CN101543830B - Comprehensive utilization method for recycling manganese oxide slag - Google Patents
Comprehensive utilization method for recycling manganese oxide slag Download PDFInfo
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- CN101543830B CN101543830B CN200910061904.4A CN200910061904A CN101543830B CN 101543830 B CN101543830 B CN 101543830B CN 200910061904 A CN200910061904 A CN 200910061904A CN 101543830 B CN101543830 B CN 101543830B
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- manganese oxide
- slag
- oxide slag
- manganese
- cement
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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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a comprehensive utilization method for recycling manganese oxide slag. The method comprises the following steps: (1) screen separation; (2) dilution and agitation; (3) integrated separation; (4) dehydrating and drying; (5) package; and (6) repreparation of cement retarder or mixing and pressing of walling material or repreparation of slag cement. The method has the advantages that about 30 percent of manganese oxide concentrate (content of manganese metal is over 30 percent), iron and other heavy metals in the manganese oxide slag are recycled by using integrated separation technology, and the secondary tailing part remained after the integrated separation replaces plaster to be the cement retarder, or the walling material, or the slag cement; and the method can fundamentally solve the problem of the pollution on the environment caused by the manganese oxide slag, make full and reasonable use of the resources in the manganese oxide slag, save land resource, improve the comprehensive utilization value of the manganese oxide slag and realize zero discharge of the manganese oxide slag.
Description
Technical field
The present invention relates to recovery and the comprehensive utilization technique field of industrial residue, the method for comprehensive utilization that a kind of manganese oxide slag reclaims specifically.
Background technology
Manganese oxide (manganese dioxide) is the chief component of pyrolusite, and pyrolusite is a kind of common manganese mineral, and some manganese oxide ore exceedes 60% containing manganese, is important manganese ore.Manganese oxide ore is that other manganese ores become, in the deposit of the formation such as marsh, Hu Hai, also can form manganese oxide ore, after electrolysis is refined, its product can be used for preparing high-purity manganese oxide concentrate, be to produce the primary raw materials such as manganese sulfate, electrolytic manganese metal, activated manganese dioxide, electrolytic manganese dioxide, four manganese oxide, be widely used in multiple fields such as steel and iron industry, aluminium alloy industry, magnetic material industry, chemical industry.
But China's manganese resource is poor, manganese ore grade is low.Meanwhile, it is huge that electrolytic manganese process is processed the waste residue amount producing after manganese oxide ore, and 1 ton of manganese metal of every extraction will produce the manganese oxide slag of 2-4 ton.China's manganese slag annual emissions exceedes 2,000,000 tons at present, and utilization rate is extremely low.For a long time, to the processing of manganese slag all do not find comprehensive, effectively utilize approach, be to adopt to pile up or the mode of landfill substantially, thus, the land resource amount taking increases year by year, polluted underground water source, mineral resources waste is serious, and production cost rises year by year.
How further to reclaim the high-grade manganese oxide concentrate in manganese oxide slag, and to remainder comprehensive utilization, be that people wish the target of making great efforts for a long time.The open name of application for a patent for invention, CN1080950A that the open name of application for a patent for invention, CN1830865A that the open name of CN1837120A is called " cement that utilizes electrolytic manganese residues to produce " is called " utilizing electrolytic manganese residues to produce the method for ecological cementing material " is called the application for a patent for invention of " moulded coal taking Electrolytic Manganese Metal Residues as component ", is all that electrolytic manganese residues has been done to the trial that part is utilized.All patents are all using electrolytic manganese residues as raw material, produce cement, ecological cementing material, moulded coal, all the manganese oxide concentrate containing in electrolytic manganese residues is not recycled, thereby do not fully utilize manganese slag completely, the pollution of manganese slag to environment can not be thoroughly solved, manganese oxide slag zero-emission can not be realized.
Summary of the invention
The object of the invention is to develop a kind of manganese oxide slag and reclaim the method for comprehensive utilization, utilize total score selecting technology to reclaim the heavy metal such as manganese oxide concentrate (manganese metal content is more than 30%) and iron of 30% left and right in manganese oxide slag, after comprehensive sorting, remaining secondary tailings retarder is as cement retarder, or as materials for wall, or substitute traditional cement as slag cements part; Fundamentally solve the pollution problem of manganese oxide slag to environment, make the resource in manganese oxide slag obtain fully, reasonably utilize, economize the land resource, the comprehensive reutilization that improves manganese oxide slag is worth, and substantially realizes the zero-emission of manganese oxide slag.
