-46.0 wt.%.
In a preferred embodiment of the present invention, the ratio of the titanium-containing iron ore to the ferrosilicon alloy is 100: 12-35, and mixing uniformly.
In a preferred embodiment of the present invention, wherein the titaniferous iron ore is ilmenite containing the components: fe2O3：15.1～17.5％，FeO：25.8～27.8％，TiO2：43.4～45.6％,CaO：0.8～0.9％，SiO2：4.6～5.6％，MgO：0.9～1.1％，Al2O3: 1.0 to 1.3%, and the balance unavoidable impurities.
In a preferred embodiment of the invention, the ilmenite and the ferrosilicon alloy powder are mixed and blended in a mass ratio of 100: 12-21.
In a preferred embodiment of the invention, wherein the reaction conditions in the electric furnace are: under the protection of inert atmosphere, heating to 1250-1500 ℃ and preserving heat for 10-120 minutes; the inert atmosphere is Ar and N2One or more of He and mixed gas of He; more preferably at 1450 ℃ of 1300 ℃ for 0.5-2 h.
In a preferred embodiment of the present invention, the ferrosilicon powder has a grain size of 75 μm or less of 90 wt% or more, and the ferrotitanium-containing mineral has a grain size of 75 μm or less of 70 wt% or more.
In a preferred embodiment of the present invention, the titaniferous iron ore is dried in an oven before the reduction reaction. Preferably, the drying is performed in a drying oven at 100-110 ℃ for 4-12h to remove moisture, volatile acids, and the like.
In a preferred embodiment of the present invention, the grinding is performed by grinding the reaction product cooled in the electric furnace to a particle size of 80 wt% or more below 75 μm.
Preferably, the magnetic separation intensity during the magnetic separation is 120-240 kA/m.
In a preferred embodiment of the invention, the electric furnace is a resistance furnace.
In a more preferred embodiment of the present invention, the titaniferous iron ore includes, but is not limited to, ilmenite, high-grade vanadium titano-magnetite, and low-grade vanadium titano-magnetite. Particularly, the utilization rate of valuable components such as titanium, vanadium and the like is very low no matter the low-grade vanadium titano-magnetite adopts a ore blending blast furnace smelting method or a coal-based reduction-magnetic separation technology. In order to solve the technical problem, preferably, the titaniferous iron ore is low-grade vanadium titano-magnetite, and after magnetic separation, an iron-containing magnetic substance and a titanium-, vanadium-and chromium-containing nonmagnetic substance are respectively obtained. The method of the invention has the advantages that the recovery rates of iron, titanium, vanadium and chromium in the low-grade vanadium-titanium magnetite ore can reach more than 70%, 80% and 90%, and the obtained iron-containing magnetic substance and titanium, vanadium and chromium-containing nonmagnetic substance can be used as raw materials for subsequent production.
Wherein, when the raw material ore is low-grade vanadium titano-magnetite, the chemical reaction that it can take place with ferrosilicon alloy powder reduction reaction includes: fe3O4+FeSi2＝4Fe+2SiO2,Fe3O4+2Si＝3Fe+2SiO2,Fe3O4+2FeSi2＝5Fe+4SiO,Fe3O4+4Si＝3Fe+4SiO,4FeTiO3+FeSi2＝3Fe+2FeTi2O5+2SiO,2FeTiO3+Si＝Fe+FeTi2O5+SiO,8FeTiO3+FeSi2＝5Fe+4FeTi2O5+2SiO2,4FeTiO3+Si＝2Fe+2FeTi2O5+SiO2，Fe(Fe,V)2O4+6Si+4FeTiO3＝2(Fe,V)Ti2O5+5Fe+6SiO,Fe(Fe,V)2O4+4FeTiO3+3Si＝5Fe+3SiO2+2(Fe,V)Ti2O5。
Wherein, when the raw material ore is ilmenite, the chemical reaction which can be carried out between the raw material ore and the ferrosilicon alloy powder comprises the following steps: fe3O4+FeSi2＝4Fe+2SiO2,Fe3O4+2Si＝3Fe+2SiO2,Fe3O4+2FeSi2＝5Fe+4SiO,Fe3O4+4Si＝3Fe+4SiO,4FeTiO3+FeSi2＝3Fe+2FeTi2O5+2SiO,2FeTiO3+Si＝Fe+FeTi2O5+SiO,8FeTiO3+FeSi2＝5Fe+4FeTi2O5+2SiO2,4FeTiO3+Si＝2Fe+2FeTi2O5+SiO2。
(III) advantageous effects
The invention has the beneficial effects that:
