CN110373542A - A kind of method of powdered biomass reduction manganese oxide ore - Google Patents
A kind of method of powdered biomass reduction manganese oxide ore Download PDFInfo
- Publication number
- CN110373542A CN110373542A CN201910810700.XA CN201910810700A CN110373542A CN 110373542 A CN110373542 A CN 110373542A CN 201910810700 A CN201910810700 A CN 201910810700A CN 110373542 A CN110373542 A CN 110373542A
- Authority
- CN
- China
- Prior art keywords
- manganese
- added
- pulp
- sulfuric acid
- powdered biomass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B47/00—Obtaining 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of methods of powdered biomass reduction manganese oxide ore.(1) manganese oxidation miberal powder is first added into water or dilute sulfuric acid pulp, then it is slowly added to the concentrated sulfuric acid into pulp liquid, powdered biomass is added after being stirred to react 60-120 minutes, maintain temperature of reaction system, continue after being stirred to react 60-180 minutes, obtains prereduction ore pulp；(2) water or dilute sulfuric acid are added into prereduction ore pulp, after being stirring evenly and then adding into reducing agent reduction 60-120 minutes, manganese sulfate leachate can both be made；(3) manganese sulfate leachate is neutralized, removal of impurities, is separated by solid-liquid separation, and can be prepared by manganese sulfate solution.In conclusion the present invention, which has, overcomes the shortcomings of existing direct reducing leaching technology, sequential reduction process reducing agent consumption is reduced, improves manganese rate of reduction and reducing leaching rate, reduces waste residue yield, reduces the beneficial effect that manganese oxide ore leaches cost.
Description
Technical field
The present invention relates to a kind of methods of powdered biomass reduction manganese oxide ore, belong to hydrometallurgy and chemical field.
Background technique
Manganese oxide ore cannot use sulfuric acid directly to leach, become the application difficult point in industry due to containing a large amount of tetravalent manganeses.
Currently, manganese oxide ore generally use solid reductant C or gaseous reducing agent (CO, H2) 850 DEG C or so high temperature also
Original roasting, by MnO therein2Sulfuric acid leaching is reused after being reduced to MnO.
Its reaction is
Reduction roasting: MnO2+ C=MnO+CO
MnO2+ CO=MnO+CO2
MnO2+H2=MnO+H2O
Sulfuric acid leaching: MnO+H2SO4=MnSO4+H2O
Manganese oxide ore reduction roasting energy consumption is high, and baking flue gas is containing the pollution such as solid particulate matter, oxysulfide, nitrogen oxides
Object, qualified discharge after need to being handled；It is reoxidized to prevent the MnO after reduction from contacting with air, product of roasting needs quenching.
Therefore, although this method reduction effect is ideal, process is complicated, processing cost is higher.
The hot spot that acidleach manganese oxide ore is always industry research, the method master reported at present are reduced directly in sulfuric acid system
There are two mine one-step method, SO2And sulfite reduction method etc., biomass reduction method, organic matter reduction method, iron filings and ferrous reduction
Method etc..
Two mine one-step method are more mature, but S will be generated under the conditions of initial acid concentrations are higher0, a large amount of nascent state S0Attachment
On ore particle surface, due to its with strong-hydrophobicity and it is non-conductive hinder the progress of tetravalence manganese oxide reduction reaction, need to heat
Or increase reduction dosage could obtain more satisfied manganese leaching rate.Though two mine one-step method are improved through numerous studies, there are still
Reducing agent usage amount is big, the reaction time is long, and solution iron content is high, except iron difficulty and the big disadvantage of the quantity of slag, limits its popularization and answers
With.
SO2And sulfite reduction method is more demanding to system pH control, pH value is low, and reducing agent utilization rate is low；PH value
Height, leaching process is slower, and reduction process side reaction will generate manganous dithionate, has certain influence to manganese sulfate solution quality.
Biomass reduction method reducing agent is from a wealth of sources, but the reaction time is long, and large amount of organic is residual in solution after leaching
It stays, it is difficult to remove.
The manganese such as organic matter reduction method such as formaldehyde, methanol, oxalic acid, aniline, benzene alcohol, glucose leaching rate is high, but due to reduction
Agent is at high cost, and actual production is difficult to receive.
In conclusion manganese oxide ore direct reducing leaching technical maturity is not able to satisfy needs of production still at present.Study carefully
Its reason is mainly that the tetravalent manganese direct-reduction in manganese oxide ore is more difficult to divalent, carries out prereduction to manganese oxide ore, will
A large amount of tetravalent manganeses are reduced to trivalent, and further reduce ore particle diameter, improve reaction specific surface area, can utmostly reduce subsequent
The difficulty of reduction can not only improve reduction rate, and reducing agent consumption can also be greatly lowered.