The present invention proposes on the basis of manganese oxide slag being carried out to assay.Data show according to one's analysis, in manganese oxide slag, contain: manganese oxide (MnO) approximately 18.26%, alundum (Al2O3) (Al
2o
3) approximately 6.68%, silica (SiO
2) approximately 48.6%, di-iron trioxide (Fe
2o
3) approximately 6.8%, sulfur trioxide (SO
3) approximately 23.6%, wherein, except the content of manganese oxide is higher, silica and sulfur trioxide content are more.
The method of comprehensive utilization that manganese oxide slag of the present invention reclaims, its step is as follows:
(1) screening: electrolysis rear oxidation manganese slag is sieved, adopt screening plant, the granularity of manganese oxide slag is definite according to the requirement of total score optional equipment, and granularity is at 10～120 orders/cm
2between, through screening, remove impurity etc., ensure the granularity that enters total score optional equipment material;
(2) dilution is stirred: add water to dilute stirring, make native impurity and manganese oxide slag maximum disengaging to the greatest extent in manganese oxide slag;
(3) comprehensive sorting: adopt the equipment of patent applied for to carry out comprehensive sorting, number of patent application is 200910061341.9, and name is called permanent-magnet drum eccentric inner surface axial sorting method and apparatus; Number of patent application is 200910061407.4, and name is called permanent-magnet arc-shaped groove inner surface axial sorting method and apparatus; In above equipment utilization manganese oxide slag, (manganese mineral belongs to weak magnetic mineral (relative magnetic susceptibility coefficient X=100～600 × 10-6cm to the difference of the relative magnetic susceptibility coefficient of each composition
3/ g)), manganese oxide slag is carried out to sorting, reclaim concentrate and heavy metal part in manganese oxide slag;
(4) dehydrate: manganese oxide concentrate is dehydrated;
(5) packaging: reaching into the manganese oxide ore of ore deposit grade (manganese metal content is 30%) of sub-electing from manganese oxide slag packed;
(6) compositely make cement retarder or mixing, materials for wall or the composite slag cements of making are made in compacting:
1. composite produce concrete retardation agent:
Gypsum is one of requisite raw material in cement production process, and its Main Function is first, the whole setting time that regulates cement, is the set retarder of cement, SO in general cement
3content is 1.5～3.5%, and the main chemical compositions of gypsum is CaSO
42H
2o, in theory SO
3content 46.5%, the general low-grade gypsum SO of employing when actual use
3content is more than 30%, manganese oxide slag SO
3content 20% left and right, can utilize manganese oxide slag to substitute gypsum, and its incorporation is between 5～15%.
First, remove the harmful components in manganese oxide slag.For example titanium pigment, makes it convert phosphate to, has eliminated the impact of titanium pigment on manufacture of cement, manganese oxide slag is done to necessary modification, because the existence of titanium pigment can cause the unstable of cement setting time, affects cement quality;
Manganese oxide slag is substituted to gypsum in the ratio between 5～15%, join in clinker, as cement retarder;
Or 2. mix, suppress and make materials for wall:
Burnt-free walling material, mainly with flyash, lime, gypsum, gather materials and the raw material such as a small amount of cement by certain proportioning through mixing, make after compressing; Manganese oxide slag after comprehensive sorting in materials for wall for replacing gypsum and part to gather materials, because of its fine size, and the water that contains 30% left and right, can be not treated directly and after flyash, lime, cement mixing, make the burnt-free walling material of various uses;
According to cement: 5-20%, lime: 4-10%, flyash: 10-40%, the burnt-free walling material of the weight ratio of manganese oxide slag: 30-75% through mixing, making after compressing, lightweight, its intensity, between 20～30Mpa, can be used as load bearing wall materials for wall and uses;
Change the burnt-free walling material that manganese oxide slag and flyash, lime, cement proportion can be made into various uses, if incorporation between 5～70%, the color of materials for wall is black, has certain decorative effect;
Or the 3. composite slag cements of making:
Through sorting rear oxidation manganese slag, its main component is dihydrate gypsum CaSO
42H
2o and quartzy SiO
2, activity is extremely low, after proper temperature (600 DEG C～900 DEG C) calcining, can excite its activity, can partly replace cement, and between substitute proportion 10～15%, the property indices of cement can not decline.