the invention provides a separation and enrichment method of valuable components in titaniferous iron minerals, which comprises the steps of mixing the titaniferous iron minerals (including but not limited to vanadium titano-magnetite and ilmenite) with ferrosilicon alloy powder, using the ferrosilicon alloy powder as a reducing agent, heating in an electric furnace together, preserving heat to perform a reduction reaction, converting the valuable components such as iron, titanium and the like in the titaniferous iron minerals into iron-containing magnetic substances and titanium-containing nonmagnetic substances, grinding into fine powder, and performing magnetic separation. Wherein the recovery rates of the iron, the titanium, the vanadium and the chromium respectively reach more than 70 percent, 80 percent and 90 percent. The nonmagnetic material obtained is different according to different raw material ores and whether the raw material ores contain elements such as vanadium, chromium and the like, and for vanadium titano-magnetite, the nonmagnetic material contains vanadium and chromium besides titanium.
Compared with the prior art that the method adopts blast furnace smelting to join in bulk ores, the method of the invention can not only efficiently recover the valuable components of iron, vanadium and chromium, but also enrich titanium, thus being beneficial to subsequent treatment or production application as raw materials. Compared with the traditional coal-based reduction-magnetic separation technology which is not a blast furnace method, the process of the invention is simple, is very suitable for industrial large-scale production and application, and can improve the recovery rate of vanadium, iron, titanium and chromium.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments in order to better explain the present invention.
In the following examples, the feed ores of examples 1-7 were low grade vanadium titano-magnetite and the feed ores of examples 8-15 were ilmenite.
Example 1
The embodiment provides a method for separating and enriching valuable components in low-grade vanadium-titanium magnetite, which mainly comprises the steps of using a titanium-containing iron ore as a raw material and using a ferrosilicon alloy as a reducing agent, heating and preserving heat in an electric furnace, wherein a reduction reaction is generated during the heating and heat preservation, so that the valuable components of iron, vanadium and titanium in the raw material ore are converted into a magnetic iron-containing substance and a non-magnetic substance containing titanium, vanadium and chromium, the magnetic iron-containing substance and the non-magnetic substance containing titanium, vanadium and chromium are ground into fine powder, and then the fine powder is separated and enriched by magnetic separation equipment, so that the separation and enrichment of iron, titanium, vanadium and chromium in the titanium-containing iron ore are realized. The method comprises the following steps:
s1, drying pretreatment of the low-grade vanadium titano-magnetite: and (3) putting the low-grade vanadium titano-magnetite into a drying oven at the temperature of 105-110 ℃ for drying for 4-5 h, wherein the content of the low-grade vanadium titano-magnetite is 75 wt% when the particle size is below 75 mu m.
S2, preparing materials: and (3) uniformly mixing the dried low-grade vanadium titano-magnetite processed by the S1 with ferrosilicon alloy powder (72% of silicon + 28% of iron) according to the mass ratio of 100:23 to obtain a mixture. Wherein the ferrosilicon powder has a grain size of 75 μm or less of about 90 wt%.
S3, reduction: and (3) heating the mixture in a resistance furnace, preserving the heat for 120min after the temperature reaches 1300 ℃ under the protection of nitrogen atmosphere, and then cooling to room temperature along with the furnace.
S4, grinding the cooled reaction product to a particle size of less than 75 μm and accounting for more than 80 wt%, and carrying out magnetic separation at a field strength of 160KA/m to respectively obtain a ferrimagnetic substance and a nonmagnetic substance containing titanium, vanadium and chromium.
The main component of the magnetic substance is metallic iron, and the main components of the non-magnetic substance are silicon dioxide and titanium oxide. In this example, the recovery rates of iron, titanium, vanadium and chromium were 71%, 82%, 88% and 95%, respectively.
