CN106756127A - A kind of method of iron and manganese in extraction solid - Google Patents
A kind of method of iron and manganese in extraction solid Download PDFInfo
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- CN106756127A CN106756127A CN201611174538.XA CN201611174538A CN106756127A CN 106756127 A CN106756127 A CN 106756127A CN 201611174538 A CN201611174538 A CN 201611174538A CN 106756127 A CN106756127 A CN 106756127A
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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
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- 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
- C22B1/08—Chloridising roasting
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
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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
- 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
- C22B7/04—Working-up slag
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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
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- General Life Sciences & Earth Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of method for extracting valuable metal in solid, and in particular to a kind of method that iron and manganese are extracted from steel plant's vanadium slag, manganese spar, rhodonite and alabandite, belong to comprehensive utilization of resources field.It is comprised the following steps：Iron content, manganese solid powder, sodium chloride, ammonium chloride powders will be dried to mix by a certain percentage.Mixture is put into alumina crucible, alumina crucible is put into shaft furnace, high-purity argon gas are connected with shaft furnace, argon gas enters from shaft furnace bottom, and top goes out.Shaft furnace is warmed up to uniform temperature, held for some time.After shaft furnace insulation terminates, alumina crucible is taken out from shaft furnace, the slag after cooling is transferred in container, to solubilization liquid in container, mixture solution filtered, separate solid-liquid, obtain the filter residue of the filtrate of iron content and manganese, deferrization and manganese.The leaching rate of this technique manganese is more than 95%, while the leaching rate of iron is more than 55%.
Description
Technical field
The present invention relates to a kind of method that iron and manganese are extracted from steel plant's vanadium slag, manganese spar, rhodonite and alabandite,
Belong to comprehensive utilization of resources field.
Background technology
Manganese is good deoxidier and desulfurizing agent in steelmaking process；In colored metallurgical industrial, with manganese dioxide and height
The form of potassium manganate is used as oxidant；In alloy production, for producing Al-Mg-Mn alloy.In nature, most common manganese
Oxide have：Pyrolusite (MnO2), psilomelane (mMnOMnO2·nH2O), meta-manganic acid ore (MnO2·nH2O), manganite
(MnO2·Mn(OH)2) and braunite (Mn2O3) etc., MnO, Mn2O3、Mn3O4And MnO2It is water insoluble, due to the manganese in manganese ore
Valence state is generally tetravalence, therefore, the wet-leaching of manganese ore is mainly by adding reducing agent acidleach.With manganese demand increasingly
Increase severely, the poor production and sustainable development that just govern China's manganese systems product of manganese resource, therefore, from low-grade manganese and
The research that manganese is extracted in secondary resource turns into the task of top priority.
It is Chinese to produce 400,000 tons or so vanadium slags every year, substantial amounts of valuable metal iron and manganese are contained in vanadium slag.FeO contains in vanadium slag
It is 30-40wt.% to measure, and MnO contents are 7.44-10.67wt.%.The main thing of vanadium slag mutually has：Spinel (vanadium iron spinelle, manganese
Vanadic spinel and the brilliant point of ferrotianium point), silicate phase (mangan fayalite) and metal iron phase.Iron and manganese are main with bivalent form presence
In vanadium galaxite ((Mn, Fe) V2O4) and mangan fayalite ((Mn, Fe)2SiO4) in.The comprehensive utilization of industrial vanadium slag now
Vanadium extraction is mainly calcined, while vanadium is oxidized, the high price that bivalent manganese is also oxidized to causes the extraction needs addition reduction of manganese
Agent.Document report extracts the manganese in vanadium slag by sulfuric acid leaching, and the recovery rate of manganese is 76.02%.Vanadium slag is used as iron content and manganese
Secondary resource, the ferrimanganic in high efficiente callback vanadium slag is necessary.Meanwhile, manganese is to having special affinity, shadow to mitochondria
The conducting power of nerve synapse is rung, if the manganese in vanadium slag cannot be reclaimed effectively, environment can also be caused harm.
The content of the invention
The invention aims to extract manganese and iron from solid, specifically, it is applied to extract steel plant's vanadium slag, water chestnut
Manganese ore, rhodonite and iron and manganese in alabandite, it is comprised the following steps：
1) will dry steel plant's vanadium slag, manganese spar, rhodonite or alabandite powder, sodium chloride, ammonium chloride powders and compare by certain
Example is mixed.Mixture is put into alumina crucible, alumina crucible is put into shaft furnace, high-purity argon gas, argon are connected with shaft furnace
Gas enters from shaft furnace bottom, and top goes out.Shaft furnace is warmed up to uniform temperature, held for some time takes solid powder from shaft furnace
Go out, in atmosphere natural cooling.
2) by step 1) in alumina crucible in mixture be transferred in container, add solution wherein, solution and
The volume/mass ratio of mixture is more than 5, mixture solution is placed at room temperature 5-100 minutes；
3) by step 2) obtain mixture solution filtering, separate solid-liquid, obtain iron content, manganese or manganese and iron mixing filtrate
With deferrization, manganese or manganese and the mixed filter residue of iron.