Summary of the invention
The object of the present invention is to provide a kind of methods of powdered biomass reduction manganese oxide ore.The present invention, which has, to be overcome
The deficiency of existing direct reducing leaching technology reduces sequential reduction process reducing agent consumption, improves manganese rate of reduction and reduction
Leaching rate reduces waste residue yield, reduces the characteristics of manganese oxide ore leaches cost.
Technical solution of the present invention: a kind of method of powdered biomass reduction manganese oxide ore, includes following steps:
(1) manganese oxidation miberal powder is first added into water or dilute sulfuric acid pulp, the concentrated sulfuric acid is then slowly added into pulp liquid, stirring is anti-
Powdered biomass is added after answering 60-120 minutes, maintains temperature of reaction system, continues after being stirred to react 60-180 minutes, obtain
Prereduction ore pulp；
(2) water or dilute sulfuric acid are added into prereduction ore pulp, after being stirring evenly and then adding into reducing agent reduction 60-120 minutes,
Both manganese sulfate leachate can be made；
(3) manganese sulfate leachate is neutralized, removal of impurities, is separated by solid-liquid separation, and can be prepared by manganese sulfate solution.
In the method for powdered biomass reduction manganese oxide ore above-mentioned, in the step (1), manganese oxide ore includes soft manganese
Mine, manganese nodule, electrolytic manganese anode slag, mine/dust and slag containing manganese dioxide.
It, will by solid-to-liquid ratio 1:0.5-2 in the step (1) in the method for powdered biomass reduction manganese oxide ore above-mentioned
Manganese oxidation miberal powder adds water or dilute sulfuric acid pulp.
In the method for powdered biomass reduction manganese oxide ore above-mentioned, in the step (1), it is slowly added into pulp liquid
The concentrated sulfuric acid makes sulfuric acid concentration >=650g/l in pulp liquid.
In the method for powdered biomass reduction manganese oxide ore above-mentioned, in the step (1), powdered biomass is rice straw powder
One or more of end, stalk powder, husk powder, flour, powder size >=100 mesh, powdered biomass additional amount are
The 2-10% of manganese quality.
In the method for powdered biomass reduction manganese oxide ore above-mentioned, in the step (1), maintenance temperature of reaction system is
Greater than 333K.
In the method for powdered biomass above-mentioned reduction manganese oxide ore, in the step (2), by solid-to-liquid ratio 1:0.5-2 to
Water or dilute sulfuric acid are added in prereduction ore pulp.
In the method for powdered biomass reduction manganese oxide ore above-mentioned, in the step (2), reducing agent is oxalic acid, peroxide
Change one or both of hydrogen, glucose.
Compared with prior art, the invention has the following advantages:
Manganese oxide powder is added into water or dilute sulfuric acid pulp by solid-to-liquid ratio 1:0.5-2, the concentrated sulfuric acid is added into pulp liquid, makes to starch
Change sulfuric acid concentration >=650g/l in liquid, the process is highly exothermic, and maintenance system reaction temperature is greater than 333K, continues to stir 60-120
Powdered biomass is added after minute, powdered biomass is added according to the 3-10% of manganese quality, to improve reaction efficiency, biomass powder
Last granularity need to be finely ground to >=100 mesh.In the reaction system, powdered biomass granularity and reaction speed, powder dosage and acid
Consume closely related, powder size is smaller, and reaction speed is faster, and the reaction time is shorter, and required powder dosage is fewer, and acid consumption is got over
It is low.
Cellulose and strong sulfuric acid response in powdered biomass, generate hemicellulose, and hemicellulose further reacts generation
The compound of a large amount of new life particulate carbons and part with aldehyde radical, at the same it is highly exothermic, it maintains and further increases temperature of reaction system.
Newborn particulate carbon particle diameter is nanoscale, has great specific surface area and chemical reactivity, under constant stirring
Evenly spread to solution system.Newborn nano-sized carbon and aldehyde radical substance is reacted with the MnO2 in manganese oxide ore, by manganese therein
It is reduced to trivalent or divalent from tetravalence, reaction equation is as follows:
2MnO2+2H2SO4+ C=2MnSO4+2H2O+CO2
(C-HxOy)+mMnO2+mH2SO4→mSO4+mCO2+mH2O
Moreover, under the catalysis of complex system and temperature action, MnO2Automatic oxidation reduction reaction, portion are occurred into for part
Point tetravalent manganese is converted into manganic.Temperature of reaction system is maintained to be greater than 333K, and both complete after being persistently stirred to react 60-180 minutes
At manganese oxide ore pre-reduction.Manganese oxide ore prereduction slurries obtained are reacted easily quickly to be restored by a large amount of reducing agents, and
Obtain good manganese leaching rate.
