CN108928853A - A kind of comprehensive reutilization method of manganese ore leaching slag - Google Patents
A kind of comprehensive reutilization method of manganese ore leaching slag Download PDFInfo
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- CN108928853A CN108928853A CN201810928631.8A CN201810928631A CN108928853A CN 108928853 A CN108928853 A CN 108928853A CN 201810928631 A CN201810928631 A CN 201810928631A CN 108928853 A CN108928853 A CN 108928853A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0009—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic 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
- C22B47/00—Obtaining manganese
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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
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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
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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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- Ceramic Engineering (AREA)
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Structural Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of comprehensive reutilization methods of manganese ore leaching slag, specifically includes the following steps: 1) dump leaching: manganese ore leaching slag and reduction organic agent being mixed, sulfuric acid is added and carries out dump leaching；2) enhanced leaching: dump leaching terminates, and water, leaching is added, and filtering takes filtrate, obtains ferric sulfate-manganese sulfate mixed liquor；Obtained filter residue is silica coarse fodder, obtains white carbon black as refractory material or by purification；3) extraction and separation: the ferric sulfate that upper step is obtained-manganese sulfate mixed liquor carries out extraction and separation, obtains ferrous sulfate liquid and manganese sulfate liquid, and the pH for adjusting ferrous sulfate liquid is 4-6, and iron filings are added, controls temperature crystallisation by cooling, obtains ferrous sulfate product；The manganese sulfate liquid condensing crystallizing that will be obtained, obtains high-purity sulphuric acid manganese product.
Description
Technical field
The invention belongs to the comprehensive utilization of resources technical fields of manganese ore leaching slag, are related to a kind of synthesis of manganese ore leaching slag
Recoverying and utilizing method.
Background technique
China's manganese resource is abundant, widely distributed, and manganese is China's economy as a kind of important metallurgy, chemical raw material
Development and regional economy construction are made that huge contribution.In the development and utilization of manganese resource, mainly with mn site doping and electricity
The form for solving manganese metal is used for steel and iron industry, remaining is mainly utilized in the industries such as fertilizer, feed, chemical industry.Mineral processing is ring
It protects risk and occupies high field, wherein manganese resource utilizes field, the most prominent with the environmental issue of the leached mud of manganese ore wet processing
Out.
At present majority manganese processing enterprise be all waste residue is transported to stockyard, build a dam stockpiling or landfill, since manganese wet process adds
The rate of recovery of work is not generally high, therefore manganese slag all remains the manganese of 5-10%, and other using metallic element with iron etc..Letter
Single stockpiling handles not only land occupation, and there is a large amount of harmful elements (substance), penetrates into soil, surface water and groundwater
In Heavy environmental pollution potential problem.After the nineties, China has carried out the comprehensive utilizating research to manganese slag, in baseset
In terms of producing construction material as ingredient.But attribute of manganese ore leaching slag itself determines that it can only match on a small quantity as additive
The materials such as material production cement, are not suitable for widely applying in terms of building materials, therefore the utilization of resources of manganese slag does not obtain essence always
Improvement.
In conclusion a kind of new way, new method that manganese slag green resource recycles is explored, with great environment society
Economic benefit.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of comprehensive reutilization method of manganese ore leaching slag, is a kind of
The green utilization recovery method of manganese ore leaching slag, the present invention be directed to manganese ore leaching slag, have investigated it is a kind of green processing manganese slag, reach
To the method for resource comprehensive utilization, manganese iron, preparation high added value high purity manganese sulfate and the ferrous sulfate in recycling manganese slag first is produced
Product, remaining silica coarse fodder is sold as raw material for refractory after having mentioned manganese iron.This method environment-protecting clean, low cost are high
Benefit solves the environmental issue of manganese slag, and economic results in society are significant, the metal resources such as manganese iron can be recycled to greatest extent, to manganese
Slag carries out comprehensive reutilization by all kinds of means.