In order to make the reduction reaction more sufficient, save energy consumption and improve the recovery rate of each component as much as possible, the low-grade vanadium titano-magnetite preferably has a proportion of more than 70 wt% with a particle size of less than 75 μm; preferably, the ferrosilicon powder has a grain size of 75 μm or less of 90 wt% or more.
Example 2
The present embodiment is different from embodiment 1 in that:
in step S2, mixing the low-grade vanadium titano-magnetite and ferrosilicon alloy powder according to a ratio of 100: 28, uniformly mixing, and then pre-pressing and agglomerating; wherein, the silicon-iron alloy powder contains 70 percent of silicon and 30 percent of iron.
In step S3, the resistance furnace is heated to 1350 ℃ under the protection of argon atmosphere, and the reaction is carried out for 2h under the condition of heat preservation.
In step S4, the mixture is ground to a particle size of 80% or more below 75 μm and then magnetically separated at a field strength of 200 KA/m. Respectively obtaining the iron-containing magnetic substance and the titanium, vanadium and chromium-containing nonmagnetic substance.
In this example, the recovery rates of iron, vanadium, chromium and titanium were 70%, 85%, 84% and 93%, respectively.
Example 3
The present embodiment is different from embodiment 1 in that:
in step S2, mixing the low-grade vanadium titano-magnetite and ferrosilicon alloy powder according to a ratio of 100: 28 mass ratio, and then pressing into a block. Wherein, the silicon-iron alloy powder contains 75 percent of silicon and 25 percent of iron.
In step S3, the resistance furnace is heated to 1400 ℃ under the protection of nitrogen atmosphere, and the reaction is carried out for 1 hour under the condition of heat preservation.
In step S4, the mixture is ground to a particle size of 80% or more below 75 μm and then magnetically separated at a field strength of 120 KA/m. Respectively obtaining the iron-containing magnetic substance and the titanium, vanadium and chromium-containing nonmagnetic substance.
In this example, the recovery rates of iron, vanadium, chromium and titanium were 71%, 86%, 81% and 92%, respectively.
Example 4
The present embodiment is different from embodiment 1 in that:
in step S2, mixing the low-grade vanadium titano-magnetite and ferrosilicon alloy powder according to a ratio of 100: 25 percent by mass, and 74 percent of silicon and 26 percent of iron in the ferrosilicon alloy powder.
In step S3, heating to 1400 ℃ under the protection of argon atmosphere, and reacting for 2h under heat preservation.
In step S4, the mixture is ground to a particle size of 80% or more below 75 μm and then magnetically separated at a field strength of 200 KA/m. Respectively obtaining the iron-containing magnetic substance and the titanium, vanadium and chromium-containing nonmagnetic substance.
In this example, the recovery rates of iron, vanadium, chromium and titanium were 76%, 80%, 81% and 93%, respectively.
Example 5
The present embodiment is different from embodiment 1 in that:
in step S2, mixing the low-grade vanadium titano-magnetite and ferrosilicon alloy powder according to a ratio of 100: 26 percent by mass, and 70 percent of silicon and 30 percent of iron in the ferrosilicon alloy powder.
In step S3, under the protection of argon atmosphere, heating to 1450 ℃, and reacting for 30min under heat preservation.
In step S4, the mixture is ground to a particle size of 80% or more below 75 μm and then magnetically separated at a field strength of 240 KA/m. Respectively obtaining the iron-containing magnetic substance and the titanium, vanadium and chromium-containing nonmagnetic substance.
In this example, the recovery rates of iron, vanadium, chromium and titanium were 74%, 83%, 86% and 96%, respectively.
Example 6
The present embodiment is different from embodiment 1 in that:
in step S2, mixing the low-grade vanadium titano-magnetite and ferrosilicon alloy powder according to a ratio of 100: 22 mass percent, and the silicon and the iron in the ferrosilicon alloy powder are 75 percent and 25 percent.
In step S3, the mixture is heated to 1430 ℃ under the protection of argon atmosphere, and the reaction is carried out for 1.5h under the condition of heat preservation.
In step S4, grinding to 80% or more of particle size below 75 μm, and magnetically separating at 180 KA/m. Respectively obtaining the iron-containing magnetic substance and the titanium, vanadium and chromium-containing nonmagnetic substance.
