CN106957963A - Handle the method and system of tailings in vanadium extraction - Google Patents

Handle the method and system of tailings in vanadium extraction Download PDF

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Publication number
CN106957963A
CN106957963A CN201710250410.5A CN201710250410A CN106957963A CN 106957963 A CN106957963 A CN 106957963A CN 201710250410 A CN201710250410 A CN 201710250410A CN 106957963 A CN106957963 A CN 106957963A
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China
Prior art keywords
gallium
iron
tailings
vanadium
entrance
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CN201710250410.5A
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Chinese (zh)
Inventor
宋文臣
王静静
李红科
曹志成
汪勤亚
吴道洪
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Jiangsu Province Metallurgical Design Institute Co Ltd
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Jiangsu Province Metallurgical Design Institute Co Ltd
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Priority to CN201710250410.5A priority Critical patent/CN106957963A/en
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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
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • 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
    • 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
    • C22B58/00—Obtaining gallium or indium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • 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 the method and system of processing tailings in vanadium extraction, method includes：Tailings in vanadium extraction and reduction coal are subjected to mixed-forming, obtain mixing pelletizing；Mixing pelletizing is subjected to reduction roasting processing, metallized pellet is obtained；Metallized pellet is subjected to mill ore magnetic selection processing, iron powder containing gallium and rich vanadium slag is obtained；Rich vanadium slag is mixed with sodium salt and sodium oxide baking processing is carried out, water-soluble sodium vanadate clinker is obtained；Water-soluble sodium vanadate clinker is subjected to Soaking treatment, vanadic anhydride and the first tailings is obtained；Gallium iron powder will be contained and carry out extrusion forming, iron anode containing gallium is obtained, and the progress electrolysis processing of gallium iron anode will be contained, the earth of positive pole containing gallium and electrolytic iron is obtained；Gallium in the earth of positive pole containing gallium is extracted, gallium and the second tailings is obtained.The comprehensive reutilization of iron in tailings in vanadium extraction, vanadium and gallium element can be realized using this method, electrolytic iron, vanadic anhydride and gallium is respectively obtained, tailings in vanadium extraction utilization rate is fundamentally solved low and long-term stack the problem thrown aside.

Description

Handle the method and system of tailings in vanadium extraction
Technical field
The present invention relates to metal smelt field, specifically, the present invention relates to the method and system of processing tailings in vanadium extraction.
Background technology
Climb steel vanadium titano-magnetite and smelted in blast furnace and obtain pig iron containing vanadium, then made by selective oxidation molten iron after vanadium aoxidizes Into slag, V is obtained2O5Content is 14~22% vanadium slag, obtains leached mud, i.e. vanadium extraction tail after oxidized roasting, wet-leaching About 300,000 tons of tailings in vanadium extraction about discharges every year in slag, national vanadium enterprise, and with continuous excessive, the vanadium extraction tail of vanadium enterprise production capacity The discharge capacity of slag will also be gradually stepped up, and so many waste residue is accumulated throughout the year, can not only take a large amount of soils, and can cause environment Pollution.
TFe contents about 30~40%, SiO in typical tailings in vanadium extraction2Content about 10~2%, TiO2Content about 8~15%, Cr2O3Content about 2~5%, MnO contents about 4~7%, V2O5Content about 1~4%, Ga contents about 0.010~0.015%, can be with Find out, all iron content is more than 30% in tailings in vanadium extraction, total vanadium (V2O5) content is 1~4% or so, the content about 0.012 of gallium~ 0.014%, these beneficial metals are if recycling, will greatly improve resource utilization.
Chinese patent CN102337444A proposes technology for producing vanadium chromium manganese alloyed pig iron by melting vanadium extraction tailings, by tailings in vanadium extraction powder Feed particles are made to mix with coke, ilmenite, lime stone, dolomite and fluorite, containing vanadium and chromium manganese is obtained by smelting furnace melting Alloy pig iron.But above method is present that operating procedure is complicated, technological process is long, pay a large amount of energy consumptions makes tailings in vanadium extraction time again Arrived containing vanadium, chromium, gallium molten iron state, in some sense for do not obtain the product of real vanadium, chromium, gallium, final product Added value is not high.
Chinese patent CN101713007A proposes a kind of technique side of directly producing sponge iron by carrying out deep reduction on extracted vanadium tailings Method, using lignite as reducing agent, addition CaO increases the Na in basicity collaboration tailings as slag former simultaneously2O、K2O and SiO2、Al2O3 The resistant mineral of reaction generation class zeolite, this product is to obtain sponge iron by secondary grinding and two sections of low intensity magnetic separations.This method Have the disadvantage the recovery for only only accounting for iron in tailings in vanadium extraction, cause the waste of other valuable elements.
Therefore, the means of existing processing tailings in vanadium extraction are further improved.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, the present invention One purpose is the method and system for proposing processing tailings in vanadium extraction.Using this method can realize iron in tailings in vanadium extraction, vanadium and The comprehensive reutilization of gallium element, respectively obtains electrolytic iron, vanadic anhydride and gallium, fundamentally solves tailings in vanadium extraction profit It is low and long-term stack the problem thrown aside with rate.
In the first aspect of the present invention, the present invention proposes a kind of method for handling tailings in vanadium extraction.According to the reality of the present invention Example is applied, this method includes：Tailings in vanadium extraction and reduction coal are subjected to mixed-forming, to obtain mixing pelletizing；By the mixing ball Group carries out reduction roasting processing, to obtain metallized pellet；The metallized pellet is subjected to mill ore magnetic selection processing, so as to To rich vanadium slag and iron powder containing gallium；The rich vanadium slag is mixed with sodium salt and sodium oxide baking processing is carried out, it is water-soluble to obtain Property sodium vanadate clinker；The water-soluble sodium vanadate clinker is subjected to Soaking treatment, to obtain vanadic anhydride and the first tailings； The iron powder containing gallium is subjected to extrusion forming, to obtain iron anode containing gallium, and the iron anode containing gallium electrolysis processing is subjected to, To obtain the earth of positive pole containing gallium and electrolytic iron；And the gallium in the earth of positive pole containing gallium is extracted, to obtain gallium With the second tailings.