A kind of comprehensive reutilization method of manganese ore leaching slag of the present invention, specifically includes the following steps:
1) dump leaching: manganese ore leaching slag and reduction organic agent are mixed, and sulfuric acid is added and carries out dump leaching；
2) enhanced leaching: dump leaching terminates, and water, leaching is added, and filtering takes filtrate, obtains ferric sulfate-manganese sulfate mixing
Liquid；
Obtained filter residue is silica coarse fodder, obtains white carbon black as refractory material or by purification；
3) extraction and separation: the ferric sulfate that upper step is obtained-manganese sulfate mixed liquor carries out extraction and separation, obtains ferrous sulfate
Liquid and manganese sulfate liquid, the pH for adjusting ferrous sulfate liquid is 4-6, and iron filings are added, controls temperature crystallisation by cooling, obtains sulfuric acid
Ferrous product；
The manganese sulfate liquid condensing crystallizing that will be obtained, obtains high-purity sulphuric acid manganese product.
Manganese ore leaching slag described in step 1) of the present invention, manganese content are greater than 1%, and iron content is greater than 3%.
Reduction organic agent described in step 1) is sawdust, corn stover, cornstarch, tapioca starch, bagasse, wheat bran, wheat
Chaff organic matter or biomass, dosage are the 100%-200% of theoretical amount.
Addition acid described in step 1) carries out dump leaching, and when dump leaching requires acid condition, and the 100- that acid is theoretical amount is added
140%, the dump leaching time is 2-24h at normal temperature.
The pH that ferrous sulfate liquid is adjusted described in step 3) is 4-6, and ammonium hydrogen carbonate is added and adjusts ferrous sulfate liquid
PH is 4-6.
Control temperature crystallisation by cooling described in step 3), crystallisation by cooling temperature are -10--5 DEG C.
Compared with the prior art, the advantages of the present invention are as follows:
1, operation of the present invention process is simple, the raw material used i.e. sawdust, corn stover, cornstarch, tapioca starch, sugarcane
Slag, wheat bran, wheat bran organic matter or biomass, it is from a wealth of sources and at low cost, it is conducive to expand industrialized production.
2, the present invention generates during dump leaching, leaching, separation, crystallization etc. are each without pernicious gas, and treatment process reaches
Environment-protecting clean.
3, present invention production obtained high purity manganese sulfate, ferrous sulfate, refractory material and white carbon black product quality it is good and
Market effect is good, can generate higher economic results in society.
4, the present invention is that friendly processing is carried out to manganese ore leaching slag, to society and environmental protection important in inhibiting.
Detailed description of the invention
Fig. 1 is the flow diagram of this method.
Specific embodiment
With embodiment, the invention will be further described below, but the invention is not limited to these embodiments.
Embodiment 1:
Take Guangxi Qinzhou manganese ore factory manganese ore leaching slag 1kg, this leached mud manganese content 2.12%, iron content 12.37%.
Sawdust 50g is added, is stirring evenly and then adding into the 30ml concentrated sulfuric acid, after room temperature dump leaching 12h, 200ml water, stirring is added
It leaches, filtering is taken filtrate, obtains ferric sulfate-manganese sulfate mixed liquor, separated using abstraction technique to manganese iron ion.It obtains
The heating of iron content ionic liquid, temperature is maintained at 50 DEG C, and the iron filings of 20g are added, and adjusting liquid ph is 4-5.Obtained sulfuric acid is sub-
Ferrous solution freezing and crystallizing at -5 DEG C obtains errous sulfate crystal.The condensing crystallizing of high purity liquid containing manganese obtains manganese sulfate product.
Embodiment 2:
Take Guangxi Qinzhou manganese ore factory ferric manganese ore leached mud 2kg, this leached mud manganese content 6.4%, iron content 45.5%.
Corn stover 600g is added, is stirring evenly and then adding into the 800ml concentrated sulfuric acid, after room temperature dump leaching 8h, 5L water, stirring is added
It leaches, filtering is taken filtrate, obtains ferric sulfate-manganese sulfate mixed liquor, separated using abstraction technique to manganese iron ion.Iron content
Ionic liquid heating, temperature is maintained at 80 DEG C, and the iron filings of 800g are added, and adjusting liquid ph is 4-5.Obtained ferrous sulfate is molten
Liquid freezing and crystallizing at -10 DEG C obtains errous sulfate crystal.Obtained high purity liquid containing manganese, condensing crystallizing obtain manganese sulfate crystalline substance
Body.
Embodiment 3:
Take Guangxi Qinzhou manganese ore factory manganese ore leaching slag 5kg, this leached mud manganese content 6.6%, iron content 35.8%.