The advantage of the method for comprehensive utilization that manganese oxide slag of the present invention reclaims is: utilize total score selecting technology to reclaim 30% left and right in manganese oxide slag and can reach the heavy metal such as manganese oxide concentrate and iron into ore deposit grade (manganese metal content 30%), save mineral resources; By remaining secondary tailings retarder after total score selecting technology, as cement retarder, in cement production process, alternative 5～15% gypsum, has reduced the consumption of gypsum; Can be used as producing burnt-free walling material by remaining secondary tailings part after the sorting of total score selecting technology, in the manufacturing process of burnt-free walling material, can mix 5～75% manganese oxide slag, the intensity of the burnt-free walling material of making is between 20～30MPa, can be used as load bearing wall or dividing wall uses, relatively traditional burnt-free walling material, product weight is light, and intensity is high; Excite its activity by remaining secondary tailings part after the sorting of total score selecting technology, make slag cements, part place of cement; Fundamentally solve the pollution problem of manganese oxide slag to environment, make the resource in manganese oxide slag obtain fully, reasonably utilize, economize the land resource, the comprehensive reutilization that improves manganese oxide slag is worth, and has realized the zero-emission of manganese oxide slag.
Detailed description of the invention
Embodiment mono-
The method of comprehensive utilization that manganese oxide slag reclaims, its step is as follows:
(1) screening: electrolysis rear oxidation manganese slag is sieved, adopt screening plant, the granularity of manganese oxide slag is definite according to the requirement of total score optional equipment, and granularity is 10～120 orders/cm
2, through screening, remove impurity etc., ensure to enter the granularity of total score optional equipment material;
(2) dilution is stirred: add water to dilute stirring, make native impurity and manganese oxide slag maximum disengaging to the greatest extent in manganese oxide slag;
(3) comprehensive sorting: adopt the equipment of patent applied for to carry out comprehensive sorting, number of patent application is 200910061341.9, and name is called permanent-magnet drum eccentric inner surface axial sorting method and apparatus; Number of patent application is 200910061407.4, and name is called permanent-magnet arc-shaped groove inner surface axial sorting method and apparatus; In above equipment utilization manganese oxide slag, (manganese mineral belongs to weak magnetic mineral (relative magnetic susceptibility coefficient X=100～600 × 10-6cm to the difference of the relative magnetic susceptibility coefficient of each composition
3/ g)), manganese oxide slag is carried out to sorting, reclaim concentrate and heavy metal part in manganese oxide slag;
(4) dehydrate: manganese oxide concentrate is dehydrated;
(5) packaging: reaching into the manganese oxide ore of ore deposit grade (manganese metal content is 30%) of sub-electing from manganese oxide slag packed;
(6) composite produce concrete retardation agent:
First, remove the harmful components in manganese oxide slag.For example titanium pigment, makes it convert phosphate to, has eliminated the impact of titanium pigment on manufacture of cement, manganese oxide slag is done to necessary modification, because the existence of titanium pigment can cause the unstable of cement setting time, affects cement quality;
Manganese oxide slag is substituted to gypsum in the ratio between 5～15%, join in clinker, as cement retarder.