Thus, the method for processing tailings in vanadium extraction according to embodiments of the present invention is by the way that tailings in vanadium extraction and reduction coal are mixed into Type is obtained mixing pelletizing, and mixing pelletizing is carried out into reduction roasting processing, metallized pellet is obtained, first by tailings in vanadium extraction Ferriferous oxide is reduced, and then is handled by mill ore magnetic selection, isolated iron powder containing gallium and rich vanadium slag；It is follow-up by rich vanadium slag with Sodium salt is mixed and carries out sodium oxide baking processing, and the vanadium in rich vanadium slag is converted into water-soluble sodium vanadate clinker, then will be water-soluble Property sodium vanadate clinker carry out Soaking treatment, to obtain vanadic anhydride product and the first tailings；It can will contain gallium iron powder simultaneously Carry out extrusion forming and prepare iron anode containing gallium, and gallium iron anode will be contained to carry out electrolysis processing, obtain electrolysis iron product and contain The gallium earth of positive pole, so that the separation of iron is realized, and then using traditional sour leaching-extraction-electrolytic method to the gallium in the earth of positive pole containing gallium Extracted, to obtain gallium product and the second tailings.Thus, the present processes realize trade waste vanadium extraction tail The comprehensive reutilization of vanadium, iron and gallium in slag, respectively obtains the vanadic anhydride, electrolytic iron and gallium product of high-quality, from The problem that the low and long-term stacking of tailings in vanadium extraction utilization rate is thrown aside fundamentally is solved, with significant economic benefit and Environmental Effect Benefit.
In addition, the method for processing tailings in vanadium extraction according to the above embodiment of the present invention can also have technology additional as follows Feature：
In some embodiments of the invention, by the tailings in vanadium extraction and the reduction coal according to mass ratio 100:(15~ 25) mixed-forming is carried out.Thus, it is possible to significantly improve the degree of metalization for the metallized pellet that sequential reduction calcination process is obtained.
In some embodiments of the invention, the reduction roasting processing is entered at a temperature of 1200~1400 degrees Celsius What 30~90min of row was completed.Thus, it is possible to further improve the degree of metalization for the metallized pellet that reduction is obtained.
In some embodiments of the invention, by the rich vanadium slag and the sodium salt according to mass ratio 100:(10~30) are entered Row mixing.Thus, it is possible to effectively promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
In some embodiments of the invention, the sodium salt is included in sodium carbonate, sodium chloride and sodium sulphate at least One of.Thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
In some embodiments of the invention, the sodium oxide baking processing is at a temperature of 600~900 degrees Celsius Carry out what 1~2h was completed.Thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
In some embodiments of the invention, the Soaking treatment further comprises：By the water-soluble sodium vanadate clinker Soaking treatment is carried out, to obtain containing vanadium solution；Described precipitation processing will be carried out containing vanadium solution, be sunk to obtain ammonium poly-vanadate Form sediment；Ammonium poly-vanadate precipitation is subjected to calcination processing, to obtain vanadic anhydride.Thus, it is possible to effectively obtain Gao Pin The vanadic anhydride product of matter.
In some embodiments of the invention, the electrolysis processing further comprises：By the iron anode containing gallium in ferrous iron Ion concentration is during 30~50g/L, ammonium chloride concentration are the electrolyte that 130~170g/L, pH are 4~6, and is taken the photograph 50~60 Family name's degree, current density are 100~300A/m2Under conditions of carry out the electrolysis processing.Thus, it is possible to effectively obtain high-quality Electrolysis iron product.
In the second aspect of the present invention, the present invention proposes a kind of method for the processing tailings in vanadium extraction for implementing preceding embodiment System.Embodiments in accordance with the present invention, the system includes：Shaped device, the shaped device has tailings in vanadium extraction entrance, gone back Raw coal entrance and the outlet of mixing pelletizing；First calciner, first calciner has mixing pelletizing entrance and metallization Pelletizing is exported, and the mixing pelletizing entrance is connected with the mixing pelletizing outlet；Mill ore magnetic selection device, the mill ore magnetic selection device With metallized pellet entrance, the outlet of iron powder containing gallium and rich vanadium slag outlet, the metallized pellet entrance and the metallization ball Group outlet is connected；Second calciner, second calciner has rich vanadium slag entrance, sodium salt entrance, air intake and water Dissolubility sodium vanadate clinker is exported, and the rich vanadium slag entrance is connected with the rich vanadium slag outlet；Water immersion, the water immersion tool There are water-soluble sodium vanadate clinker entrance, vanadic anhydride outlet and the outlet of the first tailings, the water-soluble sodium vanadate clinker entrance It is connected with the water-soluble sodium vanadate clinker outlet；Extrusion forming device, the extrusion forming device has the entrance of iron powder containing gallium With the outlet of iron anode containing gallium, the entrance of iron powder containing gallium is connected with the iron powder containing gallium outlet；Electrolysis unit, the electrolysis unit With the entrance of iron anode containing gallium, electrolyte entrance, the earth of positive pole containing gallium outlet and electrolytic iron outlet, the entrance of iron anode containing gallium and The outlet of iron anode containing gallium is connected；There is gallium extraction element, the gallium extraction element entrance of the earth of positive pole containing gallium, gallium to export With the outlet of the second tailings, the entrance of the earth of positive pole containing gallium is connected with the earth of positive pole containing gallium outlet.
Thus, the system of processing tailings in vanadium extraction according to embodiments of the present invention is by the way that tailings in vanadium extraction and reduction coal are being molded Mixed-forming is carried out in device to obtain mixing pelletizing, and mixing pelletizing is supplied into the first calciner at progress reduction roasting Reason, obtains metallized pellet, is first reduced the ferriferous oxide in tailings in vanadium extraction, and then using mill ore magnetic selection device to gold Belong to pellet and carry out mill ore magnetic selection processing, so as to isolated iron powder containing gallium and rich vanadium slag；It is follow-up to supply rich vanadium slag and sodium salt Sodium oxide baking processing is carried out into the second calciner, the vanadium in rich vanadium slag is converted into water-soluble sodium vanadate clinker, then Water-soluble sodium vanadate clinker is supplied into water immersion and carries out Soaking treatment, to obtain vanadic anhydride product and the first tail Slag；While can will contain gallium iron powder and progress extrusion forming is supplied into extrusion forming device prepare iron anode containing gallium, and will Iron anode containing gallium, which is supplied into electrolysis unit, carries out electrolysis processing, electrolysis iron product and the earth of positive pole containing gallium is obtained, so as to realize iron Separation, and then the gallium in the earth of positive pole containing gallium is carried using traditional sour leaching-extraction-electrolysis process by gallium extraction element Take, to obtain gallium product and the second tailings.Thus, the system of the processing tailings in vanadium extraction of the application realizes industrial waste The comprehensive reutilization of vanadium, iron and gallium in thing tailings in vanadium extraction, respectively obtains the vanadic anhydride, electrolytic iron and gallium of high-quality Product, fundamentally solve tailings in vanadium extraction utilization rate it is low and it is long-term stack the problem thrown aside, with significant economic benefit and Environmental benefit.
In addition, the system of processing tailings in vanadium extraction according to the above embodiment of the present invention can also have technology additional as follows Feature：
In some embodiments of the invention, first calciner is reduction roasting device, the second roasting dress It is set to sodium oxide baking device.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become from description of the accompanying drawings below to embodiment is combined Substantially and be readily appreciated that, wherein：
Fig. 1 is the method flow schematic diagram of processing tailings in vanadium extraction according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram of the processing tailings in vanadium extraction according to further embodiment of the present invention；
Fig. 3 is the system structure diagram of processing tailings in vanadium extraction according to an embodiment of the invention.
Embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and be not considered as limiting the invention.
In the description of the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not It is interpreted as indicating or implies relative importance or the implicit quantity for indicating indicated technical characteristic.Thus, define " the One ", at least one this feature can be expressed or be implicitly included to the feature of " second ".
In the present invention, unless otherwise clearly defined and limited, " connected " should be interpreted broadly, for example, it may be solid Connect or be detachably connected calmly, or integrally；Can be mechanical connection or electrical connection；It can be direct phase Even, it can also be indirectly connected to by intermediary, can be that the connection of two element internals or the interaction of two elements are closed System, unless otherwise clear and definite restriction.For the ordinary skill in the art, above-mentioned art can be understood as the case may be The concrete meaning of language in the present invention.
In the first aspect of the present invention, the present invention proposes a kind of method for handling tailings in vanadium extraction.According to the reality of the present invention Example is applied, this method includes：Tailings in vanadium extraction and reduction coal are subjected to mixed-forming, to obtain mixing pelletizing；Mixing pelletizing is entered Row reduction roasting is handled, to obtain metallized pellet；Metallized pellet is subjected to mill ore magnetic selection processing, to obtain rich vanadium slag With iron powder containing gallium；Rich vanadium slag is mixed with sodium salt and sodium oxide baking processing is carried out, to obtain water-soluble sodium vanadate clinker； Water-soluble sodium vanadate clinker is subjected to Soaking treatment, to obtain vanadic anhydride and the first tailings；Gallium iron powder will be contained to be squeezed It is molded, to obtain iron anode containing gallium, and gallium iron anode will be contained to carry out electrolysis processing, to obtain the earth of positive pole containing gallium and electrolysis Iron；And the gallium in the earth of positive pole containing gallium is extracted, to obtain gallium and the second tailings.
Method below with reference to Fig. 1~2 pair processing tailings in vanadium extraction according to embodiments of the present invention is described in detail.According to Embodiments of the invention, this method includes：
S100：Mixed-forming
In the step, tailings in vanadium extraction and reduction coal are subjected to mixed-forming, to obtain mixing pelletizing.Specifically, vanadium extraction Tailings is that vanadium titano-magnetite is smelted in blast furnace and obtains pig iron containing vanadium, then vanadium is entered stove after aoxidizing by selective oxidation molten iron Slag, obtains V2O5Content is 14~22% vanadium slag, vanadium slag oxidized roasting, the leached mud obtained after wet-leaching, national vanadium again About 300,000 tons of tailings in vanadium extraction about discharges every year in enterprise, and with continuous excessive, the discharge of tailings in vanadium extraction of vanadium enterprise production capacity Amount will also be gradually stepped up, and so many waste residue is accumulated throughout the year, can not only take a large amount of soils, and can cause environmental pollution.Allusion quotation TFe contents about 30~40%, SiO in type tailings in vanadium extraction2Content about 10~2%, TiO2Content about 8~15%, Cr2O3Content about 2 ~5%, MnO content about 4~7%, V2O5Content about 1~4%, Ga contents about 0.010~0.015%, it can be seen that vanadium extraction tail All iron content is more than 30% in slag, total vanadium (V2O5) content be 1~4% or so, the content about 0.012~0.014% of gallium, this A little beneficial metals are if recycling, will greatly improve resource utilization.
Embodiments in accordance with the present invention, the proportioning of vanadium tailing soil and reduction coal for preparing mixing pelletizing is not limited especially System, those skilled in the art can be selected according to actual needs, according to a particular embodiment of the invention, can be by vanadium extraction tail Slag and reduction coal are according to mass ratio 100:(15~25) mixed-forming is carried out.Inventor has found, by being incorporated going back for said ratio Raw coal, can significantly improve the degree of metalization for the metallized pellet that sequential reduction is obtained, after testing, the metal that sequential reduction is obtained The degree of metalization of pellet is not less than 90%, thereby may be ensured that the high-recovery of iron.
S200：Reduction roasting
In the step, mixing pelletizing is subjected to reduction roasting processing, to utilize reduction coal to the iron oxygen in mixing pelletizing Compound is reduced, and obtains metallized pellet.
Embodiments in accordance with the present invention, the condition of reduction roasting processing is not particularly restricted, and those skilled in the art can To be selected according to actual needs, according to a particular embodiment of the invention, reduction roasting processing is Celsius 1200~1400 Carry out what 30~90min was completed at a temperature of degree.Inventor is by many experiments, by carrying out reduction roasting at the temperature disclosed above Processing, effectively can be reduced to iron simple substance, and ensure that barium oxide is not reduced to by the ferriferous oxide mixed in pelletizing Simple substance, so as to realize the separation of vanadium and iron, if temperature is too high, can make barium oxide be also reduced to simple substance, it is impossible to realize vanadium The selective reduction of oxide and ferriferous oxide, if temperature is too low or the time is too short, can cause the reduction of reduction reaction efficiency.