Water or dilute sulfuric acid are added into prereduction ore pulp, is stirring evenly and then adding into reducing agent and further restores 60-120 minutes
Afterwards, manganese sulfate leachate can both be made, leachate is neutralized, clean, manganese sulfate solution can be both made in separation of solid and liquid.
After the process that newborn particulate carbon is formed can also pass through powdered biomass and concentrated sulfuric acid effect generation outside reaction system
Reaction system is added, functions and effects are consistent.
The applicable oxide ore of prereduction of the present invention includes pyrolusite, psilomelane, hausmannite, braunite, manganese nodule, manganese anode
Mine, dust and the slag containing manganese dioxide such as slag, Mn series alloy dust.
The present invention overcomes that existing direct reducing leaching technology reducing agent consumption is big, extraction time is long, leaching rate is low, the quantity of slag
Greatly, the deficiencies of at high cost is leached, the reducing agents consumption 40-50% such as glucose, hydrogen peroxide, oxalic acid can be reduced, improves manganese also
Former rate, manganese leaching rate are more than or equal to 98%, reduce waste residue yield, reduce manganese oxide ore and leach cost.
In conclusion the present invention, which has, overcomes existing direct reducing leaching technical deficiency, manganese rate of reduction and reduction are improved
Leaching rate reduces waste residue yield, reduces the beneficial effect that manganese oxide ore leaches cost.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
Embodiment 1:
(1) it takes 1000g pyrolusite powder (Mn=40%), the pulp of 500ml dilute sulfuric acid is added, after stirring evenly into pulp liquid
It is slowly added to the 1000ml concentrated sulfuric acid, 12g husk powder is added after being stirred to react 60mim, powder size is 200 mesh, maintains reaction
System temperature is greater than 333K, is stirred to react 60min and prereduction ore pulp is made.3000ml water is added into prereduction ore pulp, slowly
Leachate is obtained after 70g glucose reduction reaction 120min is added, leachate obtains sulphur by neutralizing, cleaning, be separated by solid-liquid separation
Sour manganese solution, solution Mn2+Concentration is 85.2g/l.
(2) it takes 1000g pyrolusite powder (Mn=40%), 800ml water slurry is added, after stirring evenly slowly into pulp liquid
The 1500ml concentrated sulfuric acid is added, 40g stalk powder is added after being stirred to react 120mim, powder size is 100 mesh, maintains reaction system
Temperature is greater than 333K, is stirred to react 180min and prereduction ore pulp is made.5000ml water is added into prereduction ore pulp, is slowly added to
Leachate is obtained after 90g oxalic acid reduction reaction 60min, it is molten that leachate is by neutralizing, cleaning, separation of solid and liquid obtains manganese sulfate
Liquid, solution Mn2+Concentration is 50.6g/l.
(3) it takes 1000g pyrolusite powder (Mn=40%), 2000ml water slurry is added, delay after stirring evenly into pulp liquid
It is slow that the 2000ml concentrated sulfuric acid is added, 35g straw powder is added after being stirred to react 60mim, powder size is 120 mesh, maintains reactant
It is that temperature is greater than 333K, is stirred to react 150min and prereduction ore pulp is made.2000ml water is added into prereduction ore pulp, slowly adds
Leachate is obtained after entering 150ml hydrogen peroxide (30%) reduction 100min, leachate is by neutralizing, cleaning, be separated by solid-liquid separation and make
Obtain manganese sulfate solution, solution Mn2+Concentration is 60.8g/l.
(4) 1000g manganese nodule miberal powder (Mn=30%) is taken, the pulp of 900ml dilute sulfuric acid is added, to pulp liquid after stirring evenly
In be slowly added to the 1200ml concentrated sulfuric acid, be stirred to react after 80mim and 25g husk powder be added, powder size is 300 mesh, remains anti-
It answers system temperature to be greater than 333K, is stirred to react 120min and prereduction ore pulp is made.2000ml water is added into prereduction ore pulp, delays
Slow be added after 70ml hydrogen peroxide (30%) restores 120min obtains leachate, and leachate, which passes through neutralization, removal of impurities, is separated by solid-liquid separation, is
Manganese sulfate solution, solution Mn is made2+Concentration is 69.7g/l.