Wherein step 1) in the steel plant's vanadium slag, manganese spar, rhodonite or the alabandite Powder Particle Size that add it is micro- in 48-200
Between rice.
Wherein step 1) in sodium chloride be in order to and NH4Cl and MnCl2The fused salt of low melting point is formed, is not involved in chlorination
Reaction, can select one or more chlorides from alkali metal chloride or alkaline earth metal chloride, form fused salt.
Wherein step 1) in ammonium chloride addition cause steel plant's vanadium slag, manganese spar, rhodonite or iron in alabandite powder,
Manganese or manganese and iron are extracted and can carried out, and sodium chloride quality accounts for the 15%-60% of sodium chloride and ammonium chloride quality.Ammonium chloride and steel
The mass ratio of factory's vanadium slag, manganese spar, rhodonite or alabandite powder is more than 1.
Wherein step 1) in shaft furnace be warmed up to 500-1000 DEG C.
Wherein step 1) in shaft furnace insulation 1-6h.
Wherein step 2) in solution be water, hydrochloric acid solution or sulfuric acid solution.
Feature of the present invention is as follows：
(1) present invention have found one kind can be with the side of iron and manganese in high efficiency extraction iron content (divalence) and manganese (divalence) solid
Method.
NH4Cl+1/4Fe2SiO4=1/4SiO2+1/2H2O+1/2FeCl2+NH3
NH4Cl+1/4Fe2TiO4=1/4TiO2+1/2H2O+1/2FeCl2+1/4NH3
NH4Cl+1/2FeCr2O4=1/2Cr2O3+1/2H2O+1/2FeCl2+NH3
NH4Cl+1/2FeV2O4=1/2V2O3+1/2H2O+1/2FeCl2+1/2NH3
NH4Cl+1/4Mn2SiO4=1/4SiO2+1/2H2O+1/2MnCl2+NH3
NH4Cl+1/4Mn2TiO4=1/4TiO2+1/2H2O+1/2MnCl2+NH3
NH4Cl+1/2MnV2O4=1/2V2O3+1/2H2O+1/2MnCl2+1/2NH3
2NH4Cl+MnO=2NH3+H2O+MnCl2
(2) this method sodium chloride (NaCl) and ammonium chloride (NH4Cl) mixture, the quality of ammonium chloride and the quality of vanadium slag
Than more than 1.This is significantly different with the sulfuric acid leaching of manganese in document vanadium slag；
(3) at 500-1000 DEG C, ammonium chloride is decomposed this method reaction temperature at high temperature, and chlorination is formed from new under low temperature
Ammonium, ammonium chloride can be reused；
Specific embodiment
Instantiation described herein is used only for explaining the present invention, is not intended to limit the present invention, art technology
Personnel should be appreciated that the method for the present invention is not limited in extraction steel plant vanadium slag, manganese spar, rhodonite or alabandite powder
Iron, manganese or manganese and iron.
Embodiment 1
(granularity is 48-120 micron, and FeO contents are 37wt.%, and MnO contents are to dry steel plant vanadium slags powder by 40 grams
5.93wt.%) mixed with 10 grams of sodium chloride powders and 40 grams of ammonium chloride powders machineries, be put into crucible.Crucible is placed in be connected with it is high-purity
In the shaft furnace of argon gas, 800 DEG C are warmed up to, are incubated 4h, after insulation terminates, alumina crucible taken out from shaft furnace, after cooling
Slag is transferred in beaker, to solubilization liquid in beaker, mixture solution is filtered, and separates solid-liquid, obtains the filtrate of iron content and manganese, is taken off
The filter residue of iron and manganese.The recovery rate of iron (manganese) is calculated according to following formula：
The recovery rate of the iron=quality of iron (in filtrate in the quality/40 gram vanadium slag powder of iron) × 100, the recovery rate of manganese is also used
Similar formula is calculated.
Embodiment 2
(granularity is 48-120 micron, and FeO contents are 37wt.%, and MnO contents are to dry steel plant vanadium slags powder by 40 grams
5.93wt.%.) mixed with 15 grams of potassium chloride powder and 50 grams of ammonium chloride powders machineries, it is put into crucible.Crucible is placed in be connected with it is high-purity
In the shaft furnace of argon gas, 800 DEG C are warmed up to, are incubated 4h, after insulation terminates, alumina crucible taken out from shaft furnace, after cooling
Slag is transferred in beaker, to solubilization liquid in beaker, mixture solution is filtered, and separates solid-liquid, obtains the filtrate of iron content and manganese, is taken off
The filter residue of iron and manganese.
Embodiment 3
(granularity is 48-120 micron, and FeO contents are 37wt.%, and MnO contents are to dry steel plant vanadium slags powder by 40 grams
5.93wt.%) mixed with 20 grams of sodium chloride powders and 60 grams of ammonium chloride powders machineries, be put into crucible.Crucible is placed in be connected with it is high-purity
In the shaft furnace of argon gas, 800 DEG C are warmed up to, are incubated 4h, after insulation terminates, alumina crucible taken out from shaft furnace, after cooling
Slag is transferred in beaker, to solubilization liquid in beaker, mixture solution is filtered, and separates solid-liquid, obtains the filtrate of iron content and manganese, is taken off
The filter residue of iron and manganese.
