CN105087916B - A kind of method that ferric manganese ore concentrate prepares oxide pellet - Google Patents
A kind of method that ferric manganese ore concentrate prepares oxide pellet Download PDFInfo
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- CN105087916B CN105087916B CN201510546924.6A CN201510546924A CN105087916B CN 105087916 B CN105087916 B CN 105087916B CN 201510546924 A CN201510546924 A CN 201510546924A CN 105087916 B CN105087916 B CN 105087916B
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Abstract
The invention discloses a kind of method that ferric manganese ore concentrate prepares oxide pellet, this method is after ferric manganese ore is crushed and ground, with humic acid modified alta-mud and carbonaceous reductant mixing, pelletizing；Gained green-ball produces ferric manganese ore finished ball agglomerate by drying, preheating, be calcined and cool down；This method, as binding agent, can effectively improve the intensity of green-ball and agglomerates by using humic acid modified alta-mud, and use carbonaceous reductant simultaneously, can reduce sintering temperature, further improve roasting ball intensity；In addition, method for preparing modified bentonite has the low advantage of simple technique, less energy consumption, cost, raw material sources are wide, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of method that ferric manganese ore concentrate prepares oxide pellet, belong to metallurgical engineering material and prepare neck
Domain.
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 643,510,000 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%.
At present, with economy and industrial expansion, the particularly high speed development of steel industry, demand of the market to manganese ore
Amount is increasing.Thus, the breach between the consumption and Ore Yield of Chinese manganese ore is increased year by year, and China relies within 2014
The manganese ore amount of import is up to 6,470,000 t.The main cause for causing this situation is that China's manganese ore grade is low, and high-grade high-quality is rich
Manganese resource does not almost have, and the manganese ore 100% of production medium-low carbon ferromanganese depends on import.The average grade of China's manganese ore exists
20% or so, generally containing higher Si, Fe, P, wherein Fe contents are above standard (Mn/Fe<7) account for 73%, overwhelming majority category
The SiO in ferric manganese ore and Ferromanganese Ore, and ore2Content be up to more than 10%, using the manganese ore of this type need carry out
Ore dressing and pyrogenic attack.
The ore dressing of manganese ore has the techniques such as gravity treatment, high intensity magnetic separation, again-magnetic separation, strong magnetic-flotation, and one can be removed by ore dressing
A little gangue minerals, improve manganese grade, but be due to the close symbiosis of ferrimanganic, disseminated grain size in China's ferric manganese ore and ferrimanganic ore resources
Carefully, it is that ferromanganese difficult to realize is separated only by ore-dressing technique, obtained high ferro manganic concerntrate must enter blast furnace process again after agglomeration
Mn-rich slag realizes separation between iron and manganese, or carries out electric furnace smelting high carbon ferromanganese.The composition and granularity of feed stock for blast furnace are that production is smelted in influence
The key factor of product grade and technical-economic index.Fine ore, which enters stove, can substantially reduce the gas permeability of furnace charge, deteriorate the distribution of furnace gas,
Cause the rise of charge level flame and flue dust to lose increase and material suspension phenomenon, and cause serious thorn fire in production, collapse material.Therefore, iron
Manganese ore agglomeration is the very important link of comprehensive utilization for realizing ferric manganese ore resource.
Ferromanganese Ore agglomeration mainly includes ferrimanganic sintering mineral powder and manganese beneficiation concentrate prepares acidity, fluxed pelletses etc..Due to
Natural manganese ore rock land is soft, crystal water content is high, scaling loss is big, suitable liquid phase and output are difficult to control and cause ferrimanganic miberal powder
Solid burnup needed for ore deposit sintering is high, and thus caused problem of environmental pollution is notable.With the increasingly dilution of Ferromanganese Ore fine ore, ferrimanganic choosing
The ratio more and more higher that ore deposit concentrate occupies, therefore Ferromanganese Ore concentrate prepares acid pellet becomes more and more important.But, due to iron
There is following defect during pelletizing is prepared in manganese ore concentrate：1) balling property is poor, causes bentonite adhesive consumption high；2)
Baking property is poor, causes the problems such as sintering temperature is high, pellet strength is poor big, is mutually difficult to give birth to mainly due to suitable pelletizing consolidation
Into domestic and foreign scholars match somebody with somebody the fluxed manganese oxide ore pelletizing of carbon technique productions using interior, although its metallurgical performance is substantially better than manganese burning
Ore deposit is tied, but the intensity of such fluxed pelletses is poor, can only meet the use of small blast furnace.