Sawdust 1kg is added, is stirring evenly and then adding into the 3000ml concentrated sulfuric acid, after room temperature dump leaching 6h, 10L water, stirring leaching is added
Out, it filters, takes filtrate, obtain ferric sulfate-manganese sulfate mixed liquor, ammonium hydrogen carbonate is added, so that ph is kept 5-6, hydrogen-oxygen is obtained by filtration
Change iron precipitating, ferric hydroxide precipitate heats 450 degrees Celsius, obtains di-iron trioxide product.Remaining ammonium manganous sulfate solution continues
Ammonium hydrogen carbonate is added, reaction generates high purity manganese sulfate.
Ferrous sulfate quality obtained in embodiment meets the requirement of primes.
The preferable specific implementation method of the above, only the invention patent, but the protection scope of this patent does not limit to
In this, for those of ordinary skill in the art, skill of the anyone skilled in the art in present disclosure
Within the scope of art, any changes or substitutions that can be easily thought of, should all be included within the scope of the present invention, therefore of the invention
Protection scope should be subject to the scope of protection of the claims.
Claims (6)
1. a kind of comprehensive reutilization method of manganese ore leaching slag, which is characterized in that specifically includes the following steps:
1) dump leaching: manganese ore leaching slag and reduction organic agent are mixed, and sulfuric acid is added and carries out dump leaching；
2) enhanced leaching: dump leaching terminates, and water, leaching is added, and filtering takes filtrate, obtains ferric sulfate-manganese sulfate mixed liquor；
Obtained filter residue is silica coarse fodder, obtains white carbon black as refractory material or by purification；
3) extraction and separation: the ferric sulfate that upper step is obtained-manganese sulfate mixed liquor carries out extraction and separation, obtains ferrous sulfate liquid
With manganese sulfate liquid, the pH for adjusting ferrous sulfate liquid is 4-6, and iron filings are added, controls temperature crystallisation by cooling, obtains ferrous sulfate
Product；
The manganese sulfate liquid condensing crystallizing that will be obtained, obtains high-purity sulphuric acid manganese product.
2. a kind of comprehensive reutilization method of manganese ore leaching slag according to claim 1, it is characterised in that: step 1) institute
The manganese ore leaching slag stated, manganese content are greater than 1%, and iron content is greater than 3%.
3. a kind of comprehensive reutilization method of manganese ore leaching slag according to claim 1, it is characterised in that: step 1) institute
The reduction organic agent stated is sawdust, corn stover, cornstarch, tapioca starch, bagasse, wheat bran, wheat bran organic matter or biology
Matter, dosage are the 100%-200% of theoretical amount.
4. a kind of comprehensive reutilization method of manganese ore leaching slag according to claim 1, it is characterised in that: step 1) institute
The addition acid stated carries out dump leaching, and when dump leaching requires acid condition, the 100-140% that acid is theoretical amount is added, the dump leaching time is normal
Lower temperature is 2-24h.
5. a kind of comprehensive reutilization method of manganese ore leaching slag according to claim 4, it is characterised in that: step 3) institute
The pH for the adjusting ferrous sulfate liquid stated is 4-6, is that ammonium hydrogen carbonate is added to adjust the pH of ferrous sulfate liquid as 4-6.
6. a kind of comprehensive reutilization method of manganese ore leaching slag according to claim 1, it is characterised in that: step 3) institute
The control temperature crystallisation by cooling stated, crystallisation by cooling temperature are -10--5 DEG C.
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| CN201810928631.8A CN108928853A (en) | 2018-08-15 | 2018-08-15 | A kind of comprehensive reutilization method of manganese ore leaching slag |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790594A (en) * | 2019-10-16 | 2020-02-14 | 铜仁学院 | Method for producing secondary element water-soluble fertilizer from manganese slag |
| CN111847518A (en) * | 2020-06-28 | 2020-10-30 | 广西锰华新能源科技发展有限公司 | Efficient recycling method of silicomanganese slag |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790594A (en) * | 2019-10-16 | 2020-02-14 | 铜仁学院 | Method for producing secondary element water-soluble fertilizer from manganese slag |
| CN111847518A (en) * | 2020-06-28 | 2020-10-30 | 广西锰华新能源科技发展有限公司 | Efficient recycling method of silicomanganese slag |
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Application publication date: 20181204 |