(5) 1000g manganese nodule miberal powder (Mn=30%) is taken, the pulp of 1000ml dilute sulfuric acid is added, to pulp after stirring evenly
It is slowly added to the 1200ml concentrated sulfuric acid in liquid, 40g straw powder is added after being stirred to react 100mim, powder size is 300 mesh, is maintained
Temperature of reaction system is greater than 333K, is stirred to react 150min and prereduction ore pulp is made.1500ml water is added into prereduction ore pulp,
Leachate is obtained after being slowly added to 60g glucose reduction 120min, leachate obtains sulphur by neutralizing, cleaning, be separated by solid-liquid separation
Sour manganese solution, solution Mn2+Concentration is 77.6g/l.
(6) 1000g electrolytic manganese anode slag (Mn=44%) is taken, the pulp of 500ml dilute sulfuric acid is added, to pulp after stirring evenly
It is slowly added to the 600ml concentrated sulfuric acid in liquid, 20g flour powder is added after being stirred to react 60mim, powder size is 200 mesh, remains anti-
It answers system temperature to be greater than 333K, is stirred to react 70min and prereduction ore pulp is made.3000ml water is added into prereduction ore pulp, delays
Leachate is obtained after slow addition 90g glucose reduction 120min, leachate obtains sulfuric acid by neutralization, removal of impurities, separation of solid and liquid
Manganese solution, solution Mn2+Concentration is 102.2mg/l.
(7) 1000g electrolytic manganese anode slag (Mn=44%) is taken, the pulp of 800ml dilute sulfuric acid is added, to pulp after stirring evenly
It is slowly added to the 900ml concentrated sulfuric acid in liquid, 50g husk powder is added after being stirred to react 90mim, powder size is 100 mesh, remains anti-
It answers system temperature to be greater than 333K, is stirred to react 180min and prereduction ore pulp is made.3000ml water is added into prereduction ore pulp, delays
Slowly leachate is obtained after addition 75g oxalic acid reduction 60min, it is molten that leachate is by neutralizing, cleaning, separation of solid and liquid obtains manganese sulfate
Liquid, solution Mn2+Concentration is 90.1mg/l.
(8) 1000g electrolytic manganese anode slag (Mn=44%) is taken, the pulp of 700ml dilute sulfuric acid is added, to pulp after stirring evenly
It is slowly added to the 1200ml concentrated sulfuric acid in liquid, 40g stalk powder is added after being stirred to react 60mim, powder size is 200 mesh, is maintained
Temperature of reaction system is greater than 333K, is stirred to react 160min and prereduction ore pulp is made.3000ml water is added into prereduction ore pulp,
Leachate is obtained after being slowly added to 120ml hydrogen peroxide (30%) reduction 120min, leachate is by neutralization, removal of impurities, solid-liquid point
From obtaining manganese sulfate solution, solution Mn2+Concentration is 83.6mg/l.
Claims (8)
1. a kind of method of powdered biomass reduction manganese oxide ore, it is characterised in that: include following steps:
(1) manganese oxidation miberal powder is first added into water or dilute sulfuric acid pulp, is then slowly added to the concentrated sulfuric acid into pulp liquid, is stirred to react
Powdered biomass is added after 60-120 minutes, maintains temperature of reaction system, continues after being stirred to react 60-180 minutes, obtain pre-
Restore ore pulp；
(2) water or dilute sulfuric acid are added into prereduction ore pulp, after being stirring evenly and then adding into reducing agent reduction 60-120 minutes, both may be used
Manganese sulfate leachate is made；
(3) manganese sulfate leachate is neutralized, removal of impurities, is separated by solid-liquid separation, and can be prepared by manganese sulfate solution.
2. the method for powdered biomass reduction manganese oxide ore according to claim 1, it is characterised in that: the step (1)
In, manganese oxide ore includes pyrolusite, manganese nodule, electrolytic manganese anode slag, mine/dust and slag containing manganese dioxide.
3. the method for powdered biomass reduction manganese oxide ore according to claim 1, it is characterised in that: the step (1)
In, manganese oxidation miberal powder is added into water or dilute sulfuric acid pulp by solid-to-liquid ratio 1:0.5-2.
4. the method for powdered biomass reduction manganese oxide ore according to claim 1, it is characterised in that: the step (1)
In, it is slowly added to the concentrated sulfuric acid into pulp liquid, makes sulfuric acid concentration >=650g/l in pulp liquid.
5. the method for powdered biomass reduction manganese oxide ore according to claim 1, it is characterised in that: the step (1)
In, powdered biomass be one or more of straw powder, stalk powder, husk powder, flour, powder size >=100 mesh,
Its powdered biomass additional amount is the 2-10% of manganese quality.
6. the method for powdered biomass reduction manganese oxide ore according to claim 1, it is characterised in that: the step (1)
In, maintain temperature of reaction system to be greater than 333K.