Many scholars have carried out alta-mud modification research, and oxidation ball is prepared to solve current difficult pelletizing, difficult roasting material
The technical barrier of group.Research shows that humic acid modified alta-mud can effectively be modified the balling property of difficult pelletizing material, patent document
" a kind of method for preparing modified bentonite and its application are for bentonite modified method (application number：201410430843.5)”
A kind of Whote-wet method method for preparing modified bentonite and its application are disclosed, preparation method is by natural calcium-base bentonite grounds travel
After broken, heating response in the sodium hydroxide solution containing sodium humate is added to, after the completion of reaction, is separated by filtration, gained filter cake is done
It is dry, grind, obtain modified alta-mud.The modified alta-mud obtained is used for into iron concentrate pelletization can be obviously improved green-ball
Intensity.But, bentonitic Whote-wet method is modified, long flow path, and modified product filtering, dry energy consumption height, time are long, to this
The large-scale industrial application of product and energy-conserving and environment-protective are unfavorable.
The consolidation of ferrimanganic concentrate acid pellet is different from conventional iron ore and manganese oxide ore pelletizing, because its Mn-Fe ratio is low,
Ferrimanganic symbiosis is close, impurity (SiO2、Al2O3) content is high, causes suitable Binder Phase and rational pelletizing during oxidizing roasting
Ore deposit microstructure is difficult to control to, therefore, according to current domestic manganese resource feature, carries out the pelletizing and baking property of ferrimanganic concentrate
Research, realizes Ferromanganese Ore resource high-efficiency, utilizes rationally, on a large scale, further improve manganeisen furnace charge quality, reduce fuel
Consumption, reduces the discharge of pollutant, and the sustainable development tool of nation manganese industry is of great significance.
The content of the invention
There is balling property for Ferromanganese Ore concentrate pelletizing in the prior art poor, cause bentonite adhesive consumption high；
And baking property is poor, cause the problems such as sintering temperature is high, pellet strength is poor, the purpose of the present invention is to be to provide a kind of utilization
The method that special humic acid modified bentonite prepares ferric manganese ore concentrate acid pellet as binding agent, this method can be effectively
Improve green ball strength and roasting ball intensity.
In order to realize the technical purpose of the present invention, oxide pellet is prepared the invention provides a kind of ferric manganese ore concentrate
Method, this method be ferric manganese ore is broken and after grinding, with humic acid modified alta-mud and carbonaceous reductant in mass ratio
100:0.5~1.5:0.5~2.0 mixes, pelletizing；Gained green-ball produces ferric manganese ore by drying, preheating, be calcined and cool down
Finished product oxide pellet；
Described humic acid modified alta-mud is prepared via a method which to obtain：Sodium humate and organic quaternary ammonium salt are mixed
After spray solution is into natural calcium-base bentonite, briquetting shaping, gained agglomerate sequentially passes through ageing, drying, broken and grinding, obtains
To humic acid modified alta-mud；Wherein, the butt mass ratio of sodium humate, organic quaternary ammonium salt and calcium-base bentonite three be 5~
30:1~5:100.
Technical scheme is used for by using humic acid modified alta-mud made from specific process as binding agent
Ferromanganese Ore pelletizing production, can effectively improve the intensity of green-ball and agglomerates, and greatly reduce Peng Run soil compared with the prior art
The usage amount of class binding agent.Meanwhile, by using carbonaceous reductant can regulate and control Ferromanganese Ore pelletizing generated in roasting process it is suitable
Suitable manganese iron axinite and mangan fayalite consolidation phase, sintering temperature can be reduced by more than 50 DEG C by being not added with reducing agent relatively, make ball
Group's intensity is further improved.
