CN107574299A - A kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method - Google Patents
A kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method Download PDFInfo
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Abstract
The invention discloses a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method, this method is to carry out particulate Ferromanganese Ore, Ground limestone and quick lime to carry out two-stage roasting after drying with ore deposit, mixing agglomeration, gained agglomerate, obtains being calcined agglomerate；The roasting agglomerate passes through levigate, magnetic separation, obtains that gangue content is low, especially the low magnetic concentrate of the constituent content such as harmful element lead, phosphorus, can be as the quality raw materials of smelting manganese-series alloy；This method is especially suitable for the harmful elements such as lead, phosphorus and the close symbiosis of iron, manganese mineral, isomorphous Ferromanganese Ore.
Description
Technical field
The present invention relates to a kind of method of low-grade Ferromanganese Ore ore dressing, and in particular to a kind of leaded fired containing beusite
De- lead dephosphorization is realized, the pyrogenic process beneficiation method of magnetic concentrate is obtained, belongs to metallurgical raw material preconditioning technique field.
Background technology
Manganese is a kind of important strategic resource, and 90% manganese disappears as the deoxidier and desulfurizing agent and alloying element of molten steel
Consume in steel industry, 10% is used for other relevant industries.It is 64351.7 ten thousand t that China's manganese ore, which adds up proved reserves, reserves
592040000 t, the provinces and regions such as Guangxi, Hunan, Guizhou, Sichuan, Liaoning, Yunnan are mainly distributed on, account for national manganese resource gross reserves
90%.
At present, as the development of economy and industrial expansion, particularly steel industry, market are got over to the demand of manganese ore
Come bigger.Thus, the breach between the consumption and Ore Yield of Chinese manganese ore increases year by year, and China relies on import within 2014
Manganese ore amount be up to 6,470,000 t.The main reason for causing this situation is that China's manganese ore grade is low, the high-quality rich manganese ore of high-grade
Resource does not almost have, and the manganese ore 100% for producing medium-low carbon ferromanganese depends on import.Resource it is poor, miscellaneous, thin the features such as constrain
The efficient utilization of manganese ore.The average grade of China's manganese ore generally contains higher Si, Fe, P, Pb, wherein P 20% or so
The manganese ore of content overproof accounts for 49.6%.In addition, ferrimanganic polymetallic ore resource often altogether, associated silver, lead, zinc, cobalt etc., manganese average grade
Only 15%, reserves account for 19%.
Low-grade iron ore could be used for Mn series alloy smelting after must carrying out ore dressing.The ore dressing of manganese ore has gravity treatment, Qiang Ci
The techniques such as choosing, again-magnetic separation, strong magnetic-flotation, some gangue minerals can be removed by ore dressing, improve manganese grade.But China's manganese
Ore structures are complicated, and disseminated grain size is thin, and valuable mineral is combined closely with gangue, selects smelting difficulty larger, for iron, manganese mineral with having
The simple Ferromanganese Ore of the evil embedding cloth of element, the separation of ferromanganese mineral and gangue can be realized using the beneficiation method of routine.But by
The close symbiosis of ferrimanganic in China's ferrimanganic ore resources, disseminated grain size is thin, and the smelting harmful element such as lead, phosphorus is substituted with lattice more, class
Matter with elephant form preservation in iron, manganese mineral, be having for difficult to realize ferromanganese and harmful element only by conventional ore-dressing technique
Effect separation.Although Mn-rich slag method can effectively remove the harmful elements such as lead, phosphorus, Mn-rich slag method smelting temperature height is, it is necessary to disappear
Substantial amounts of fuel and reducing agent are consumed, produces substantial amounts of solid, gas pollutant.
The content of the invention
The problem of for the harmful elements such as lead phosphorus in low-grade Ferromanganese Ore ore dressing process and ferromanganese minerals separation difficulty, the present invention
Purpose be to be to provide a kind of migration by being calcined the objectionable impurities elements such as the generation of regulation and control magnetic iron and manganese oxides and lead phosphorus,
And then the beneficiation method of the separation of harmful element such as iron and manganese oxides and lead phosphorus is realized by way of mill ore magnetic selection.
In order to realize above-mentioned technical purpose, the invention provides a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method, this method
It is to carry out particulate Ferromanganese Ore, Ground limestone and quick lime to carry out two after drying with ore deposit, mixing agglomeration, gained agglomerate
Section roasting, obtain being calcined agglomerate；The roasting agglomerate passes through levigate, magnetic separation, obtains magnetic concentrate；
Wherein, particulate Ferromanganese Ore, Ground limestone and quick lime meet that Mn and Fe mass ratio is in 0.25~3.0 with ore deposit
Between, CaO and SiO2Mass ratio is between 0.05~0.45；And P2O5/(MnO2+Fe2O3) mass ratio be not higher than 5%,
PbO/(MnO2+Fe2O3+SiO2) mass ratio be not higher than 8%.
Technical scheme is using low-grade Ferromanganese Ore as raw material, by strictly controlling the ratio with each component in ore deposit,
Using high temperature solid state reaction, the generation of magnetic Mn ferrite and the removing of lead phosphorus impurities in roasting process are controlled, realizes ferromanganese
With the separation of the harmful element such as lead phosphorus, and high-quality magnetic concentrate is obtained.The harmful elements such as lead phosphorus are difficult to during two-stage roasting
Into in ferromanganese composite oxides lattice, lead phosphorus etc. generates the liquid phase of low melting point with quartz, iron, manganese mineral, in certain roasting
At a temperature of by regulating and controlling CaO/SiO2Mass ratio, can adjust roasting agglomerate in the size of amount of liquid phase and the boundary of partial liquid phase
Surface properties, and then regulate and control the migration of the harmful elements such as growth and the lead phosphorus of ferromanganese composite oxides, realize harmful element lead and phosphorus
Simultaneous removing；So as to provide mineralogy bar for roasting agglomerate mill ore magnetic selection separation ferro manganese composite oxides and harmful element
Part.Furthermore, it is possible to carry out dispensing using a variety of Ferromanganese Ores, Mn/Fe mass ratioes in compound are controlled to be between 0.25~3.0,
Ferromanganese composite oxides in the range of this Mn/Fe ratio have preferable magnetic, are easy to ferromanganese combined oxidation during magnetic separation
Thing and gangue efficiently separate.In addition, iron-bearing mineral main in Ferromanganese Ore is bloodstone, goethite, limonite, manganese-bearing mineral
For pyrolusite, manganese carbonate ore etc.；Main gangue mineral is quartz.Harmful element lead, phosphorus are mainly embedding to be distributed in manganese, iron mineral.
The quartz contained in Ferromanganese Ore can be rationally utilized, by P2O5/(MnO2+Fe2O3)、PbO/(MnO2+Fe2O3+SiO2) control and closing
Suitable ratio, during two-stage roasting, by regulating and controlling the generation of the liquid phase in roasting process and amount of liquid phase so that phosphorus, lead etc. have
Evil element synchronization enters gangue mineral, simultaneously because the chemical property of iron, manganese element is extremely similar, the phase easily in roasting process
Mutually substitution, generate ferromanganese composite oxides.Therefore, smelting can be directly obtained from low-grade ferrous manganese ore by technical scheme
Refine the quality raw materials of Mn series alloy.
Preferable scheme, SiO in particulate Ferromanganese Ore, Ground limestone and quick lime2Gross mass percentage composition be in
0.01%~30% scope.
More preferably scheme, the granularity of the particulate Ferromanganese Ore be -200 mesh grades shared by mass ratio be 100%, -400
Mass ratio shared by mesh grade is not less than 50%.Manganese, lead, Phosphate minerals Khenpo fine size, valuable mineral and arteries and veins in particulate Ferromanganese Ore
Stone is combined closely, need preferentially by levigate to the required particle diameter of the granularity of raw material, solid phase reaction is fully carried out, at the same guarantee by
Green briquette prepared by compound has certain intensity in dry and roasting process.
Preferable scheme, the two-stage roasting process are：One section of roasting is first carried out at a temperature of 800 DEG C~1000 DEG C, then
Two-stage calcination is carried out at a temperature of 1200 DEG C~1350 DEG C.
The iron mineral that mainly includes is bloodstone, goethite, limonite etc. in the particulate Ferromanganese Ore of the present invention, main manganese
Mineral are pyrolusite, manganese carbonate ore etc.；Main gangue mineral is quartz；Harmful element is lead, phosphorus, and lead and phosphorus are main embedding to be distributed in
In manganese, iron mineral.Technical scheme controls generation and the lead phosphorus of the compound oxysome of ferromanganese by the way of two-stage roasting
The migration of harmful element, first when being calcined at a temperature of 800 DEG C~1000 DEG C, it can rationally utilize the quartz contained in Ferromanganese Ore
Deng the P in raw material is calcined2O5/(MnO2+Fe2O3)、PbO/(MnO2+Fe2O3+SiO2) control suitable ratio condition
Under, pass through liquid phase generation and amount of liquid phase in temperature adjustable agglomerate so that the harmful element such as phosphorus, lead synchronously enters gangue mineral；
When temperature is further increased to 1100 DEG C~1350 DEG C, because the chemical property of iron, manganese element is extremely similar, easily it is being calcined
During mutually substitute, generate ferromanganese composite oxides.Therefore removing and the manganese of lead phosphorus can be effectively realized by two-stage roasting
Ferritic generation.
More preferably scheme, the time of one section of roasting is 10~60min.
More preferably scheme, the time of the two-stage calcination is 30~180min.
More preferably scheme, control system liquid phase quality content is 1%~15% in one section of roasting process.
More preferably scheme, control system amount of liquid phase is 10%~25% during the two-stage calcination.Roasted by adjusting
The interfacial property of liquid content and partial liquid phase in agglomerate is burnt, and then growth and the lead phosphorus of ferromanganese composite oxides can be regulated and controled
Deng the migration of harmful element.
The calcination atmosphere of more preferably scheme, one section of roasting and two-stage calcination is air atmosphere.
More preferably scheme, it is that -200 mesh grade proportions are 100% that the roasting agglomerate is levigate to granularity.Ore grinding is extremely
Appropriate granularity is advantageous to the magnetic separation separation of the ferrimanganic oxysome of generation.
Magnetic concentrate prepared by the present invention can be directly as smelting manganese-series alloy quality raw materials.
Tailings is the enrichment tailings of lead and phosphorus after magnetic separation separation in technical scheme.
Compared with the prior art, the advantageous effects that technical solution of the present invention is brought：
1) technical scheme is by strictly controlling the ratio with various components in ore deposit, in high temperature solid state reaction process
In, it is possible to achieve the generation of liquid phase and the interfacial property of amount of liquid phase and partial liquid phase in agglomerate in regulation and control roasting process, so as to
Promote the harmful element synchronous migrations such as phosphorus, lead to enter gangue mineral, while the life of high magnetic ferromanganese composite oxides can be controlled
Into being advantageous to magnetic separation and realize efficiently separating for magnetic concentrate and objectionable impurities.
2) technical scheme is first that raw material realizes that the de- lead dephosphorization preparation of a step can be straight using low-grade ferromanganese
The quality raw materials as smelting manganese-series alloy are connect, realize the efficient increment processing of low-grade ferromanganese resource, this method is low-grade
The ferromanganese rate of recovery in ferrous manganese ore reaches more than 90%, and the removal efficiency of lead and phosphorus reaches more than 91%.
3) technical scheme is simple to operate, cost is low, added value is high, is advantageous to industrialized production.
Embodiment
Following examples are intended to further illustrate present invention, rather than limit the scope of the invention.
Embodiment 1：
With TMn14%, TFe28%, SiO218%, PbO 3.5%, P2O50.82% Ferromanganese Ore mixture is raw material,
Using Ground limestone, quick lime as flux, regulation compound dual alkalinity 0.05, compound is finely ground to -200 mesh grade accountings
100%, -400 mesh grade proportions are 50%；Then compound is subjected to pelletizing, 8~12mm pelletizing is made, wherein mixed
It is 8% to close material moisture, pelletizing is placed in 120 DEG C of drying boxes dry bulb group is dried to obtain；Dry bulb group is placed in Muffle furnace, one
Section sintering temperature is 1000 DEG C, time 10min, and two-stage calcination temperature is 1350 DEG C, time 30min；After cooling, it will be calcined
It is 100% that agglomerate is levigate to mass percent shared by -200 mesh grades, and magnetic separation is carried out under 1000Gs magnetic field intensity.Gained magnetic
Manganese, the rate of recovery of iron are 95.3% and 93.5% in concentrate selection, and the removal efficiency of lead is 94.8%, and the removal efficiency of phosphorus is 95.6%.
Gained magnetic concentrate can be directly as high-quality Mn series alloy smelting furnace material.
Embodiment 2：
With TMn 12%, TFe 48%, SiO25.5%, PbO 2.1%, P2O50.87% Ferromanganese Ore mixture is original
Material, using Ground limestone, quick lime as flux, regulation compound dual alkalinity 0.45, compound is finely ground to -200 mesh grades
Accounting 100%, -400 mesh grade proportions are 65%；Then compound is subjected to briquetting, diameter 10cm, a height of 10mm is made
Agglomerate, wherein mixture moisture be 5%, pelletizing is placed in 120 DEG C of drying boxes dry agglomerate is dried to obtain；Dry agglomerate is put
In Muffle furnace, one section of sintering temperature is 800 DEG C, time 60min, and two-stage calcination temperature is 1200 DEG C, time 180min；
After cooling, will be calcined the levigate extremely mass percent shared by -200 mesh grades of agglomerate is 100%, is entered under 950Gs magnetic field intensity
Row magnetic separation.Manganese, the rate of recovery of iron are 94.1% and 92.6% in gained magnetic concentrate, and the removal efficiency of lead is 93.2%, and phosphorus takes off
Except rate is 94.5%.Gained magnetic concentrate can be directly as high-quality Mn series alloy smelting furnace material.
Embodiment 3：
With TMn 37.5%, TFe 15%, SiO29.8%, PbO2.6%, P2O50.65% Ferromanganese Ore mixture is original
Material, using Ground limestone, quick lime as flux, regulation compound dual alkalinity 0.30, compound is finely ground to -200 mesh grades
Accounting 100%, -400 mesh grade proportions are 60%；Then compound is subjected to briquetting, diameter 10cm, a height of 10mm is made
Agglomerate, wherein mixture moisture be 5%, pelletizing is placed in 120 DEG C of drying boxes dry agglomerate is dried to obtain；Dry agglomerate is put
In Muffle furnace, one section of sintering temperature is 900 DEG C, time 30min, and two-stage calcination temperature is 1300 DEG C, time 90min；
After cooling, will be calcined the levigate extremely mass percent shared by -200 mesh grades of agglomerate is 100%, is entered under 800Gs magnetic field intensity
Row magnetic separation.Manganese, the rate of recovery of iron are 90.8% and 92.1% in gained magnetic concentrate, and the removal efficiency of lead is 91.9%, and phosphorus takes off
Except rate is 92.2%.Gained magnetic concentrate can be directly as high-quality Mn series alloy smelting furnace material.
Comparative example 1：
Mn-Fe ratio is low in the comparative example
With TMn9%, TFe45%, SiO210.2%, PbO2.3%, P2O50.62% Ferromanganese Ore mixture is raw material,
Using Ground limestone, quick lime as flux, regulation compound dual alkalinity 0.30, compound is finely ground to -200 mesh grade accountings
100%, -400 mesh grade proportions are 60%；Then compound is subjected to briquetting, diameter 10cm, a height of 10mm group is made
Block, wherein mixture moisture are 5%, pelletizing are placed in 120 DEG C of drying boxes dry agglomerate is dried to obtain；Dry agglomerate is placed in horse
Not in stove, one section of sintering temperature is 950 DEG C, time 20min, and two-stage calcination temperature is 1300 DEG C, time 90min；Cooling
Afterwards, will be calcined the levigate extremely mass percent shared by -200 mesh grades of agglomerate is 100%, and magnetic is carried out under 800Gs magnetic field intensity
Choosing.Manganese, the rate of recovery of iron are 70.1% and 72.7% in gained magnetic concentrate, and the removal efficiency of lead is 70.3%, the removal efficiency of phosphorus
For 72.4%.Gained magnetic concentrate can not be directly as high-quality Mn series alloy smelting furnace material.
Comparative example 2：
In the comparative example basicity not the present invention protect in the range of
With TMn 14%, TFe28%, SiO218%, PbO 3.5%, P2O50.82% Ferromanganese Ore mixture is original
Material, using Ground limestone, quick lime as flux, regulation compound dual alkalinity 0.01, compound is finely ground to -200 mesh grades
Accounting 100%, -400 mesh grade proportions are 50%；Then compound is subjected to pelletizing, 8~12mm pelletizing is made, its
Middle mixture moisture is 8%, pelletizing is placed in 120 DEG C of drying boxes dry bulb group is dried to obtain；Dry bulb group is placed in Muffle furnace
In, one section of sintering temperature is 1000 DEG C, time 15min, and two-stage calcination temperature is 1325 DEG C, time 60min；After cooling,
It is 100% that the levigate extremely mass percent shared by -200 mesh grades of agglomerate, which will be calcined, and magnetic separation is carried out under 1000Gs magnetic field intensity.
Manganese, the rate of recovery of iron are 74.5% and 73.8% in gained magnetic concentrate, and the removal efficiency of lead is 71.2%, and the removal efficiency of phosphorus is
73.4%.Gained magnetic concentrate can not be directly as high-quality Mn series alloy smelting furnace material.
Comparative example 3：
In the comparative example basicity not the present invention protect in the range of
With TMn 14%, TFe28%, SiO218%, PbO 3.5%, P2O50.82% Ferromanganese Ore mixture is original
Material, using Ground limestone, quick lime as flux, regulation compound dual alkalinity 0.65, compound is finely ground to -200 mesh grades
Accounting 100%, -400 mesh grade proportions are 50%；Then compound is subjected to pelletizing, 8~12mm pelletizing is made, its
Middle mixture moisture is 8%, pelletizing is placed in 120 DEG C of drying boxes dry bulb group is dried to obtain；Dry bulb group is placed in Muffle furnace
In, one section of sintering temperature is 900 DEG C, time 40min, and two-stage calcination temperature is 1300 DEG C, time 90min；, will after cooling
It is 100% to be calcined the levigate extremely mass percent shared by -200 mesh grades of agglomerate, and magnetic separation is carried out under 900Gs magnetic field intensity.Institute
In magnetic concentrate manganese, the rate of recovery of iron be 65.1% and 62.8%, the removal efficiency of lead is 70.5%, and the removal efficiency of phosphorus is
71.5%.Gained magnetic concentrate can not be directly as high-quality Mn series alloy smelting furnace material.
Comparative example 4：
In the comparative example temperature not the present invention protect in the range of
With TMn 15%, TFe 27%, SiO216%, PbO 3.3%, P2O50.75% Ferromanganese Ore mixture is original
Material, using Ground limestone, quick lime as flux, regulation compound dual alkalinity 0.01, compound is finely ground to -200 mesh grades
Accounting 100%, -400 mesh grade proportions are 50%；Then compound is subjected to pelletizing, 8~12mm pelletizing is made, its
Middle mixture moisture is 8%, pelletizing is placed in 120 DEG C of drying boxes dry bulb group is dried to obtain；Dry bulb group is placed in Muffle furnace
In, one section of sintering temperature is 700 DEG C, time 60min, and two-stage calcination temperature is 1050 DEG C, time 60min；, will after cooling
It is 100% to be calcined the levigate extremely mass percent shared by -200 mesh grades of agglomerate, and magnetic separation is carried out under 1000Gs magnetic field intensity.Institute
In magnetic concentrate manganese, the rate of recovery of iron be 64.8% and 63.7%, the removal efficiency of lead is 54.5%, and the removal efficiency of phosphorus is
56.1%.Gained magnetic concentrate can not be directly as high-quality Mn series alloy smelting furnace material.