Claims (7)
1. a kind of method for extracting iron and manganese in solid, is applied to extract steel plant's vanadium slag, manganese spar, rhodonite or alabandite
Iron, manganese or manganese and iron in powder, it is characterised in that comprise the following steps：
1) will dry steel plant's vanadium slag, manganese spar, rhodonite or alabandite powder, sodium chloride, ammonium chloride powders and mix by a certain percentage
It is even；Mixture is put into alumina crucible, alumina crucible is put into shaft furnace, be connected with high-purity argon gas in shaft furnace, argon gas from
Shaft furnace bottom enters, and top goes out；Shaft furnace is warmed up to uniform temperature, held for some time takes out solid powder from shaft furnace,
Natural cooling in air；
2) by step 1) in alumina crucible in mixture be transferred in container, solution, solution and mixing are added wherein
The volume/mass ratio of thing is more than 5, mixture solution is placed at room temperature 5-100 minutes；
3) by step 2) the mixture solution filtering that obtains, solid-liquid is separated, obtain the filtrate of iron content, manganese or manganese and iron mixing and de-
Iron, manganese or manganese and the mixed filter residue of iron.
2. a kind of method for extracting iron and manganese in solid according to claim 1, it is characterised in that wherein step 1) in add
Steel plant's vanadium slag, manganese spar, rhodonite or alabandite Powder Particle Size between 48-120 microns.
3. a kind of method for extracting iron and manganese in solid according to claim 1, it is characterised in that wherein step 1) in chlorination
Sodium be in order to and NH4Cl and MnCl2Form the fused salt of low melting point, reaction be not involved in chlorination, can from alkali metal chloride or
One or more chlorides are selected in alkaline earth metal chloride, fused salt is formed.
4. a kind of method for extracting iron and manganese in solid according to claim 1, it is characterised in that wherein step 1) in chlorination
The addition of ammonium causes steel plant's vanadium slag, manganese spar, rhodonite or iron, manganese or manganese and iron are extracted and can carried out in alabandite powder,
Sodium chloride quality accounts for the 15%-60% of sodium chloride and ammonium chloride quality；Ammonium chloride and vanadium slag, manganese spar, rhodonite or sulphur manganese
The mass ratio of miberal powder is more than 1.
5. a kind of method for extracting iron and manganese in solid according to claim 1, it is characterised in that wherein step 1) in shaft furnace
It is warmed up to 500-1000 DEG C.
6. a kind of method for extracting iron and manganese in solid according to claim 1, it is characterised in that wherein step 1) in shaft furnace
Insulation 1-6h.
7. a kind of method for extracting iron and manganese in solid according to claim 1, it is characterised in that wherein step 1) in solution
It is water, hydrochloric acid solution or sulfuric acid solution.
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| CN201611174538.XA CN106756127B (en) | 2016-12-19 | 2016-12-19 | A kind of method of iron and manganese in extraction solid |
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| CN201611174538.XA CN106756127B (en) | 2016-12-19 | 2016-12-19 | A kind of method of iron and manganese in extraction solid |
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| CN106756127B CN106756127B (en) | 2018-11-27 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1581762A1 (en) * | 1988-10-03 | 1990-07-30 | Научно-производственное объединение по защите атмосферы, водоемов, использованию вторичных энергоресурсов и охлаждению металлургических агрегатов на предприятиях черной металлургии | Method of processing manganese-containing raw material |
| CN1188155A (en) * | 1997-12-26 | 1998-07-22 | 清华大学 | Method for extracting mixed rare earth oxide by salmiac roasting black weathering slime |
| CN1587423A (en) * | 2004-07-21 | 2005-03-02 | 清华大学 | Method for recovering manganese from low content manganese carbonate raw ore |
| CN101550491A (en) * | 2009-05-16 | 2009-10-07 | 谢永巨 | Method for extracting nickel or cobalt from nickel ore with chloridizing roasting-leaching method |
-
2016
- 2016-12-19 CN CN201611174538.XA patent/CN106756127B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1581762A1 (en) * | 1988-10-03 | 1990-07-30 | Научно-производственное объединение по защите атмосферы, водоемов, использованию вторичных энергоресурсов и охлаждению металлургических агрегатов на предприятиях черной металлургии | Method of processing manganese-containing raw material |
| CN1188155A (en) * | 1997-12-26 | 1998-07-22 | 清华大学 | Method for extracting mixed rare earth oxide by salmiac roasting black weathering slime |
| CN1587423A (en) * | 2004-07-21 | 2005-03-02 | 清华大学 | Method for recovering manganese from low content manganese carbonate raw ore |
| CN101550491A (en) * | 2009-05-16 | 2009-10-07 | 谢永巨 | Method for extracting nickel or cobalt from nickel ore with chloridizing roasting-leaching method |
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