Humic acid modified bentonite adhesive in technical scheme passes through sodium humate and organic quaternary ammonium salt pair
Natural calcium-base bentonite carries out modification altogether and obtained.The Na in briquetting and ageing process+It can enter calcium base with quaternary ammonium cation row
Replace part Ca in montmorillonite crystal layer2+, organic quaternary ammonium salt can be inserted smoothly in the lamella of montmorillonite, will cover the support of flake interlamellar spacing
Greatly, it may advantageously facilitate further being smoothed out for sodium modification；Particularly enter between the functional group of organic quaternary ammonium salt and humic acid
Row chemical bonding, organic organic modification for being connected, being conducive to calcium-base bentonite is all formd in montmorillonite lamella with outside.
The humic acid modified bentonite adhesive can be used for Ferromanganese Ore pelletizing, not only improve green ball strength and roasting ball intensity, and significantly
Reduce binding agent usage amount.
Humic acid method for preparing modified bentonite employed in technical scheme has simple to operate, energy consumption
Less, the low advantage of cost, raw material sources are wide, it is easy to accomplish industrialized production.
The method that the ferric manganese ore concentrate of the present invention prepares oxide pellet also includes following preferred scheme：
It is preferred that scheme in, ferric manganese ore, which crushes, be ground to granularity meets the mass percentage content of -200 mesh grades not
Less than 80%, and specific surface area is not less than 1500cm2/g.It is preferred that scheme in, carbonaceous reductant granularity meet -200 mesh grades
Mass percentage content be not less than 95%.It is preferred that scheme in, humic acid bentone soil granularity meets -200 mesh grades
Mass percent is not less than 99%.The Task-size Controlling of humic acid modified alta-mud, carbonaceous reductant and carbon containing iron dust containing is one
Determine scope and be conducive to pelletizing.
It is preferred that scheme in, reducing agent is at least one of coke powder, anthracite, semi-coke, biomass carbon.It is preferred that these
Carbonaceous reductant can effectively reduce sintering temperature, so as to improve the phenomenon that the pellet strength as caused by high-temperature roasting is reduced.
It is preferred that scheme in, described preheating be temperature be 950 DEG C~1040 DEG C under conditions of, insulation 6min~
10min。
It is preferred that scheme in, roasting be temperature be 1240 DEG C~1300 DEG C under conditions of, be incubated 8min~12min.
It is preferred that scheme in, by natural calcium-base bentonite is broken, the levigate mass percent to granularity satisfaction -1mm grades
After content is not less than 90%, by spray pattern into the natural calcium-base bentonite after levigate addition sodium humate and organic quaternary ammonium
Mixed salt solution, then briquetting is molded under 15~25MPa pressure conditions；It is drying, broken after gained agglomerate is aged 3~10 days
And grinding, produce humic acid modified alta-mud.It is preferred that humic acid modified alta-mud preparation method have flow it is short, operation letter
The low advantage of single, energy consumption.The humic acid modified alta-mud particularly prepared is used for high ferrous manganese ore pelletizing, can effectively improve life
The intensity of ball and agglomerates, and the usage amount of Peng Run great soil group binding agents is greatly reduced compared with the prior art.
It is preferred that scheme in, the water of natural calcium-base bentonite and sodium humate solution mixture is controlled in briquetting forming process
It is 20~50wt% to divide content.Appropriate moisture can expand ca-montmorillonite, and ca-montmorillonite crystal layer spacing becomes
Greatly, be conducive to ion exchange, it is modified.
It is preferred that scheme in, described organic quaternary ammonium salt is dimethyldioctadecylammonium ammonium chloride, trimethyloctadecyl
At least one of ammonium chloride and trimethyl cetyl ammonium bromide.It is preferred that organic quaternary ammonium salt at least contain molecular weight phase
To larger chain alkyl and quaternary ammonium cationic groups, quaternary ammonium cation can be bonded with sodium humate acid ion, and long-chain
Alkyl can be to organically-modified inside natural calcium-base bentonite.
The sodium humate and organic quaternary ammonium mixed salt solution of the present invention is that commercially available sodium humate and organic quaternary ammonium salt are dissolved in water
Obtain.
It is preferred that scheme in, drying temperature is not higher than 80 DEG C.
Compared with the prior art, the advantageous effects that technical scheme is brought：
1) a kind of humic acid modified alta-mud is obtained by simple, inexpensive method；
2) humic acid modified alta-mud is used for Ferromanganese Ore pelletizing production as binding agent, can effectively improve green-ball and roasting ball
The intensity of group, and the usage amount of Peng Run great soil group binding agents is greatly reduced compared with the prior art.