Embodiment bis-
The method of comprehensive utilization that manganese oxide slag reclaims, its step is as follows:
(1) screening: electrolysis rear oxidation manganese slag is sieved, adopt screening plant, the granularity of manganese oxide slag is definite according to the requirement of total score optional equipment, and granularity is 10～120 orders/cm
2, through screening, remove impurity etc., ensure to enter the granularity of total score optional equipment material;
(2) dilution is stirred: add water to dilute stirring, improve its decentralization, make the maximum disengaging to the greatest extent of the medium impurity of manganese oxide slag and manganese oxide slag;
(3) comprehensive sorting: adopt the equipment of patent applied for to carry out comprehensive sorting, number of patent application is 200910061341.9, and name is called permanent-magnet drum eccentric inner surface axial sorting method and apparatus; Number of patent application is 200910061407.4, and name is called permanent-magnet arc-shaped groove inner surface axial sorting method and apparatus; In above equipment utilization manganese oxide slag, (manganese mineral belongs to weak magnetic mineral (relative magnetic susceptibility coefficient X=100～600 × 10-6cm to the difference of the relative magnetic susceptibility coefficient of each composition
3/ g)), manganese oxide slag is carried out to sorting, reclaim concentrate and heavy metal part in manganese oxide slag;
(4) dehydrate: manganese oxide concentrate is dehydrated;
(5) packaging: reaching into the manganese oxide ore of ore deposit grade (manganese metal content is 30%) of sub-electing from manganese oxide slag packed;
(6) mix, make materials for wall:
According to cement: 5～20%, lime: 4～10%, flyash: 10～40%, manganese oxide slag: the burnt-free walling material of 30～75% weight ratio through mixing, making after compressing, lightweight, its intensity, between 20～30Mpa, is used as load bearing wall materials for wall;
Meanwhile, change manganese oxide slag and flyash, lime, cement proportion are made the burnt-free walling material of various uses, if incorporation is 5～70%, the color of materials for wall is black, has certain decorative effect.
Embodiment tri-
The method of comprehensive utilization that manganese oxide slag reclaims, its step is as follows:
(1) screening: electrolysis rear oxidation manganese slag is sieved, adopt screening plant, the granularity of manganese oxide slag is definite according to the requirement of total score optional equipment, and granularity is 10～120 orders/cm
2, through screening, remove impurity etc., ensure to enter the granularity of total score optional equipment material;
(2) dilution is stirred: add water and dilute stirring, improve its decentralization, make impurity and manganese oxide slag maximum disengaging to the greatest extent in manganese oxide slag;
(3) comprehensive sorting: adopt the equipment of patent applied for to carry out comprehensive sorting, number of patent application is 200910061341.9, and name is called permanent-magnet drum eccentric inner surface axial sorting method and apparatus; Number of patent application is 200910061407.4, and name is called permanent-magnet arc-shaped groove inner surface axial sorting method and apparatus; In above equipment utilization manganese oxide slag, (manganese mineral belongs to weak magnetic mineral (relative magnetic susceptibility coefficient X=100～600 × 10-6cm to the difference of the relative magnetic susceptibility coefficient of each composition
3/ g)), manganese oxide slag is carried out to sorting, reclaim concentrate and heavy metal part in manganese oxide slag;
(4) dehydrate: manganese oxide concentrate is dehydrated;
(5) packaging: reaching into the manganese oxide ore of ore deposit grade (manganese metal content is 30%) of sub-electing from manganese oxide slag packed;
(6) the composite slag cements of making:
Through sorting rear oxidation manganese slag, its main component is dihydrate gypsum CaSO
42H
2o and quartzy SiO
2, activity is extremely low, through proper temperature (600 DEG C～900 DEG C) calcining, excites its activity, part place of cement, and substitution ratio is 10～15%, the property indices of cement can not decline.
Claims (1)
1. the method for comprehensive utilization that manganese oxide slag reclaims, is characterized in that: its step is as follows:
(1) screening: adopt screening plant to sieve electrolysis rear oxidation manganese slag, the granularity of manganese oxide slag is definite according to the requirement of total score optional equipment, and granularity is at 10～120 orders/cm
2between, through screening, remove impurity, ensure to enter the granularity of total score optional equipment material;
(2) dilution is stirred: add water to dilute stirring, make impurity and manganese oxide slag maximum disengaging to the greatest extent in manganese oxide slag;
(3) comprehensive sorting: adopt permanent-magnet drum eccentric inner surface axial sorting equipment or permanent-magnet arc-shaped groove inner surface axial sorting equipment to carry out comprehensive sorting;