S300：Mill ore magnetic selection
In the step, metallized pellet is subjected to mill ore magnetic selection processing, so as to which the vanadium in metallized pellet is separated with iron, Obtain rich vanadium slag and iron powder containing gallium.
According to some embodiments of the present invention, the mass fraction of gallium is 0.03~0.045% in iron powder containing gallium.According to this hair Other bright embodiments, the content of rich Vanadium in Vanadium Residue is 2~8%.
S400：Sodium oxide baking
In the step, rich vanadium slag is mixed with sodium salt and sodium oxide baking processing is carried out in air atmosphere, with facility The vanadium in rich vanadium slag is converted into water-soluble sodium vanadate clinker with sodium salt.
Embodiments in accordance with the present invention, the proportioning of rich vanadium slag and sodium salt is not particularly restricted, and those skilled in the art can To be selected according to actual needs, according to a particular embodiment of the invention, the mass ratio of rich vanadium slag and sodium salt can be 100: (10~30), thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the species of sodium salt is not particularly restricted, and those skilled in the art can be according to reality Border needs to be selected, according to a particular embodiment of the invention, and sodium salt can include in sodium carbonate, sodium chloride and sodium sulphate At least one of.Thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the condition of sodium oxide baking processing is not particularly restricted, people in the art Member can be selected according to actual needs, according to a particular embodiment of the invention, sodium oxide baking processing be 600~ Carry out what 1~2h was completed under 900 degrees Celsius.Thus, it is possible to ensure to be calcined positive pentavalent in obtained water-soluble sodium vanadate clinker The ratio that vanadium accounts for full vanadium is not less than 90%, so as to further improve the rate of recovery of vanadium.
S500：Soaking treatment
In the step, water-soluble sodium vanadate clinker is subjected to Soaking treatment, to obtain vanadic anhydride and the first tailings. Specifically, embodiments in accordance with the present invention, Soaking treatment may further include the following steps：
S510：Precipitation is handled
Embodiments in accordance with the present invention, Soaking treatment is carried out by water-soluble sodium vanadate clinker, and water logging condition is：Extraction temperature 80~95 degrees Celsius, the solid mass ratio of liquid is (3~10):1, extraction time is 3~15min, and water logging terminates rear separation of solid and liquid can be with Obtain containing vanadium solution, then will contain vanadium solution purification and impurity removal, acid ammonium salt precipitation processing is carried out again containing vanadium solution after removal of impurities, you can Obtain ammonium poly-vanadate precipitation.
S520：Calcination processing
Further, embodiments in accordance with the present invention, precipitation are handled obtained ammonium poly-vanadate precipitation and carry out calcination processing, Control calcining heat reacts 2h under 550 degrees Celsius and carries out deamination, to obtain vanadic anhydride product.
S600：Extrusion forming and electrolysis processing
In the step, gallium iron powder will be contained and carry out extrusion forming, to obtain iron anode containing gallium, and the progress of gallium iron anode will be contained Electrolysis is handled, to obtain the earth of positive pole containing gallium and electrolytic iron.Embodiments in accordance with the present invention, with the progress of electrolysis processing, sun Pole iron from anodic solution enters electrolyte, and is reduced to fe constantly in the form of the ferrous ion in negative electrode, and gallium is then With Ga (OH)3Solid-state form be enriched in the earth of positive pole, so as to realize the separation of gallium and iron.
Embodiments in accordance with the present invention, the condition of electrolysis processing is not particularly restricted, and those skilled in the art can root Selected according to being actually needed.
According to the specific embodiment of the present invention, electrolysis processing may further include：Gallium iron anode will be contained in ferrous iron Ion concentration is during 30~50g/L, ammonium chloride concentration are the electrolyte that 130~170g/L, pH are 4~6, and is taken the photograph 50~60 Family name's degree, current density are 100~300A/m2Under conditions of carry out electrolysis processing.Thus, it is possible to effectively further obtain Gao Pin The electrolysis iron product of matter.After testing, the mass fraction of iron is not less than 98% in gained electrolysis iron product.
S700：Gallium is extracted
In the step, the gallium in the earth of positive pole containing gallium is extracted, to obtain gallium and the second tailings.Specifically, The mass fraction of gallium about 0.10~0.15% in the earth of positive pole containing gallium, can be extracted by traditional sour leaching-extraction-electrolysis process and contained Gallium in the gallium earth of positive pole, to obtain gallium product.After testing, the mass fraction of gallium is not less than 99% in gallium product.
Thus, the method for processing tailings in vanadium extraction according to embodiments of the present invention is by the way that tailings in vanadium extraction and reduction coal are mixed into Type is obtained mixing pelletizing, and mixing pelletizing is carried out into reduction roasting processing, metallized pellet is obtained, first by tailings in vanadium extraction Ferriferous oxide is reduced, and then is handled by mill ore magnetic selection, isolated iron powder containing gallium and rich vanadium slag；It is follow-up by rich vanadium slag with Sodium salt is mixed and carries out sodium oxide baking processing, and the vanadium in rich vanadium slag is converted into water-soluble sodium vanadate clinker, then will be water-soluble Property sodium vanadate clinker carry out Soaking treatment, obtain containing vanadium solution, and vanadium solution will be contained carrying out after acid ammonium salt precipitation processing, to The ammonium poly-vanadate precipitation arrived carries out calcination processing, to obtain vanadic anhydride product and the first tailings；It can will contain gallium simultaneously Iron powder carries out extrusion forming and prepares iron anode containing gallium, and will contain the progress electrolysis processing of gallium iron anode, obtains being electrolysed iron product With the earth of positive pole containing gallium, so as to realize the separation of iron, and then traditional sour leaching-extraction-electrolytic method is used in the earth of positive pole containing gallium Gallium extracted, to obtain gallium product and the second tailings.It is computed, vanadium extraction tail is handled using the present processes Slag, the rate of recovery of product iron is more than 88%, and the rate of recovery of vanadium is more than 85%, and the rate of recovery of gallium is more than 80%.Thus, originally The method of application realizes the comprehensive reutilization of vanadium, iron and gallium in trade waste tailings in vanadium extraction, respectively obtains high-quality Vanadic anhydride, electrolytic iron and gallium product, fundamentally solve what the low and long-term stacking of tailings in vanadium extraction utilization rate was thrown aside Problem, with significant economic benefit and environmental benefit.
In the second aspect of the present invention, the present invention proposes a kind of method for the processing tailings in vanadium extraction for implementing preceding embodiment System.Embodiments in accordance with the present invention, with reference to Fig. 3, the system includes：Shaped device 100, the first calciner 200, ore grinding Concentration equipment 300, the second calciner 400, water immersion 500, extrusion forming device 600, electrolysis unit 700 and gallium extract dress Put 800.Wherein, shaped device 100 has tailings in vanadium extraction entrance 101, reduction coal entrance 102 and mixing pelletizing outlet 103；First Calciner 200 has mixing pelletizing entrance 201 and metallized pellet outlet 202, and mixing pelletizing entrance 201 goes out with mixing pelletizing Mouth 103 is connected；Mill ore magnetic selection device 300 has metallized pellet entrance 301, the outlet of iron powder containing gallium 302 and rich vanadium slag outlet 303, metallized pellet entrance 301 is connected with metallized pellet outlet 202；Second calciner 400 has rich vanadium slag entrance 401st, sodium salt entrance 402, air intake 403 and water-soluble sodium vanadate clinker outlet 404, rich vanadium slag entrance 401 go out with rich vanadium slag Mouth 303 is connected；Water immersion 500 has water-soluble sodium vanadate clinker entrance 501, vanadic anhydride outlet 502 and the first tailings Outlet 503, water-soluble sodium vanadate clinker entrance 501 is connected with water-soluble sodium vanadate clinker 404；Extrusion forming device 600 has The entrance of iron powder containing gallium 601 and the outlet of iron anode containing gallium 602, the entrance of iron powder containing gallium 601 are connected with the outlet of iron powder containing gallium 302；Electrolysis Device 700 has the entrance of iron anode containing gallium 701, electrolyte entrance 702, the outlet of the earth of positive pole containing gallium 703 and electrolytic iron outlet 704, The entrance of iron anode containing gallium 701 is connected with the outlet of iron anode containing gallium 602；Gallium extraction element 800 have the entrance of the earth of positive pole containing gallium 801, Gallium outlet 802 and the second tailings outlet 803, the entrance of the earth of positive pole containing gallium 801 are connected with the outlet of the earth of positive pole containing gallium 703.
The system of processing tailings in vanadium extraction according to embodiments of the present invention is described in detail below with reference to Fig. 3：
Embodiments in accordance with the present invention, shaped device 100 has tailings in vanadium extraction entrance 101, reduction coal entrance 102 and mixing Pelletizing outlet 103, shaped device 100 is suitable to tailings in vanadium extraction and reduction coal carrying out mixed-forming, to obtain mixing pelletizing.Tool Body, tailings in vanadium extraction is that vanadium titano-magnetite is smelted in blast furnace and obtains pig iron containing vanadium, then by selective oxidation molten iron makes vanadium oxygen Enter slag after change, obtain V2O5Content is 14~22% vanadium slag, vanadium slag oxidized roasting, the leaching obtained after wet-leaching again Slag tap, about 300,000 tons of tailings in vanadium extraction about discharges every year in national vanadium enterprise, and with continuous excessive, the vanadium extraction of vanadium enterprise production capacity The discharge capacity of tailings will also be gradually stepped up, and so many waste residue is accumulated throughout the year, can not only take a large amount of soils, and can cause ring Pollute in border.TFe contents about 30~40%, SiO in typical tailings in vanadium extraction2Content about 10~2%, TiO2Content about 8~15%, Cr2O3Content about 2~5%, MnO contents about 4~7%, V2O5Content about 1~4%, Ga contents about 0.010~0.015%, can be with Find out, all iron content is more than 30% in tailings in vanadium extraction, total vanadium (V2O5) content is 1~4% or so, the content about 0.012 of gallium~ 0.014%, these beneficial metals are if recycling, will greatly improve resource utilization.
Embodiments in accordance with the present invention, the proportioning of vanadium tailing soil and reduction coal for preparing mixing pelletizing is not limited especially System, those skilled in the art can be selected according to actual needs, according to a particular embodiment of the invention, can be by vanadium extraction tail Slag and reduction coal are according to mass ratio 100:(15~25) mixed-forming is carried out.Inventor has found, by being incorporated going back for said ratio Raw coal, can significantly improve the degree of metalization for the metallized pellet that sequential reduction is obtained, after testing, the metal that sequential reduction is obtained The degree of metalization of pellet is not less than 90%, thereby may be ensured that the high-recovery of iron.
Embodiments in accordance with the present invention, the first calciner 200 has mixing pelletizing entrance 201 and metallized pellet outlet 202, mixing pelletizing entrance 201 is connected with mixing pelletizing outlet 103, and the first calciner 200 is suitable to be gone back mixing pelletizing Former calcination process, to be reduced using reduction coal to the ferriferous oxide in mixing pelletizing, obtains metallized pellet.
According to a particular embodiment of the invention, the first calciner 200 can be reduction roasting device.
Embodiments in accordance with the present invention, the condition of reduction roasting processing is not particularly restricted, and those skilled in the art can To be selected according to actual needs, according to a particular embodiment of the invention, reduction roasting processing is Celsius 1200~1400 Carry out what 30~90min was completed at a temperature of degree.Inventor is by many experiments, by carrying out reduction roasting at the temperature disclosed above Processing, effectively can be reduced to iron simple substance, and ensure that barium oxide is not reduced to by the ferriferous oxide mixed in pelletizing Simple substance, so as to realize the separation of vanadium and iron, if temperature is too high, can make barium oxide be also reduced to simple substance, it is impossible to realize vanadium The selective reduction of oxide and ferriferous oxide, if temperature is too low or the time is too short, can cause the reduction of reduction reaction efficiency.
There is embodiments in accordance with the present invention, mill ore magnetic selection device 300 metallized pellet entrance 301, iron powder containing gallium to export 302 are connected with rich vanadium slag outlet 303, metallized pellet entrance 301 with metallized pellet outlet 202, and mill ore magnetic selection device 300 is fitted In metallized pellet is carried out into mill ore magnetic selection processing, so as to which the vanadium in metallized pellet is separated with iron, obtain rich vanadium slag and contain Gallium iron powder.
According to some embodiments of the present invention, the mass fraction of gallium is 0.03~0.045% in iron powder containing gallium.According to this hair Other bright embodiments, the content of rich Vanadium in Vanadium Residue is 2~8%.
Embodiments in accordance with the present invention, the second calciner 400 has rich vanadium slag entrance 401, sodium salt entrance 402, air Entrance 403 and water-soluble sodium vanadate clinker outlet 404, rich vanadium slag entrance 401 are connected with rich vanadium slag outlet 303, the second roasting dress Put 400 to be suitable to mix rich vanadium slag with sodium salt and carry out sodium oxide baking processing in air atmosphere, so that utilization sodium salt will Vanadium in rich vanadium slag is converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the proportioning of rich vanadium slag and sodium salt is not particularly restricted, and those skilled in the art can To be selected according to actual needs, according to a particular embodiment of the invention, the mass ratio of rich vanadium slag and sodium salt can be 100: (10~30), thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the species of sodium salt is not particularly restricted, and those skilled in the art can be according to reality Border needs to be selected, according to a particular embodiment of the invention, and sodium salt can include in sodium carbonate, sodium chloride and sodium sulphate At least one of.Thus, it is possible to effectively further promote the vanadium in rich vanadium slag to be converted into water-soluble sodium vanadate clinker.
Embodiments in accordance with the present invention, the condition of sodium oxide baking processing is not particularly restricted, people in the art Member can be selected according to actual needs, according to a particular embodiment of the invention, sodium oxide baking processing be 600~ Carry out what 1~2h was completed under 900 degrees Celsius.Thus, it is possible to ensure to be calcined positive pentavalent in obtained water-soluble sodium vanadate clinker The ratio that vanadium accounts for full vanadium is not less than 90%, so as to further improve the rate of recovery of vanadium.
Embodiments in accordance with the present invention, water immersion 500 has water-soluble sodium vanadate clinker entrance 501, vanadic anhydride The tailings outlet 503 of outlet 502 and first, water-soluble sodium vanadate clinker entrance 501 exports 404 phases with water-soluble sodium vanadate clinker Even, water immersion 500 is suitable to water-soluble sodium vanadate clinker carrying out Soaking treatment, to obtain vanadic anhydride and the first tail Slag.Specifically, embodiments in accordance with the present invention, Soaking treatment may further include the following steps：
(1) precipitation is handled
Embodiments in accordance with the present invention, by the way that water-soluble sodium vanadate clinker is carried out into Soaking treatment, water logging condition is：Leach 80~95 degrees Celsius of temperature, the solid mass ratio of liquid is (3~10):1, extraction time is 3~15min, and water logging terminates rear separation of solid and liquid It can obtain containing vanadium solution, then will contain vanadium solution purification and impurity removal, acid ammonium salt precipitation processing is carried out again containing vanadium solution after removal of impurities, It can obtain ammonium poly-vanadate precipitation.
(2) calcination processing
Further, embodiments in accordance with the present invention, precipitation are handled obtained ammonium poly-vanadate precipitation and carry out calcination processing, Control calcining heat reacts 2h under 550 degrees Celsius and carries out deamination, to obtain vanadic anhydride product.
There is embodiments in accordance with the present invention, extrusion forming device 600 entrance of iron powder containing gallium 601 and iron anode containing gallium to export 602, the entrance of iron powder containing gallium 601 is connected with the outlet of iron powder containing gallium 302, and extrusion forming device 600 is squeezed suitable for that will contain gallium iron powder It is molded, to obtain iron anode containing gallium.
Embodiments in accordance with the present invention, electrolysis unit 700 has the entrance of iron anode containing gallium 701, electrolyte entrance 702, contained Gallium earth of positive pole outlet 703 and electrolytic iron outlet 704, the entrance of iron anode containing gallium 701 are connected with the outlet of iron anode containing gallium 602, are electrolysed Device 700 is suitable to that the progress electrolysis processing of gallium iron anode will be contained, to obtain the earth of positive pole containing gallium and electrolytic iron.According to the reality of the present invention Apply example, with the progress of electrolysis processing, anode iron constantly in the form of the ferrous ion from anodic solution enters electrolyte, and Negative electrode is reduced to fe, and gallium is then with Ga (OH)3Solid-state form be enriched in the earth of positive pole, so as to realize point of gallium and iron From.
Embodiments in accordance with the present invention, the condition of electrolysis processing is not particularly restricted, and those skilled in the art can root Selected according to being actually needed, according to a particular embodiment of the invention, electrolysis processing may further include：Gallium iron anode will be contained It is during 30~50g/L, ammonium chloride concentration are the electrolyte that 130~170g/L, pH are 4~6 in ferrous ion concentration, and 50 ~60 degrees Celsius, current density be 100~300A/m2Under conditions of carry out electrolysis processing.Thus, it is possible to effectively obtain Gao Pin The electrolysis iron product of matter.After testing, the mass fraction of iron is not less than 98% in gained electrolysis iron product.
There is embodiments in accordance with the present invention, gallium extraction element 800 entrance of the earth of positive pole containing gallium 801, gallium to export 802 and Second tailings outlet 803, the entrance of the earth of positive pole containing gallium 801 and the earth of positive pole containing gallium export 703 and are connected, gallium extraction element 800 suitable for pair Gallium in the earth of positive pole containing gallium is extracted, to obtain gallium and the second tailings.Specifically, in the earth of positive pole containing gallium gallium quality Fraction about 0.10~0.15%, can extract the gallium in the earth of positive pole containing gallium by traditional sour leaching-extraction-electrolysis process, so as to Obtain gallium product.After testing, the mass fraction of gallium is not less than 99% in gallium product.
Thus, the system of processing tailings in vanadium extraction according to embodiments of the present invention is by the way that tailings in vanadium extraction and reduction coal are being molded Mixed-forming is carried out in device to obtain mixing pelletizing, and mixing pelletizing is supplied into the first calciner at progress reduction roasting Reason, obtains metallized pellet, is first reduced the ferriferous oxide in tailings in vanadium extraction, and then using mill ore magnetic selection device to gold Belong to pellet and carry out mill ore magnetic selection processing, isolated iron powder containing gallium and rich vanadium slag；It is follow-up to supply rich vanadium slag and sodium salt to the Sodium oxide baking processing is carried out in two calciners, the vanadium in rich vanadium slag is converted into water-soluble sodium vanadate clinker, then by water Dissolubility sodium vanadate clinker, which is supplied into water immersion, carries out Soaking treatment, obtains containing vanadium solution, and it is acid to contain vanadium solution progress After ammonium salt precipitation processing, calcination processing is carried out to obtained ammonium poly-vanadate precipitation, to obtain vanadic anhydride product and first Tailings；While can will contain gallium iron powder and progress extrusion forming is supplied into extrusion forming device prepare iron anode containing gallium, and Gallium iron anode will be contained and supply into electrolysis unit progress electrolysis processing, electrolysis iron product and the earth of positive pole containing gallium are obtained, so as to realize The separation of iron, and then the gallium in the earth of positive pole containing gallium is extracted using traditional sour leaching-extraction-electrolysis process, to obtain Gallium product and the second tailings.It is computed, tailings in vanadium extraction is handled using the system of the application, the rate of recovery of product iron is 88% More than, the rate of recovery of vanadium is more than 85%, and the rate of recovery of gallium is more than 80%.Thus, the system of the application realizes Industry Waste The comprehensive reutilization of vanadium, iron and gallium in gurry tailings in vanadium extraction, respectively obtains the vanadic anhydride, electrolytic iron and metal of high-quality Gallium product, fundamentally solves the problem that the low and long-term stacking of tailings in vanadium extraction utilization rate is thrown aside, with significant economic benefit And environmental benefit.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only description Property, without limiting the present invention in any way.
Embodiment 1
By tailings in vanadium extraction (TFe contents 30wt%, V2O5Content 1wt%, Ga content 0.010wt%) and reduction coal according to matter Amount is than being 100:15 progress mixed-forming processing obtain mixing pelletizing.Mixing pelletizing is carried out into reduction roasting processing to be metallized Pelletizing, 1200 DEG C of sintering temperature, time 30min, the degree of metalization of metallized pellet is 90%.Metallized pellet is subjected to ore grinding Magnetic separation is handled, and obtains iron powder containing gallium (containing gallium 0.030wt%) and rich vanadium slag (V2O5Content 2wt%).By rich vanadium slag and sodium salt according to Mass ratio 100:Sodium oxide baking is carried out in air atmosphere after 10 mixing to obtain water-soluble sodium vanadate clinker (positive pentavalent vanadium is accounted for The ratio of full vanadium is 92%), sodium oxide baking temperature is 600 DEG C, and the time is 2h, and water-soluble sodium vanadate clinker is entered into water-filling Vanadic anhydride (V is obtained after leaching-purification-precipitation-calcining2O5Content 98.5wt%) and the first tailings.Gallium iron powder will be contained to be squeezed into Type prepares iron anode containing gallium, then will contain gallium iron anode in Fe2+Concentration 30~50g/L, NH4Cl 130~170g/L, pH=4~ In 6 electrolyte, in 50~60 DEG C, 100~300A/m of current density2Under the conditions of electrolytic separation iron and gallium, respectively obtain electrolysis Iron (TFe content 98.5wt%) and the earth of positive pole containing gallium (containing gallium 0.10wt%), will contain the gallium earth of positive pole and carry out sour leaching-extraction-electrolysis Processing, obtains gallium (Ga content 99wt%) and the second tailings.Whole process iron recovery 88%, vanadium recovery 85%, gallium The rate of recovery 80%.
Embodiment 2
By tailings in vanadium extraction (TFe contents 35wt%, V2O5Content 2wt%, Ga content 0.012wt%) and reduction coal according to matter Amount is than being 100:20 progress mixed-forming processing obtain mixing pelletizing.Mixing pelletizing is carried out into reduction roasting processing to be metallized Pelletizing, 1300 DEG C of sintering temperature, time 60min, the degree of metalization of metallized pellet is 92%.Metallized pellet is subjected to ore grinding Magnetic separation is handled, and obtains iron powder containing gallium (containing gallium 0.036wt%) and rich vanadium slag (V2O5Content 4wt%).By rich vanadium slag and sodium salt according to Mass ratio 100:Sodium oxide baking is carried out in air atmosphere after 20 mixing to obtain water-soluble sodium vanadate clinker (positive pentavalent vanadium is accounted for The ratio of full vanadium is 94%), sodium oxide baking temperature is 700 DEG C, and the time is 1.5h, and water-soluble sodium vanadate clinker is entered into water-filling Vanadic anhydride (V is obtained after leaching-purification-precipitation-calcining2O5Content 98.9wt%) and the first tailings.Gallium iron powder will be contained to be squeezed into Type prepares iron anode containing gallium, then will contain gallium iron anode in Fe2+Concentration 30~50g/L, NH4Cl130~170g/L, pH=4~6 Electrolyte in, in 50~60 DEG C, 100~300A/m of current density2Under the conditions of electrolytic separation iron and gallium, respectively obtain electrolytic iron (TFe content 99wt%) and the earth of positive pole containing gallium (contain gallium 0.12wt%), will contain the gallium earth of positive pole and carry out sour leaching-extraction-electrolysis processing, Obtain gallium (Ga content 99wt%) and the second tailings.Whole process iron recovery 89%, vanadium recovery 86%, the gallium rate of recovery 82%.