3) supplying carbonaceous reductant carries out pelletizing, can regulate and control Ferromanganese Ore pelletizing and suitable ferromanganese is generated in roasting process
Oxide and mangan fayalite consolidation phase, compared with not with addition of the Ferromanganese Ore pelletizing of reducing agent, its sintering temperature can reduce by 50 DEG C
More than.
Embodiment
Following examples are intended to further illustrate present invention, rather than limit the protection model of the claims in the present invention
Enclose.
Embodiment 1
When natural calcium-base bentonite is modified, first by the commercially available sodium humates of 5g and the commercially available trimethyloctadecyl ammonium chlorides of 2g
Dissolved, then be sprayed into 100g calcium-base bentonites with 30mL water, in 25MPa pressure lower lock blocks after mixing.By gained agglomerate
Ageing is dried after 10 days at 80 DEG C.Again by dry agglomerates and weight/mass percentage composition shared by being ground to -200 mesh grades is
100%, that is, obtain humic acid modified alta-mud.When carrying out pelletizing using this humic acid modified alta-mud, using granularity as -200 mesh
The ferric manganese ore concentrate that weight/mass percentage composition shared by grade is 80% is raw material, and the humic acid modification of addition mass ratio 1.0% is swollen
Mixing, pelletizing after profit soil and 1.0% anthracite, gained shatter strength of green pellet is 15.0 times/0.5m, and compression strength is 24N/
It is individual；In 1000 DEG C of preheating temperature, preheating time 8min, 1260 DEG C of sintering temperature during roasting time 10min, is calcined the resistance to compression of ball
Intensity is 2530N/.
Embodiment 2
When natural calcium-base bentonite is modified, first by the commercially available sodium humates of 30g and the commercially available trimethyl cetyl brominations of 1g
Ammonium 60mL water dissolves, then is sprayed into 100g calcium-base bentonites, in 20MPa pressure lower lock blocks after mixing.By gained group
Block is dried after being aged 5 days at 80 DEG C.Again by dried agglomerates, be ground to weight/mass percentage composition shared by -200 mesh grades
For 99%, that is, obtain humic acid modified alta-mud.When carrying out pelletizing using humic acid modified alta-mud, with shared by -200 mesh grades
The ferric manganese ore concentrate that weight/mass percentage composition is 90% is raw material, add mass ratio 1.5% humic acid modified alta-mud and
Mixing, pelletizing after 1.5% coke powder, gained shatter strength of green pellet are 20.0 times/0.5m, and compression strength is 30N/；In preheating
1000 DEG C of temperature, preheating time 8min, 1275 DEG C of sintering temperature, during roasting time 12min, the compression strength of roasting ball is
2790N/.
Embodiment 3
When natural calcium-base bentonite is modified, first by the commercially available sodium humates of 20g and the commercially available dimethyldioctadecylammonium base chlorine of 5g
Change ammonium 50mL water to dissolve, then be sprayed into 100g calcium-base bentonites, in 15MPa pressure lower lock blocks after mixing.By gained
Agglomerate is dried after being aged 10 days at 80 DEG C.Again by dried agglomerates, be ground to quality percentage shared by -200 mesh grades
Content is 100%, that is, obtains humic acid modified alta-mud.When carrying out pelletizing using humic acid modified alta-mud, with -200 mesh grain
The shared weight/mass percentage composition of level is that 88%, specific surface area is 1500cm2/ g ferric manganese ore concentrate is raw material, adds mass ratio
After 1.5% humic acid modified alta-mud and 1.0% biomass carbon mix, pelletizing, gained shatter strength of green pellet be 18.0 times/
0.5m, compression strength is 28N/；In 1040 DEG C of preheating temperature, preheating time 6min, 1300 DEG C of sintering temperature, roasting time
During 8min, the compression strength of roasting ball is 2675N/.