In this example, the recovery rates of iron, vanadium, chromium and titanium were 71%, 88%, 83% and 97%, respectively.
Example 7
The present embodiment is different from embodiment 1 in that:
in step S2, mixing the low-grade vanadium titano-magnetite and ferrosilicon alloy powder according to a ratio of 100: 30 percent by mass, and the silicon and the iron in the ferrosilicon alloy powder are 75 percent and 25 percent.
In step S3, heating to 1450 ℃ under the protection of helium atmosphere, and reacting for 2h under heat preservation.
In step S4, grinding to 80% or more of particle size below 75 μm, and magnetically separating at field strength of 220 KA/m. Respectively obtaining the iron-containing magnetic substance and the titanium, vanadium and chromium-containing nonmagnetic substance.
In this example, the recovery rates of iron, vanadium, chromium and titanium were 78%, 81% and 96%, respectively.
Example 8
The method mainly comprises the steps of uniformly mixing ferrosilicon alloy serving as a reducing agent with ilmenite, heating in an electric furnace, keeping the temperature, carrying out reduction reaction during the heating, converting valuable components iron and titanium in the ilmenite into magnetic iron powder and non-magnetic titanium-containing materials, grinding the iron powder and the titanium-containing materials into fine powder, and separating the iron powder and the titanium-containing materials through magnetic separation equipment for further subsequent treatment and utilization.
Specifically, the method comprises the following steps:
s1, drying pretreatment of ilmenite: and (3) putting ilmenite into a drying oven at the temperature of 105-110 ℃ for drying for 4-5 h, wherein the granularity of the ilmenite is below 75 mu m and accounts for about 80 wt%. Drying in a baking oven to remove water.
Wherein the ilmenite comprises Fe2O3：15.1～17.5％，FeO：25.8～27.8％，TiO2：43.4～45.6％,CaO：0.8～0.9％，SiO2：4.6～5.6％，MgO：0.9～1.1％，Al2O3: 1.0 to 1.3%, and the balance unavoidable impurities.
S2, preparing materials: and (3) uniformly mixing the dried ilmenite treated by the S1 with ferrosilicon alloy powder (silicon 70% + iron 30%) according to the mass ratio of 100:14.6 to obtain a mixture. Wherein the ferrosilicon powder has a grain size of 75 μm or less at a ratio of about 95 wt%.
S3, reduction: and (3) heating the mixture in a resistance furnace, preserving the heat for 120min after the temperature reaches 1380 ℃ under the protection of nitrogen atmosphere, and then cooling to room temperature along with the furnace.
S4, grinding the cooled reaction product to a particle size of less than 75 mu m and more than 80 wt%, and carrying out magnetic separation at a field strength of 180KA/m to respectively obtain magnetic iron powder and nonmagnetic titanium-containing material powder. Wherein, the recovery rate of iron can reach more than 73 percent, and the recovery rate of titanium is 86 percent.
In order to make the reduction reaction more sufficient, save energy consumption and improve the recovery rate of each component as much as possible, the proportion of the grain size of the ilmenite below 75 μm is preferably more than 70 wt%; preferably, the ferrosilicon powder has a grain size of 75 μm or less of 90 wt% or more.
Example 9
The present embodiment is different from embodiment 8 in that: in step S2, the ilmenite and ferrosilicon alloy powder are mixed in a ratio of 100: 14.8, and then pre-pressing into pellets; wherein, the ferrosilicon alloy powder contains 71 percent of silicon and 29 percent of iron. In step S3, the pellets are placed into a resistance furnace under the protection of argon atmosphere, heated to 1400 ℃ by the resistance furnace, and reacted for 100min under heat preservation. In step S4, grinding to 80% or more of particle size below 75 μm, and magnetically separating at 190 KA/m. Respectively obtaining magnetic vanadium-containing iron powder and non-magnetic titanium-containing powder.
Wherein, the recovery rate of iron can reach more than 74 percent, and the recovery rate of titanium is 86 percent.