Permanent-magnet drum eccentric inner surface axial sorting equipment comprises support, pipe magnetic separator assembly is housed on support, the eccentric cylinder of eccentric cylinder assembly is housed in the pipe magnetic separator of pipe magnetic separator assembly, because pipe magnetic separator is relative with eccentric cylinder eccentric, field intensity, gradient are progressively by being decreased to greatly zero, in the larger region of bias, the material that relative magnetic susceptibility coefficient is higher is stripped from and falls within high magnetic hopper;
Permanent-magnet arc-shaped groove inner surface axial sorting equipment comprises: support and cylinder assembly, the cylinder of cylinder assembly is equipped with the permanent-magnet arc-shaped groove of concentric permanent-magnet arc-shaped groove assembly outward, permanent-magnet arc-shaped groove top open-loop design, is adsorbed on the material that cylinder relative magnetic susceptibility coefficient is higher and relies on the gravity of self directly to fall into high magnetic hopper;
The difference of the relative magnetic susceptibility coefficient of each composition in above equipment utilization manganese oxide slag, manganese mineral belongs to weak magnetic mineral, its relative magnetic susceptibility coefficient X=100～600 × 10-6cm
3/ g, carries out sorting to manganese oxide slag, reclaims concentrate and heavy metal part in manganese oxide slag;
(4) dehydrate: manganese oxide concentrate is dehydrated;
(5) packaging: reaching into the manganese oxide ore of ore deposit grade of sub-electing from manganese oxide slag packed, and the manganese metal content that enters ore deposit grade is 30%;
(6) materials for wall or the composite slag cements of making are made in composite produce concrete retardation agent or mixing, compacting:
1. composite produce concrete retardation agent:
First, remove the harmful components in manganese oxide slag, manganese oxide slag is substituted to gypsum in the ratio between 5～15%, join in clinker, as cement retarder;
2. mix, suppress and make materials for wall:
According to cement: 5～20%, lime: 4～10%, flyash: 10～40%, manganese oxide slag: the burnt-free walling material that 30～75% weight ratio is made through mixing, after compressing;
3. the composite slag cements of making:
Through sorting rear oxidation manganese slag, its main component is dihydrate gypsum CaSO
42H
2o and quartzy SiO
2, through 600 DEG C～900 DEG C temperature calcinings, excite its activity, part place of cement, substitution ratio is 10～15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200910061904.4A CN101543830B (en) | 2009-05-05 | 2009-05-05 | Comprehensive utilization method for recycling manganese oxide slag |
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|---|---|---|---|
| CN200910061904.4A CN101543830B (en) | 2009-05-05 | 2009-05-05 | Comprehensive utilization method for recycling manganese oxide slag |
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| CN101543830B true CN101543830B (en) | 2014-10-01 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774208B (en) * | 2010-02-06 | 2011-08-31 | 桂林理工大学 | Preparation method of water-quenched manganese slag insulating wall material |
| CN102199026B (en) * | 2010-03-25 | 2014-12-24 | 贵州省建筑材料科学研究设计院 | Hollow building block manufactured from electrolytic manganese residues and manufacture method thereof |
| CN102658237B (en) * | 2012-05-18 | 2014-03-26 | 北京科技大学 | Method for extraction of metal iron from steel tailings and comprehensive utilization of tail mud |
| CN102992277A (en) * | 2012-10-24 | 2013-03-27 | 马朝阳 | Method for producing sulfuric acid by using pyrite concentrate and acid-leaching electrolytic manganese residues |
| CN103553378A (en) * | 2013-11-12 | 2014-02-05 | 宁夏天元锰业有限公司 | Method for preparing cement by utilizing electrolytic manganese residue as retarder |
| CN113603377B (en) * | 2021-08-23 | 2023-01-03 | 广西凭祥市恒宇水泥有限公司 | Cement produced by utilizing electrolytic manganese slag and production method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916362A (en) * | 1996-11-22 | 1999-06-29 | Tosoh Corporation | Method for producing cement using manganese slag as raw material |
| CN1830865A (en) * | 2006-03-07 | 2006-09-13 | 吉首市大力建材有限责任公司 | Method of producing ecological cementing material using electrolytic manganese slag |
| CN101306425A (en) * | 2008-06-24 | 2008-11-19 | 卿富安 | Electrolytic manganese slag comprehensive utilization technique |
-
2009
- 2009-05-05 CN CN200910061904.4A patent/CN101543830B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916362A (en) * | 1996-11-22 | 1999-06-29 | Tosoh Corporation | Method for producing cement using manganese slag as raw material |
| CN1830865A (en) * | 2006-03-07 | 2006-09-13 | 吉首市大力建材有限责任公司 | Method of producing ecological cementing material using electrolytic manganese slag |
| CN101306425A (en) * | 2008-06-24 | 2008-11-19 | 卿富安 | Electrolytic manganese slag comprehensive utilization technique |
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| CN101543830A (en) | 2009-09-30 |
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