Embodiment 3
By tailings in vanadium extraction (TFe contents 40wt%, V2O5Content 4wt%, Ga content 0.015wt%) and reduction coal according to matter Amount is than being 100:25 progress mixed-forming processing obtain mixing pelletizing.Mixing pelletizing is carried out into reduction roasting processing to be metallized Pelletizing, 1400 DEG C of sintering temperature, time 90min, the degree of metalization of metallized pellet is 95%.Metallized pellet is subjected to ore grinding Magnetic separation is handled, and obtains iron powder containing gallium (containing gallium 0.045wt%) and rich vanadium slag (V2O5Content 8wt%).By rich vanadium slag and sodium salt according to Mass ratio 100:Sodium oxide baking is carried out in air atmosphere after 30 mixing to obtain water-soluble sodium vanadate clinker (positive pentavalent vanadium is accounted for The ratio of full vanadium is 96%), sodium oxide baking temperature is 900 DEG C, and the time is 1h, and water-soluble sodium vanadate clinker is entered into water-filling Vanadic anhydride (V is obtained after leaching-purification-precipitation-calcining2O5Content 99.2wt%) and the first tailings.Gallium iron powder will be contained to be squeezed into Type prepares iron anode containing gallium, then will contain gallium iron anode in Fe2+Concentration 30~50g/L, NH4Cl 130~170g/L, pH=4~ In 6 electrolyte, in 50~60 DEG C, 100~300A/m of current density2Under the conditions of electrolytic separation iron and gallium, respectively obtain electrolysis Iron (TFe content 99.4wt%) and the earth of positive pole containing gallium (containing gallium 0.15wt%), will contain the gallium earth of positive pole and carry out sour leaching-extraction-electrolysis Processing, obtains gallium (Ga content 99.2wt%) and the second tailings.Whole process iron recovery 93%, vanadium recovery 88%, The gallium rate of recovery 88%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means to combine specific features, structure, material or the spy that the embodiment or example are described Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changed, replacing and modification.

Claims (10)

1. a kind of method for handling tailings in vanadium extraction, it is characterised in that including：
Tailings in vanadium extraction and reduction coal are subjected to mixed-forming, to obtain mixing pelletizing；
The mixing pelletizing is subjected to reduction roasting processing, to obtain metallized pellet；
The metallized pellet is subjected to mill ore magnetic selection processing, to obtain iron powder containing gallium and rich vanadium slag；
The rich vanadium slag is mixed with sodium salt and sodium oxide baking processing is carried out, to obtain water-soluble sodium vanadate clinker；
The water-soluble sodium vanadate clinker is subjected to Soaking treatment, to obtain vanadic anhydride and the first tailings；
The iron powder containing gallium is subjected to extrusion forming, to obtain iron anode containing gallium, and the iron anode containing gallium is electrolysed Processing, to obtain the earth of positive pole containing gallium and electrolytic iron；And
Gallium in the earth of positive pole containing gallium is extracted, to obtain gallium and the second tailings.
2. according to the method described in claim 1, it is characterised in that by the tailings in vanadium extraction and the reduction coal according to mass ratio 100:(15~25) mixed-forming is carried out.
3. according to the method described in claim 1, it is characterised in that the reduction roasting processing is at 1200~1400 degrees Celsius At a temperature of carry out 30~90min complete.
4. according to the method described in claim 1, it is characterised in that by the rich vanadium slag and the sodium salt according to mass ratio 100: (10~30) are mixed.
5. method according to claim 4, it is characterised in that the sodium salt includes being selected from sodium carbonate, sodium chloride and sulfuric acid At least one of sodium.
6. method according to claim 4, it is characterised in that the sodium oxide baking processing is Celsius 600~900 Carry out what 1~2h was completed at a temperature of degree.
7. according to the method described in claim 1, it is characterised in that the Soaking treatment further comprises：
The water-soluble sodium vanadate clinker is subjected to Soaking treatment, to obtain containing vanadium solution；
Described precipitation processing will be carried out containing vanadium solution, to obtain ammonium poly-vanadate precipitation；
Ammonium poly-vanadate precipitation is subjected to calcination processing, to obtain vanadic anhydride.
8. according to the method described in claim 1, it is characterised in that the electrolysis processing further comprises：Will the iron containing gallium Anode is during 30~50g/L, ammonium chloride concentration are the electrolyte that 130~170g/L, pH are 4~6 in ferrous ion concentration, and It is 100~300A/m in 50~60 degrees Celsius, current density2Under conditions of carry out the electrolysis processing.
9. a kind of system of the method for the processing tailings in vanadium extraction described in any one of embodiment claim 1~8, it is characterised in that Including：
Shaped device, the shaped device has tailings in vanadium extraction entrance, reduction coal entrance and the outlet of mixing pelletizing；
First calciner, first calciner has mixing pelletizing entrance and metallized pellet outlet, the mixing ball Group's entrance is connected with the mixing pelletizing outlet；
Mill ore magnetic selection device, the mill ore magnetic selection device has metallized pellet entrance, the outlet of iron powder containing gallium and rich vanadium slag outlet, The metallized pellet entrance is connected with metallized pellet outlet；
Second calciner, second calciner has rich vanadium slag entrance, sodium salt entrance, air intake and water-soluble vanadic acid Sodium clinker is exported, and the rich vanadium slag entrance is connected with the rich vanadium slag outlet；
There is water immersion, the water immersion water-soluble sodium vanadate clinker entrance, vanadic anhydride outlet and the first tailings to go out Mouthful, the water-soluble sodium vanadate clinker entrance is connected with the water-soluble sodium vanadate clinker outlet；
There is extrusion forming device, the extrusion forming device entrance of iron powder containing gallium and iron anode containing gallium to export, the iron containing gallium Powder entrance is connected with the iron powder containing gallium outlet；
Electrolysis unit, the electrolysis unit has the entrance of iron anode containing gallium, electrolyte entrance, the outlet of the earth of positive pole containing gallium and electrolytic iron Outlet, the entrance of iron anode containing gallium is connected with the iron anode containing gallium outlet；
Gallium extraction element, the gallium purification is described to contain gallium with the entrance of the earth of positive pole containing gallium, gallium outlet and the outlet of the second tailings Earth of positive pole entrance is connected with the earth of positive pole containing gallium outlet.
10. system according to claim 9, it is characterised in that first calcination process is reduction roasting device, described Second calciner is sodium oxide baking device.
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CN114410988B (en) * 2021-12-10 2023-10-20 河钢承德钒钛新材料有限公司 Method for deep vanadium extraction by utilizing vanadium extraction tailings
CN114990330A (en) * 2022-05-27 2022-09-02 中国恩菲工程技术有限公司 Chromium slag harmless recycling treatment method, active micro powder material composition and active micro powder material

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