Example 10
The present embodiment is different from embodiment 8 in that: in step S2, the ilmenite and ferrosilicon alloy powder are mixed in a ratio of 100: 18 mass ratio, and then pressing into a block. Wherein, the silicon-iron alloy powder contains 72 percent of silicon and 28 percent of iron. In step S3, under the protection of nitrogen atmosphere, the block is placed in a resistance furnace, heated to 1450 ℃, and reacted for 90min with heat preservation. In step S4, the mixture is ground to a particle size of 80% or more below 75 μm and then magnetically separated at a field strength of 200 KA/m. Magnetic iron powder and non-magnetic titanium-containing powder are obtained respectively. Wherein, the recovery rate of iron can reach more than 76 percent, and the recovery rate of titanium is 83 percent.
Example 11
The present embodiment is different from embodiment 8 in that: in step S2, the ilmenite and ferrosilicon alloy powder are mixed in a ratio of 100: 15.2, and the silicon and the iron are mixed evenly, wherein the silicon and the iron are 73 percent and 27 percent respectively in the ferrosilicon alloy powder. In step S3, under the protection of argon atmosphere, the powder mixture is placed in a resistance furnace, heated to 1440 ℃, and kept for reaction for 70 min. In step S4, the mixture is ground to a particle size of 80% or more below 75 μm and then magnetically separated at a field strength of 210 KA/m. Magnetic iron powder and non-magnetic titanium-containing powder are obtained respectively. Wherein, the recovery rate of iron can reach more than 77 percent, and the recovery rate of titanium is 85 percent.
Example 12
The present embodiment is different from embodiment 8 in that: in step S2, the ilmenite and ferrosilicon alloy powder are mixed in a ratio of 100: 14.8, and pre-pressing into pellets, wherein the ferrosilicon alloy powder contains 74 percent of silicon and 26 percent of iron. In step S3, under the protection of argon atmosphere, heating to 1430 ℃, and reacting for 60min under heat preservation. In step S4, grinding to 80% or more of particle size below 75 μm, and magnetically separating at field strength of 220 KA/m. Magnetic iron powder and non-magnetic titanium-containing powder are obtained respectively. Wherein, the recovery rate of iron can reach more than 72 percent, and the recovery rate of titanium is 88 percent.
Example 13
The present embodiment is different from embodiment 8 in that: in step S2, the ilmenite and ferrosilicon alloy powder are mixed in a ratio of 100: 15.5, and the silicon and the iron are mixed evenly, wherein the silicon and the iron are 75 percent and 25 percent respectively in the ferrosilicon alloy powder. In step S3, the mixture is heated to 1450 ℃ under the protection of argon atmosphere, and the reaction is carried out for 0.5h under the condition of heat preservation. In step S4, grinding to 80% or more of particle size below 75 μm, and magnetically separating at field strength 230 KA/m. Magnetic iron powder and non-magnetic titanium-containing powder are obtained respectively. Wherein, the recovery rate of iron can reach more than 71 percent, and the recovery rate of titanium is 82 percent.
Example 14
The present embodiment is different from embodiment 8 in that: in step S2, the ilmenite and ferrosilicon alloy powder are mixed in a ratio of 100: 19 mass percent, and 70 percent of silicon and 30 percent of iron in the ferrosilicon alloy powder. In step S3, heating to 1400 ℃ under the protection of helium atmosphere, and reacting for 1.5h under heat preservation. In step S4, grinding to 80% or more of particle size below 75 μm, and magnetically separating at 180 KA/m. Magnetic iron powder and non-magnetic titanium-containing powder are obtained respectively. Wherein, the recovery rate of iron can reach more than 72 percent, and the recovery rate of titanium is 85 percent.
Example 15
The present embodiment is different from embodiment 8 in that: in step S2, the ilmenite and ferrosilicon alloy powder are mixed in a ratio of 100: 35 percent by mass, and 74 percent of silicon and 26 percent of iron in the ferrosilicon alloy powder. In step S3, heating to 1350 ℃ under the protection of helium atmosphere, and reacting for 2h under heat preservation. In step S4, the mixture is ground to a particle size of 80% or more below 75 μm and then magnetically separated at a field strength of 200 KA/m. Magnetic iron powder and non-magnetic titanium-containing powder are obtained respectively. Wherein, the recovery rate of iron can reach more than 75 percent, and the recovery rate of titanium is 81 percent.
