CN115305362A - Method for removing alkali metal by reducing and volatilizing vanadium extraction tailings - Google Patents
Method for removing alkali metal by reducing and volatilizing vanadium extraction tailings Download PDFInfo
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- CN115305362A CN115305362A CN202210842263.1A CN202210842263A CN115305362A CN 115305362 A CN115305362 A CN 115305362A CN 202210842263 A CN202210842263 A CN 202210842263A CN 115305362 A CN115305362 A CN 115305362A
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- vanadium extraction
- extraction tailings
- reducing agent
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- alkali metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- 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
- C22B1/242—Binding; Briquetting ; Granulating with binders
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for removing alkali metal from vanadium extraction tailings by reduction and volatilization, which comprises the following steps: s1, uniformly mixing vanadium extraction tailings, a reducing agent, a binder and water according to a certain proportion, and granulating the uniformly mixed materials; s2, uniformly mixing the granulated product with a reducing agent, then placing the mixture in a reducing atmosphere for reducing roasting, and separating residual reducing agent and dealkalized slag in the mixed material after cooling. According to the invention, the vanadium extraction tailings are subjected to reduction roasting in a mode of combining an internal reducing agent and an external reducing agent, the fine-grained internal reducing agent and the vanadium extraction tailings are fully mixed and contacted, the reduction reaction kinetic conditions of the vanadium extraction tailings in the reduction process are remarkably improved, the external reducing agent reacts in the reduction process to generate a large amount of carbon monoxide, the carbon monoxide and the vanadium extraction tailings are subjected to full indirect reduction reaction, the carbon monoxide and the vanadium extraction tailings are cooperated to enhance the reduction of hematite and alkali metal-containing solid solution in the vanadium extraction tailings, and sodium volatilized from the alkali metal-containing solid solution is volatilized and removed through pores among metal iron particles.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of secondary resources, and relates to a method for removing alkali metal from vanadium extraction tailings by reduction and volatilization.
Background
The vanadium resource in China is mainly enriched in vanadium titano-magnetite, wherein the vanadium is mainly utilized by adopting a process of blast furnace ironmaking, converter preparation of vanadium slag, sodium roasting and water leaching of vanadium. The vanadium extraction tailings are leaching residues after vanadium extraction, and the total amount of the vanadium extraction tailings generated in China every year is more than 60 ten thousand tons. The vanadium extraction tailings not only contain a large amount of valuable elements such as iron, titanium and vanadium, but also contain a large amount of alkali metal elements, and if the vanadium extraction tailings return to a sintering-blast furnace process, the alkali metal content in the vanadium extraction tailings is too high, so that the sintering and blast furnace alkali metal accord with aggravation, and the smooth production is seriously influenced. Therefore, the vanadium extraction tailings cannot be directly utilized at present, and only can be stockpiled, so that the environmental hazard is large, and the waste of resources such as iron, vanadium, titanium and the like can be caused. Therefore, the method for reducing the content of alkali metal elements in the vanadium extraction tailings is the key for realizing the cyclic utilization in the vanadium extraction tailings plant.
The utilization method of the vanadium extraction tailings mainly comprises the research of extracting valuable elements such as iron and vanadium and removing alkali metals in the valuable elements. The method for extracting iron and vanadium from vanadium extraction tailings mainly comprises the methods of magnetizing roasting-magnetic separation and sodium salt roasting-leaching, the methods only concern about the recovery of iron or vanadium resources in the vanadium extraction tailings, the tailings after iron extraction and vanadium extraction are not reasonably treated, a large amount of alkali metal still exists in the tailings, and the problem of environmental pollution during stockpiling is not solved. At present, the research on the dealkalized metal of the vanadium extraction tailings mainly aims at the vanadium extraction tailings with simpler occurrence state of alkali metal, and the research on the dealkalized metal of the vanadium extraction tailings mainly takes an acid leaching method and a calcium oxide leaching method. Although the acid leaching method can reach alkali metal removal rate of more than 90%, a large amount of waste acid is generated in the leaching process to cause secondary pollution, and a leaching reagent reacts with elements in the slag to easily generate insoluble matters such as calcium sulfate and the like which remain in the slag, so that the sulfur content of the leached slag is too high and the leached slag is difficult to return to an iron-making process for utilization. Excessive calcium oxide is required to be added in the calcium oxide leaching process, the method takes vanadium extraction tailings with simple alkali metal occurrence state as raw materials, the alkali metal removal rate is only about 80% at most, the excessive calcium oxide generates calcium hydroxide precipitate in the solution, the alkali metal content in the leaching residue is diluted, and the alkali metal content in the leaching residue is reduced.
In conclusion, in order to effectively utilize the vanadium extraction tailings, a method for efficiently removing alkali metal from the vanadium extraction tailings needs to be developed, waste acid and other products which are easy to cause secondary pollution are not generated in the process, the dealkalized tailings can return to an iron making process, the resource utilization in a vanadium extraction tailings plant is realized, and the method has important environmental protection significance and resource regeneration significance.
Disclosure of Invention
Aiming at the problems that the content of sodium element in the vanadium extraction tailings is high and the alkali load of a blast furnace is increased when the vanadium extraction tailings are returned to the blast furnace at present, the invention aims to provide the method for removing alkali metal by reducing, volatilizing and removing the vanadium extraction tailings, and the method has the advantages of reasonable process flow design, simple operation and no environmental pollution.
The invention provides the following technical scheme: a method for removing alkali metal by reducing, volatilizing and removing vanadium extraction tailings comprises the following steps:
s1, uniformly mixing vanadium extraction tailings, a reducing agent, a binder and water according to a certain proportion, and granulating the uniformly mixed materials to obtain a granulated product;
s2, uniformly mixing the granulated product obtained in the step S1 with a reducing agent, then placing the mixture in a reducing atmosphere for reducing roasting, cooling the mixture, separating residual reducing agent and dealkalized slag in the mixture, returning the residual reducing agent to the reducing roasting process, and returning the dealkalized slag to a sintering-blast furnace process to be used as an iron-making raw material.
Preferably, in the step S1, the reducing agent is one or more of anthracite and coke powder, and the reducing agent accounts for more than 50% of particles with the particle size of-0.074 mm.
Preferably, in the step S1, the mass ratio of the vanadium extraction tailings to the total carbon content in the reducing agent is 1.
Preferably, in step S1, the particle size of the granulated product is 0 to 30mm.
Preferably, in the step S2, the reducing agent is one or more of anthracite and coke powder, the particle size of the reducing agent is 0-30 mm, and the mass ratio of the granulated product to the total carbon content in the reducing agent is 1-2.
Preferably, in the step S2, the reduction roasting temperature is 1000 to 1300 ℃, and the reduction roasting time is 30 to 180min.
Preferably, in step S2, the alkali metal-containing smoke dust volatilized during the reduction roasting process is collected and returned to the vanadium slag sodium modification vanadium extraction process.
The beneficial technical effects of the invention are as follows:
alkali metals in the vanadium extraction tailings mainly exist in complex solid solutions, are difficult to remove by a simple leaching or roasting method, and the alkali metal-containing solid solutions are mostly wrapped by hematite, so that the difficulty of alkali metal removal is aggravated. According to the invention, the vanadium extraction tailings are subjected to reduction roasting in a mode of combining an internal reducing agent and an external reducing agent, the fine-grained internal reducing agent and the vanadium extraction tailings are fully mixed and contacted, the reduction reaction kinetic conditions of the vanadium extraction tailings in the reduction process are remarkably improved, the external reducing agent reacts in the reduction process to generate a large amount of carbon monoxide, the carbon monoxide and the vanadium extraction tailings generate a full indirect reduction reaction, the carbon monoxide and the vanadium extraction tailings cooperate to enhance the reduction of hematite and alkali metal-containing solid solution in the vanadium extraction tailings, the hematite wrapped outside the alkali metal-containing solid solution is reduced into metal iron to form a large amount of pores, and sodium volatilized from the reduction in the alkali metal-containing solid solution is removed and volatilized through the pores between the metal iron particles. The residual reducing agent after the reduction roasting can return to the reduction process, so that the high-efficiency utilization is realized, the dealkalized slag can be used as an iron-making raw material in the sintering-blast furnace process, and the alkali metal-containing smoke dust can return to the vanadium slag sodium treatment vanadium extraction process. The invention has reasonable process flow design, simple operation and no environmental pollution.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following examples further illustrate embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples.
In the examples of the present invention, unless otherwise specified, the means employed are all conventional in the art, and the reagents employed are all available from conventional commercial sources.
The technical solution of the present invention is explained in detail by the following specific examples and the accompanying drawings.
Example 1
From vanadium tailings (35.89% TFe,10.34% SiO% 2 ，10.72％TiO 2 ，4.81％Na 2 O，0.02％K 2 O) is taken as a raw material. The coke powder is used as an internal reducing agent, the grain size of 0.074mm in the coke powder accounts for 80.36%, and the mass ratio of the vanadium extraction tailings to the total carbon content in the coke powder is 1. And uniformly mixing the vanadium extraction tailings, the coke powder, 1% of starch and 8% of water, and granulating to obtain a granulated product with the granularity range of 3-10 mm. The coke powder is used as an external reducing agent, the granularity is 0-10 mm, and the mass ratio of the vanadium extraction tailings to the total carbon content in the coke powder is 1. Mixing the granulated product with coke powder, and performing reduction roasting at 1250 ℃ for 120min. And (5) cooling, and then carrying out magnetic separation to obtain the dealkalized residue and the residual coke. The dealkalization metal rate of the vanadium extraction tailings is 75.21 percentNa in the dealkalized metal product of vanadium extraction tailings 2 The O content was 1.34%.
Example 2
From vanadium tailings (35.89% TFe,10.34% SiO% 2 ，10.72％TiO 2 ，4.81％Na 2 O，0.02％K 2 O) is taken as a raw material. Anthracite is used as an internal reducing agent, the grain size of 0.074mm in the anthracite accounts for 86.98%, and the mass ratio of the vanadium extraction tailings to the total carbon content in the coke powder is 1. And uniformly mixing the vanadium extraction tailings, anthracite, 1% of starch and 8% of water, and granulating to obtain a granulated product with the granularity range of 3-10 mm. The coke powder is used as an external reducing agent, the granularity is 0-10 mm, and the mass ratio of the vanadium extraction tailings to the total carbon content in the coke powder is 1.5. Mixing the granulated product with coke powder, and performing reduction roasting at 1300 deg.C for 120min. And (5) cooling, and then carrying out magnetic separation to obtain the dealkalized residue and the residual coke. The dealkalization metal rate of the vanadium extraction tailings is 77.11 percent, and Na in the dealkalization metal product of the vanadium extraction tailings 2 The O content was 1.15%.
Example 3
From vanadium tailings (31.05% TFe,15.45% 2 ，11.15％TiO 2 ，4.72％Na 2 O，0.01％K 2 O) is taken as a raw material. The coke powder is used as an internal reducing agent, the grain size of 0.074mm in the coke powder accounts for 82.72%, and the mass ratio of the vanadium extraction tailings to the total carbon content in the coke powder is 1. And uniformly mixing the vanadium extraction tailings, the coke powder, 1% of starch and 8% of water, and granulating to obtain a granulated product with the granularity range of 3-10 mm. Anthracite is used as an externally-matched reducing agent, the granularity is 0-10 mm, and the mass ratio of the vanadium extraction tailings to the total carbon content in the anthracite is 1. Mixing the granulated product with anthracite, and reducing and roasting at 1300 ℃ for 120min. And cooling, and performing magnetic separation to obtain the dealkalized residue and residual coke. The dealkalization metal rate of the vanadium extraction tailings is 79.32 percent, and Na in the dealkalization metal product of the vanadium extraction tailings 2 The O content was 1.07%.
Comparative example 1
By vanadium tailings (35.89% TFe,10.34% 2 ，10.72％TiO 2 ，4.81％Na 2 O，0.02％K 2 O) is taken as a raw material. And uniformly mixing the vanadium extraction tailings, 1% of starch and 8% of water, granulating, wherein the granularity range of the granulated product is 3-10 mm, and oxidizing and roasting the granulated product at 1250 ℃ for 120min. Vanadium extraction tailThe slag dealkalization metal rate is 14.17 percent, and Na in the vanadium extraction tailings dealkalization metal product 2 The O content was 4.22%.
Comparative example 2
By vanadium tailings (35.89% TFe,10.34% 2 ，10.72％TiO 2 ，4.81％Na 2 O，0.02％K 2 O) is taken as a raw material. Uniformly mixing the vanadium extraction tailings, 1% of starch and 8% of water, granulating, wherein the granularity range of the granulated product is 3-10 mm, the coke powder is used as an externally-prepared reducing agent, the granularity is 0-10 mm, and the mass ratio of the vanadium extraction tailings to the total carbon content in the coke powder is 1. Mixing the granulated product with coke powder, and performing reduction roasting at 1250 ℃ for 120min. And cooling, and performing magnetic separation to obtain the dealkalized residue and residual coke. The dealkalization metal rate of the vanadium extraction tailings is 49.09 percent, and Na in the dealkalization metal product of the vanadium extraction tailings 2 The O content was 2.75%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (7)
1. A method for removing alkali metal by reducing, volatilizing and removing vanadium extraction tailings is characterized by comprising the following steps:
s1, uniformly mixing vanadium extraction tailings, a reducing agent, a binder and water according to a certain proportion, and granulating the uniformly mixed materials to obtain a granulated product;
s2, uniformly mixing the granulated product obtained in the step S1 with a reducing agent, then placing the mixture in a reducing atmosphere for reducing roasting, cooling the mixture, separating residual reducing agent and dealkalized slag in the mixture, returning the residual reducing agent to the reducing roasting process, and returning the dealkalized slag to a sintering-blast furnace process to be used as an iron-making raw material.