Claims (8)
- A kind of 1. low-grade Ferromanganese Ore pyrogenic process beneficiation method, it is characterised in that：By particulate Ferromanganese Ore, Ground limestone and quick lime Carry out carrying out two-stage roasting after drying with ore deposit, mixing agglomeration, gained agglomerate, obtain being calcined agglomerate；The roasting agglomerate warp Levigate, magnetic separation is crossed, obtains magnetic concentrate；Wherein, particulate Ferromanganese Ore, Ground limestone and quick lime with ore deposit meet Mn and Fe mass ratio be in 0.25~3.0 it Between, CaO and SiO2Mass ratio is between 0.05~0.45；And P2O5/(MnO2+Fe2O3) mass ratio be not higher than 5%, PbO/ (MnO2+Fe2O3+SiO2) mass ratio be not higher than 8%.
- A kind of 2. low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 1, it is characterised in that：Particulate Ferromanganese Ore, SiO in Ground limestone and quick lime2Gross mass percentage composition be in 0.01%~30% scope.
- A kind of 3. low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 2, it is characterised in that：The particulate ferrimanganic The granularity of ore deposit be -200 mesh grades shared by mass ratio be 100%, mass ratio shared by -400 mesh grades be not less than 50%.
- A kind of 4. low-grade Ferromanganese Ore pyrogenic process beneficiation method according to any one of claims 1 to 3, it is characterised in that：Institute Stating two-stage roasting process is：One section of roasting is first carried out at a temperature of 800 DEG C~1000 DEG C, then at a temperature of 1200 DEG C~1350 DEG C Carry out two-stage calcination.
- A kind of 5. low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 4, it is characterised in that：One section of roasting Time be 10~60min；The time of the two-stage calcination is 30~180min.
- A kind of 6. low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 4, it is characterised in that：One section of roasting During control system liquid phase quality content be 1%~15%；Control system liquid phase quality content during the two-stage calcination For 10%~25%.
- A kind of 7. low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 4, it is characterised in that：One section of roasting and two The calcination atmosphere of section roasting is air atmosphere.
- 8. a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claims 1 to 3,5~7 any one, its feature exist In：It is that -200 mesh grade proportions are 100% that the roasting agglomerate is levigate to granularity.
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| CN110776266A (en) * | 2019-11-07 | 2020-02-11 | 郑州大学 | Preparation method of building material with electromagnetic wave absorption function |
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| US1898018A (en) * | 1931-10-07 | 1933-02-21 | Meyer Mineral Separation Compa | Process of preparing ore |
| CN102912160A (en) * | 2012-10-31 | 2013-02-06 | 北京神雾环境能源科技集团股份有限公司 | Method for treating lean ferrous manganese ore by directly reducing electric furnace melting components through rotary hearth furnace |
| CN103088208A (en) * | 2013-01-16 | 2013-05-08 | 北京矿冶研究总院 | Method for treating manganese-containing and phosphorus-containing hematite |
| CN104651563A (en) * | 2015-02-13 | 2015-05-27 | 唐竹胜 | Combined method for extracting iron and dephosphorizing by reducing, smelting and dressing low-grade high-phosphorus hard-dressing iron (manganese) ore |
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2017
- 2017-09-11 CN CN201710812352.0A patent/CN107574299B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1898018A (en) * | 1931-10-07 | 1933-02-21 | Meyer Mineral Separation Compa | Process of preparing ore |
| CN102912160A (en) * | 2012-10-31 | 2013-02-06 | 北京神雾环境能源科技集团股份有限公司 | Method for treating lean ferrous manganese ore by directly reducing electric furnace melting components through rotary hearth furnace |
| CN103088208A (en) * | 2013-01-16 | 2013-05-08 | 北京矿冶研究总院 | Method for treating manganese-containing and phosphorus-containing hematite |
| CN104651563A (en) * | 2015-02-13 | 2015-05-27 | 唐竹胜 | Combined method for extracting iron and dephosphorizing by reducing, smelting and dressing low-grade high-phosphorus hard-dressing iron (manganese) ore |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776266A (en) * | 2019-11-07 | 2020-02-11 | 郑州大学 | Preparation method of building material with electromagnetic wave absorption function |
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