7. the method for powdered biomass reduction manganese oxide ore according to claim 1, it is characterised in that: the step (2)
In, water or dilute sulfuric acid are added into prereduction ore pulp by solid-to-liquid ratio 1:0.5-2.
8. the method for powdered biomass reduction manganese oxide ore according to claim 1, it is characterised in that: the step (2)
In, reducing agent is one or both of oxalic acid, hydrogen peroxide, glucose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910810700.XA CN110373542A (en) | 2019-08-29 | 2019-08-29 | A kind of method of powdered biomass reduction manganese oxide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910810700.XA CN110373542A (en) | 2019-08-29 | 2019-08-29 | A kind of method of powdered biomass reduction manganese oxide ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110373542A true CN110373542A (en) | 2019-10-25 |
Family
ID=68261079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910810700.XA Pending CN110373542A (en) | 2019-08-29 | 2019-08-29 | A kind of method of powdered biomass reduction manganese oxide ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110373542A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114737068A (en) * | 2022-03-17 | 2022-07-12 | 贵州金瑞新材料有限责任公司 | High-efficiency leaching method of high-grade pyrolusite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937973A (en) * | 2014-04-16 | 2014-07-23 | 广西民族大学 | Organic-inorganic combined pyrolusite reduction method |
| CN108660326A (en) * | 2018-05-25 | 2018-10-16 | 东北大学 | A method of reduction acidolysis-leaching is simultaneously except iron handles manganese oxide ore |
-
2019
- 2019-08-29 CN CN201910810700.XA patent/CN110373542A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937973A (en) * | 2014-04-16 | 2014-07-23 | 广西民族大学 | Organic-inorganic combined pyrolusite reduction method |
| CN108660326A (en) * | 2018-05-25 | 2018-10-16 | 东北大学 | A method of reduction acidolysis-leaching is simultaneously except iron handles manganese oxide ore |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114737068A (en) * | 2022-03-17 | 2022-07-12 | 贵州金瑞新材料有限责任公司 | High-efficiency leaching method of high-grade pyrolusite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107893160B (en) | Thiosulfate and the technique for mentioning gold from difficult-treating gold mine is prepared in situ | |
| CN101736151B (en) | Method for removing iron by oxidation and neutralization in cobalt wet smelting process | |
| CN105886769B (en) | A kind of method that nitric acid dissolves more metal alloy material collection noble metals | |
| CN106399724A (en) | Microwave reduction roasting and extracting method for manganese oxide ore | |
| CN108660326A (en) | A method of reduction acidolysis-leaching is simultaneously except iron handles manganese oxide ore | |
| CN104762474B (en) | Method for preparing ammonium molybdate through molybdenite | |
| CN106435176A (en) | Two-stage selective heterogenite leaching method | |
| CN101619388B (en) | Method for restraining generation of manganous dithionate in process of leaching sulfur dioxide gas out of pyrolusite | |
| CN104805310B (en) | Method for leaching cobalt from high-valence cobalt oxide-containing raw material | |
| CN103074496B (en) | Method for separating and purifying magnesium dioxide from anode mud | |
| WO2012113263A1 (en) | Method for removing iron and aluminum from iron-based waste material containing high-value elements through natural oxidation | |
| CN111235392A (en) | Method for deep oxidation and harmless comprehensive recovery of valuable metals from zinc sulfite slag | |
| CN110714124A (en) | Method for extracting cobalt from tungsten waste recovery slag | |
| CN110373542A (en) | A kind of method of powdered biomass reduction manganese oxide ore | |
| CN105861836B (en) | A method of collecting noble metal from more metal alloy materials | |
| CN111809066B (en) | Method for efficiently recovering cobalt from low-grade cobalt ore | |
| CN108585049B (en) | Manganous-manganic oxide and preparation method thereof | |
| CN110184455A (en) | A kind of leaching method of difficult leaching cobalt ore | |
| CN110373541A (en) | A kind of method that manganese oxide ore direct reducing leaching prepares manganese sulfate solution | |
| CN110408776A (en) | A kind of method that the accumulation of heat reduction roasting of manganese oxide ore prepares manganese sulfate solution | |
| CN114229905B (en) | Preparation method and application of manganese hydroxide | |
| CN102936649B (en) | Method for recovering nickel, cobalt, manganese and iron by roasting and leaching nickel oxide ore | |
| CN102912124B (en) | Method for recovering nickel, cobalt, manganese and iron by hydrochloric acid leaching of nickel oxide ore | |
| CN112777642B (en) | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag | |
| CN109402377A (en) | A method of control return slag composition oxidizing roasting mentions chromium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |