CN107574299B - 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 with mine, mixing agglomeration, and gained agglomerate carries out two-stage roasting after drying, obtains roasting agglomerate；The roasting agglomerate passes through levigate, magnetic separation, obtains that gangue content is low, especially the low magnetic concentrate of the constituent contents 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 methods of low-grade Ferromanganese Ore ore dressing, and in particular to a kind of leaded fired containing beusite
It realizes and takes off lead dephosphorization, obtain the pyrogenic process beneficiation method of magnetic concentrate, belong 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
It consumes in steel industry, 10% is used for other relevant industries.It is 64351.7 ten thousand t, reserves that China's manganese ore, which adds up proved reserves,
592040000 t are mainly distributed on the provinces and regions such as Guangxi, Hunan, Guizhou, Sichuan, Liaoning, Yunnan, account for national manganese resource gross reserves
90%.
Currently, with economy and industrial expansion, the especially development of steel industry, the demand of manganese ore is got in market
Come bigger.The notch between the consumption and Ore Yield of Chinese manganese ore increases year by year as a result, and China relies on import within 2014
Manganese ore amount be up to 6,470,000 t.The main reason for leading to this situation is that China's manganese ore grade is low, the high-quality rich manganese ore of high-grade
Resource is almost without 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 exceeded manganese ore of content 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 can remove some gangue minerals 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 and has
The simple Ferromanganese Ore of the evil embedding cloth of element, the separation of ferromanganese mineral and gangue may be implemented using conventional beneficiation method.But by
The close symbiosis of ferrimanganic in China's ferrimanganic ore resources, disseminated grain size is thin, and lead, phosphorus etc. smelt harmful element mostly with lattice substitution, class
Matter with elephant form preservation in iron, manganese mineral, be only having for difficult to realize ferromanganese and harmful element 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 is high, needs to disappear
A large amount of fuel and reducing agent are consumed, a large amount of solid, gas pollutant is generated.
Invention content
For the problem of the harmful elements such as lead phosphorus in low-grade Ferromanganese Ore ore dressing process and ferromanganese minerals separation hardly possible, the present invention
Purpose be to provide it is a kind of generated by roasting magnetic iron and manganese oxides and the migration of the objectionable impurities elements such as lead phosphorus,
And then the beneficiation method of the separation of the harmful elements such as iron and manganese oxides and lead phosphorus is realized by way of mill ore magnetic selection.
In order to achieve the above technical purposes, the present 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 with mine, mixing agglomeration, gained agglomerate carries out two after drying
Section roasting obtains roasting agglomerate；The roasting agglomerate passes through levigate, magnetic separation, obtains magnetic concentrate；
Wherein, particulate Ferromanganese Ore, Ground limestone and quick lime meet the mass ratio of Mn and Fe in 0.25~3.0 with mine
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 of the present invention is using low-grade Ferromanganese Ore as raw material, by strictly controlling the ratio with each component in mine,
Using high temperature solid state reaction, the magnetic generation of Mn ferrite and the removing of lead phosphorus impurities in roasting process are controlled, realizes ferromanganese
With the separation of the harmful elements 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 pass through regulate and control 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 the migration of the harmful elements such as growth and lead phosphorus for regulating and controlling ferromanganese composite oxides, realize harmful element lead and phosphorus
Simultaneous removing；To provide mineralogy item 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, controls Mn/Fe mass ratioes in mixture and is between 0.25~3.0,
There is preferable magnetism than the ferromanganese composite oxides in range in this Mn/Fe, convenient for ferromanganese combined oxidation during magnetic separation
Object and gangue efficiently separate.In addition, main iron-bearing mineral is bloodstone, goethite, limonite, manganese-bearing mineral in Ferromanganese Ore
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 liquid phase generation and amount of liquid phase in roasting process 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 generates ferromanganese composite oxides.Therefore, technical solution through the invention can directly obtain smelting from low-grade ferrous manganese ore
Refine the quality raw materials of Mn series alloy.
Preferred scheme, SiO in particulate Ferromanganese Ore, Ground limestone and quick lime2Gross mass percentage composition be in
0.01%~30% range.
More preferably scheme, it is 100%, -400 that the granularity of the particulate Ferromanganese Ore, which is mass ratio shared by -200 mesh grades,
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 grain size of the granularity of raw material, so that solid phase reaction is fully carried out, at the same guarantee by
Green briquette prepared by mixture has certain intensity in dry and roasting process.
Preferred 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 for including mainly in the particulate Ferromanganese Ore of the present invention is bloodstone, goethite, limonite etc., 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 of the present invention controls generation and the lead phosphorus of the compound oxysome of ferromanganese by the way of two-stage roasting
The migration of harmful element when first being roasted at a temperature of 800 DEG C~1000 DEG C, can rationally utilize the quartz contained in Ferromanganese Ore
Deng the P in roasting raw material2O5/(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 elements such as phosphorus, lead, which synchronize, enters gangue mineral；
When temperature is further increased to 1100 DEG C~1350 DEG C, since the chemical property of iron, manganese element is extremely similar, easily roasting
Mutually substitution in the process, generates ferromanganese composite oxides.Therefore removing and the manganese of lead phosphorus can be effectively realized by two-stage roasting
Ferritic generation.
The time of more preferably scheme, one section of roasting is 10~60min.
The time of more preferably scheme, 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.It is 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
The migration of equal harmful elements.
The calcination atmosphere of more preferably scheme, one section of roasting and two-stage calcination is air atmosphere.
More preferably scheme, it be -200 mesh grade proportions is 100% that the roasting agglomerate is levigate to granularity.Ore grinding is extremely
Appropriate granularity is conducive to the magnetic separation separation of the ferrimanganic oxysome generated.
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 of the present invention.
Compared with the prior art, the advantageous effects that technical solution of the present invention is brought：
1) technical scheme of the present invention is by strictly controlling the ratio with various components in mine, in high temperature solid state reaction process
In, the interfacial property of the generation and amount of liquid phase and partial liquid phase of liquid phase in agglomerate in regulation and control roasting process may be implemented, to
Promote the harmful elements synchronous migrations such as phosphorus, lead to enter gangue mineral, while the life of high magnetic ferromanganese composite oxides can be controlled
At being conducive to magnetic separation and realize efficiently separating for magnetic concentrate and objectionable impurities.
2) technical scheme of the present invention is for the first time 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, the efficient increment processing of low-grade ferromanganese resource is realized, this method is low-grade
The ferromanganese rate of recovery in ferrous manganese ore reaches 90% or more, and the removal efficiency of lead and phosphorus reaches 91% or more.
3) technical scheme of the present invention is easy to operate, at low cost, added value is high, is conducive to industrialized production.
Specific implementation mode
Following embodiment is intended to further illustrate the content of present invention, rather than limits 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, mixture dual alkalinity 0.05 is adjusted, mixture is finely ground to -200 mesh grade accountings
100%, -400 mesh grade proportions are 50%；Then mixture is subjected to pelletizing, the pelletizing of 8~12mm 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 calcination temperature is 1000 DEG C, time 10min, and two-stage calcination temperature is 1350 DEG C, time 30min；After cooling, it will roast
It is 100% that agglomerate is levigate to mass percent shared by -200 mesh grades, and magnetic separation is carried out under the magnetic field intensity of 1000Gs.Gained magnetic
Manganese in concentrate selection, iron the rate of recovery be 95.3% and 93.5%, 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 adjusts mixture dual alkalinity 0.45, mixture is finely ground to -200 mesh grades using Ground limestone, quick lime as flux
Accounting 100%, -400 mesh grade proportions are 65%；Then mixture 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 set
In Muffle furnace, one section of calcination temperature is 800 DEG C, time 60min, and two-stage calcination temperature is 1200 DEG C, time 180min；
After cooling, will roast agglomerate it is levigate to mass percent shared by -200 mesh grades be 100%, under the magnetic field intensity of 950Gs into
Row magnetic separation.Manganese in gained magnetic concentrate, iron the rate of recovery be 94.1% and 92.6%, the removal efficiency of lead is 93.2%, phosphorus it is de-
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 adjusts mixture dual alkalinity 0.30, mixture is finely ground to -200 mesh grades using Ground limestone, quick lime as flux
Accounting 100%, -400 mesh grade proportions are 60%；Then mixture 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 set
In Muffle furnace, one section of calcination temperature is 900 DEG C, time 30min, and two-stage calcination temperature is 1300 DEG C, time 90min；
After cooling, will roast agglomerate it is levigate to mass percent shared by -200 mesh grades be 100%, under the magnetic field intensity of 800Gs into
Row magnetic separation.Manganese in gained magnetic concentrate, iron the rate of recovery be 90.8% and 92.1%, the removal efficiency of lead is 91.9%, phosphorus it is de-
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, mixture dual alkalinity 0.30 is adjusted, mixture is finely ground to -200 mesh grade accountings
100%, -400 mesh grade proportions are 60%；Then mixture is subjected to briquetting, diameter 10cm, the group of a height of 10mm 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 calcination temperature is 950 DEG C, time 20min, and two-stage calcination temperature is 1300 DEG C, time 90min；It is cooling
Afterwards, will roast mass percent shared by levigate extremely -200 mesh grades of agglomerate is 100%, and magnetic is carried out under the magnetic field intensity of 800Gs
Choosing.Manganese in gained magnetic concentrate, iron the rate of recovery be 70.1% and 72.7%, the removal efficiency of lead is 70.3%, the removal efficiency of phosphorus
It is 72.4%.Gained magnetic concentrate cannot be directly as high-quality Mn series alloy smelting furnace material.
Comparative example 2：
In the comparative example basicity not the present invention it is protected in the range of
With TMn 14%, TFe28%, SiO218%, PbO 3.5%, P2O50.82% Ferromanganese Ore mixture is original
Material adjusts mixture dual alkalinity 0.01, mixture is finely ground to -200 mesh grades using Ground limestone, quick lime as flux
Accounting 100%, -400 mesh grade proportions are 50%；Then mixture is subjected to pelletizing, the pelletizing of 8~12mm is made,
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 calcination temperature is 1000 DEG C, time 15min, and two-stage calcination temperature is 1325 DEG C, time 60min；After cooling,
It is 100% that mass percent shared by levigate extremely -200 mesh grades of agglomerate, which will be roasted, and magnetic separation is carried out under the magnetic field intensity of 1000Gs.
Manganese in gained magnetic concentrate, iron the rate of recovery be 74.5% and 73.8%, the removal efficiency of lead is 71.2%, and the removal efficiency of phosphorus is
73.4%.Gained magnetic concentrate cannot be directly as high-quality Mn series alloy smelting furnace material.
Comparative example 3：
In the comparative example basicity not the present invention it is protected in the range of
With TMn 14%, TFe28%, SiO218%, PbO 3.5%, P2O50.82% Ferromanganese Ore mixture is original
Material adjusts mixture dual alkalinity 0.65, mixture is finely ground to -200 mesh grades using Ground limestone, quick lime as flux
Accounting 100%, -400 mesh grade proportions are 50%；Then mixture is subjected to pelletizing, the pelletizing of 8~12mm is made,
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 calcination temperature is 900 DEG C, time 40min, and two-stage calcination temperature is 1300 DEG C, time 90min；It, will after cooling
It is 100% to roast mass percent shared by levigate extremely -200 mesh grades of agglomerate, and magnetic separation is carried out under the magnetic field intensity of 900Gs.Institute
Manganese in magnetic concentrate, iron the rate of recovery 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 cannot be directly as high-quality Mn series alloy smelting furnace material.
Comparative example 4：
In the comparative example temperature not the present invention it is protected in the range of
With TMn 15%, TFe 27%, SiO216%, PbO 3.3%, P2O50.75% Ferromanganese Ore mixture is original
Material adjusts mixture dual alkalinity 0.01, mixture is finely ground to -200 mesh grades using Ground limestone, quick lime as flux
Accounting 100%, -400 mesh grade proportions are 50%；Then mixture is subjected to pelletizing, the pelletizing of 8~12mm is made,
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 calcination temperature is 700 DEG C, time 60min, and two-stage calcination temperature is 1050 DEG C, time 60min；It, will after cooling
It is 100% to roast mass percent shared by levigate extremely -200 mesh grades of agglomerate, and magnetic separation is carried out under the magnetic field intensity of 1000Gs.Institute
Manganese in magnetic concentrate, iron the rate of recovery 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 cannot be directly as high-quality Mn series alloy smelting furnace material.
Claims (7)
1. a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method, it is characterised in that：By particulate Ferromanganese Ore, Ground limestone and quick lime
It carrying out with mine, mixing agglomeration, gained agglomerate carries out one section at a temperature of 800 DEG C~1000 DEG C after drying, first and roasts, then
Two-stage calcination is carried out at a temperature of 1200 DEG C~1350 DEG C, obtains roasting agglomerate；The roasting agglomerate passes through levigate, magnetic separation, obtains
Magnetic concentrate；
Wherein, particulate Ferromanganese Ore, Ground limestone and quick lime with mine 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%.
2. a kind of 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% range.
3. a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 2, it is characterised in that：The particulate ferrimanganic
The granularity of mine is that mass ratio shared by -200 mesh grades is 100%, and mass ratio shared by -400 mesh grades is not less than 50%.
4. a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 1, it is characterised in that：One section of roasting
Time be 10~60min；The time of the two-stage calcination is 30~180min.
5. a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 1, it is characterised in that：One section of roasting
Control system liquid phase quality content is 1%~15% in the process；Control system liquid phase quality content during the two-stage calcination
It is 10%~25%.
6. a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method according to claim 1, it is characterised in that：One section of roasting and two
The calcination atmosphere of section roasting is air atmosphere.
7. according to a kind of low-grade Ferromanganese Ore pyrogenic process beneficiation method of claim 1~6 any one of them, it is characterised in that：Institute
It to granularity be -200 mesh grade proportions is 100% that it is levigate, which to state roasting agglomerate,.
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