Compared with the conventional ilmenite separating process, the reaction temperature of the invention is lower (about 1250-; on the other hand, sulfuric acid is not needed, and the waste liquid amount generated by the subsequent preparation of titanium dioxide products is reduced. The invention has simple process and is suitable for large-scale production and application. Wherein the recovery rate of iron in the ilmenite can reach more than 70 percent, and the recovery rate of titanium can reach more than 80 percent, so the separation and enrichment effects are good.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art can change or modify the technical content disclosed above into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (5)
1. A separation and enrichment method of valuable components in titanium-containing iron minerals is characterized in that the titanium-containing iron minerals and ferrosilicon alloy powder serving as a reducing agent are mixed, then are heated and kept warm in an electric furnace to carry out reduction reaction, and are ground into fine powder after the reaction is finished, and then are subjected to magnetic separation to obtain iron-containing magnetic substances and titanium-containing nonmagnetic substances; the reduction reaction system does not contain a reducing agent except ferrosilicon powder;
the silicon-iron alloy powder contains 69-75 wt% of silicon and 25-31 wt% of iron;
the titaniferous iron ore is low-grade vanadium titano-magnetite and comprises the following components: FeO: 17.0-20.0 wt%, CaO: 2.0 to 6.0 wt% of SiO2：6.0～8.0wt％，MgO：0.5～0.9wt％，Al2O3：1.3～2.5wt％，TiO2：20.0～24.0wt％，V2O5：1.6～1.8wt％，Cr2O3: 0.02-0.3 wt%, S is less than or equal to 0.05 wt%, P is less than or equal to 0.01 wt%, and the balance is inevitable impurities; wherein, TFe is 42.0-46.0 wt.%; at the moment, the mass ratio of the titanium-containing iron ore to the ferrosilicon alloy is 100: 12-35 of blending and blending;
or the titaniferous iron ore is ilmenite which comprises the following components: fe2O3：15.1～17.5％，FeO：25.8～27.8％，TiO2：43.4～45.6％,CaO：0.8～0.9％，SiO2：4.6～5.6％，MgO：0.9～1.1％，Al2O3: 1.0-1.3%, and the balance of inevitable impurities; at the moment, the ilmenite and the ferrosilicon alloy powder are mixed and blended according to the mass ratio of 100: 12-21.
2. The method for separating and enriching valuable components in the titaniferous iron ore according to the claim 1, wherein the reaction conditions in the electric furnace are as follows: under the protection of inert atmosphere, heating to 1250-1500 ℃ and preserving heat for 10-120 minutes; the inert atmosphere is Ar and N2And one or more of He.
3. The method as claimed in claim 1, wherein the ferrosilicon alloy powder has a grain size of 75 μm or less of 90 wt% or more, and the ferrosilicon-containing mineral has a grain size of 75 μm or less of 70 wt% or more.
4. The method for separating and enriching valuable components in the titaniferous iron ore according to claim 1, wherein the titaniferous iron ore is subjected to drying treatment in an oven before reduction reaction.
5. The method for separating and enriching valuable components in titanium-containing iron ore according to claim 1, wherein the grinding into fine powder is to grind the reaction product cooled in an electric furnace into particles with a size of 75 μm or less and accounting for 80 wt%, and the magnetic separation intensity is 120-240 kA/m during magnetic separation.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910068307.8A CN109609759B (en) | 2019-01-24 | 2019-01-24 | Separation and enrichment method of valuable components in titanium-iron-containing mineral |
| PCT/CN2019/075013 WO2020151034A1 (en) | 2019-01-24 | 2019-02-14 | Method for separation and enrichment of valuable components from titanium-containing iron mineral |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910068307.8A CN109609759B (en) | 2019-01-24 | 2019-01-24 | Separation and enrichment method of valuable components in titanium-iron-containing mineral |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109609759A CN109609759A (en) | 2019-04-12 |
| CN109609759B true CN109609759B (en) | 2020-11-03 |
Family
ID=66019176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910068307.8A Active CN109609759B (en) | 2019-01-24 | 2019-01-24 | Separation and enrichment method of valuable components in titanium-iron-containing mineral |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109609759B (en) |