2. The method for removing alkali metals from vanadium extraction tailings through reduction and volatilization according to claim 1, wherein in step S1, the reducing agent is one or more of anthracite and coke powder, and the particle size of the reducing agent is more than 50% of that of particles with the particle size of-0.074 mm.
3. The method for removing alkali metals from vanadium extraction tailings by reduction and volatilization according to claim 1, wherein in step S1, the mass ratio of the vanadium extraction tailings to the total carbon content in the reducing agent is 1.
4. The method for removing alkali metal from vanadium extraction tailings by reductive volatilization according to claim 1, wherein in step S1, the particle size of the granulated product is 0-30 mm.
5. The method for removing alkali metals from vanadium extraction tailings through reduction and volatilization according to claim 1, wherein in step S2, the reducing agent is one or more of anthracite and coke powder, the particle size of the reducing agent is 0-30 mm, and the mass ratio of the granulated product to the total carbon content in the reducing agent is 1.
6. The method for removing alkali metals from vanadium extraction tailings by reduction volatilization according to claim 1, wherein in the step S2, the reduction roasting temperature is 1000-1300 ℃, and the reduction roasting time is 30-180 min.
7. The method for removing alkali metals from vanadium extraction tailings through reduction and volatilization according to claim 1, wherein in step S2, the alkali metal-containing smoke dust volatilized in the reduction roasting process is collected and then returned to the vanadium extraction process of vanadium slag sodium modification.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3890425A (en) * | 1974-03-21 | 1975-06-17 | Southwire Co | Redox treatment of alunite ore |
| US3942974A (en) * | 1975-02-10 | 1976-03-09 | Kennecott Copper Corporation | Manganese nodule pelletizing |
| US4298581A (en) * | 1980-04-15 | 1981-11-03 | Cabot Corporation | Process for recovering chromium, vanadium, molybdenum and tungsten values from a feed material |
| CN103602820A (en) * | 2013-10-11 | 2014-02-26 | 河北钢铁股份有限公司承德分公司 | Method for efficiently recovering iron, vanadium and chromium from extracted vanadium tailings |
| CN103898315A (en) * | 2014-03-20 | 2014-07-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for pelletization calcination of vanadium slag |
| CN106480310A (en) * | 2015-08-31 | 2017-03-08 | 鞍钢股份有限公司 | A kind of alkali-metal method in removing metallurgical dust sludge |
| CN109593968A (en) * | 2019-02-15 | 2019-04-09 | 四川大裂谷钒业有限公司 | From the method for high calcium vanadium slag Green vanadium extraction |
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- 2022-07-18 CN CN202210842263.1A patent/CN115305362B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3890425A (en) * | 1974-03-21 | 1975-06-17 | Southwire Co | Redox treatment of alunite ore |
| US3942974A (en) * | 1975-02-10 | 1976-03-09 | Kennecott Copper Corporation | Manganese nodule pelletizing |
| US4298581A (en) * | 1980-04-15 | 1981-11-03 | Cabot Corporation | Process for recovering chromium, vanadium, molybdenum and tungsten values from a feed material |
| CN103602820A (en) * | 2013-10-11 | 2014-02-26 | 河北钢铁股份有限公司承德分公司 | Method for efficiently recovering iron, vanadium and chromium from extracted vanadium tailings |
| CN103898315A (en) * | 2014-03-20 | 2014-07-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for pelletization calcination of vanadium slag |
| CN106480310A (en) * | 2015-08-31 | 2017-03-08 | 鞍钢股份有限公司 | A kind of alkali-metal method in removing metallurgical dust sludge |
| CN109593968A (en) * | 2019-02-15 | 2019-04-09 | 四川大裂谷钒业有限公司 | From the method for high calcium vanadium slag Green vanadium extraction |
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