| WO (1) | WO2020151034A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337709B (en) * | 2021-06-01 | 2022-05-10 | 四川省有色矿冶科技有限公司 | Method for reducing titanium content in vanadium-titanium magnetite concentrate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1338969A (en) * | 1971-03-01 | 1973-11-28 | Ici Australia Ltd | Production of metallic iron concentrate and titanium oxide concentrate |
| DE102004053676B4 (en) * | 2004-11-03 | 2010-02-25 | Outotec Oyj | Process and plant for the production of titanium slag from ilmenite |
| CN102352423B (en) * | 2011-10-20 | 2013-04-24 | 攀枝花慧泰金属新材料有限公司 | Method for selecting and smelting titanium from vanadium titanomagnetite at low temperature |
| CN103008098A (en) * | 2012-12-25 | 2013-04-03 | 东北大学 | Solid phase reinforcement reduction-magnetic separation method of vanadium titano-magnetite |
| CN104313310A (en) * | 2014-10-10 | 2015-01-28 | 昆明理工大学 | Method for adding silicon iron powder to increase carbon thermal reduction velocity of vanadium-titanium magnetite concentrate |
| CN105907948B (en) * | 2016-06-27 | 2017-12-01 | 东北大学 | The method of the low-grade magnetic separation of metallized pellet containing chromic vanadium-titanium ferroferrite separation |
-
2019
- 2019-01-24 CN CN201910068307.8A patent/CN109609759B/en active Active
- 2019-02-14 WO PCT/CN2019/075013 patent/WO2020151034A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| CN109609759A (en) | 2019-04-12 |
| WO2020151034A1 (en) | 2020-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102041377B (en) | Method for recovering iron, vanadium and chromium in vanadium-titanium magnetite concentrate | |
| CN105907948A (en) | Magnetic separation method for low-grade chromium-containing vanadium titanium magnetite metalized pellet | |
| WO2017190393A1 (en) | Method for extracting iron and titanium with ferrotitanium complex ore as raw material and filtering device | |
| CN105925743A (en) | Method for preparing ultrapure iron through gas base vertical furnace direct reduction of ultrahigh-grade iron concentrate | |
| CN111254344B (en) | Preparation method of ferrovanadium alloy | |
| CN109609759B (en) | Separation and enrichment method of valuable components in titanium-iron-containing mineral | |
| CN110643775B (en) | Resource utilization method of vanadium-containing steel slag | |
| CN114289726A (en) | FeSiBPNbCu nanocrystalline magnetic powder and preparation method thereof | |
| CN107557567B (en) | A kind of method of high-phosphorus iron ore dephosphorization | |
| CN113234880A (en) | Method for smelting vanadium-rich pig iron from vanadium-containing steel slag and vanadium extraction tailings | |
| CN111518976A (en) | Method for producing ferro-silico-aluminum alloy by using low-grade iron ore powder | |
| CN103740929A (en) | Additive and method for reinforcing separation of manganese and iron through magnetic roasting-magnetic separation of high-iron manganese oxide ore | |
| CN113549726B (en) | Method for strengthening gas-based solid reduction of chromite | |
| CN109666793B (en) | Method for preparing high-titanium-iron alloy by electro-aluminothermic process | |
| CN115404339A (en) | Method for developing and utilizing oolitic high-phosphorus iron ore | |
| CN109554543B (en) | Utilization method of low-grade vanadium titano-magnetite | |
| CN113564351A (en) | Method for preparing chromium-containing nickel iron ore oxidized pellets by using chromite and laterite-nickel ore | |
| CN110342517B (en) | Method for directly producing titanium carbide from vanadium titano-magnetite | |
| CN103725871A (en) | Additive and method for strengthening separation of iron and manganese of high-ferromanganese ore | |
| CN107419090A (en) | A kind of separation method of vanadium titano-magnetite and application | |
| CN107022678B (en) | Method for preparing ferronickel concentrate by selectively reducing laterite-nickel ore | |
| CN103834802A (en) | Titanium pellet for smelting high titanium slag and preparation method thereof | |
| CN110592400A (en) | Novel vanadium extraction and dressing combined method for high-silicon low-calcium stone coal | |
| CN113337709B (en) | Method for reducing titanium content in vanadium-titanium magnetite concentrate | |
| CN113462891B (en) | Method for preparing stainless steel mother liquor from chromium-containing nickel iron ore pellets |
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 |