Comparative example 1
Natural calcium-base bentonite (unmodified) is used for binding agent：
Pelletizing is carried out by binding agent of natural calcium-base bentonite, using weight/mass percentage composition shared by -200 mesh grades as 85%,
Specific surface area is 1550cm2/ g ferrimanganic concentrate is raw material, adds the natural calcium-base bentonite and 1.5% of mass ratio 2.0%
Mixing, pelletizing after anthracite, gained shatter strength of green pellet are 6.0 times/0.5m, and compression strength is 15N/；In preheating temperature
1000 DEG C, preheating time 8min, 1265 DEG C of sintering temperature, during roasting time 10min, the compression strength of roasting ball is only 1860N/
It is individual.
Comparative example 2
Pelletizing is not carried out with addition of reducing agent：
When natural calcium-base bentonite is modified, 15g commercially available sodium humates 40mL water is dissolved first, then will wherein add
100g calcium-base bentonites, in 20MPa pressure lower lock block after mixing.Dried after gained nodulizing is aged 10 days at 80 DEG C.Again
By dry agglomerates, weight/mass percentage composition shared by -200 mesh grades is ground to for 100%, that is, obtains humic acid bentone
Soil.When carrying out pelletizing using humic acid modified alta-mud, using weight/mass percentage composition shared by -200 mesh grades as 90%, specific surface area
For 1730cm2/ g ferrimanganic concentrate is raw material, adds mixing, pelletizing, gained after the humic acid modified alta-mud of mass ratio 1.5%
Shatter strength of green pellet is 18.0 times/0.5m, and compression strength is 25N/；In 1000 DEG C of preheating temperature, preheating time 8min, roasting
1270 DEG C of temperature, during roasting time 12min, the compression strength of roasting ball is 2050N/, hence it is evident that roasted during less than with addition of reducing agent
Burn the compression strength of pelletizing.When sintering temperature is improved to 1345 DEG C, when roasting time is 10min, the compression strength of roasting ball can
Reach 2700N/, with embodiment 2 with addition of 1.5% coke powder and sintering temperature by 1275 DEG C when obtain be calcined the strong of ball
Degree is suitable.
Claims (9)
1. a kind of method that ferric manganese ore concentrate prepares oxide pellet, it is characterised in that：After ferric manganese ore is crushed and ground,
With humic acid modified alta-mud and carbonaceous reductant in mass ratio 100:0.5~1.5:0.5~2.0 mixes, pelletizing；
Gained green-ball produces ferric manganese ore oxide pellet by drying, preheating, be calcined and cool down；
Described humic acid modified alta-mud is prepared via a method which to obtain：Natural calcium-base bentonite is broken, levigate to grain
After the mass percentage content of degree satisfaction -1mm grades is not less than 90%, by spray pattern to the natural calcium base swelling after levigate
Sodium humate and organic quaternary ammonium mixed salt solution are added in soil, then briquetting is molded under 15~25MPa pressure conditions；Gained agglomerate
After ageing 3~10 days, drying, broken and grinding produce humic acid modified alta-mud；Wherein, sodium humate, organic quaternary ammonium salt
Butt mass ratio with natural calcium-base bentonite three is 5~30:1~5:100.
2. the method that ferric manganese ore concentrate according to claim 1 prepares oxide pellet, it is characterised in that：Described height
The mass percentage content that Ferromanganese Ore crushed, be ground to granularity -200 mesh grades of satisfaction is not less than 80%, and specific surface area is not low
In 1500cm2/g。
3. the method that ferric manganese ore concentrate according to claim 1 prepares oxide pellet, it is characterised in that：Described charcoal
Matter reducing agent is at least one of coke powder, anthracite, semi-coke, biomass carbon.
4. the method that ferric manganese ore concentrate according to claim 3 prepares oxide pellet, it is characterised in that：Described charcoal
The mass percentage content that matter reducing agent granularity meets -200 mesh grades is not less than 95%.
5. the method that ferric manganese ore concentrate according to claim 1 prepares oxide pellet, it is characterised in that：Described is pre-
Heat is under conditions of temperature is 950 DEG C~1040 DEG C, to be incubated 6min~10min.
6. the method that ferric manganese ore concentrate according to claim 1 prepares oxide pellet, it is characterised in that：Described roasting
Burning is under conditions of temperature is 1240 DEG C~1300 DEG C, to be incubated 8min~12min.
7. the method that ferric manganese ore concentrate according to claim 1 prepares oxide pellet, it is characterised in that：Briquetting is molded
During control the moisture of natural calcium-base bentonite and sodium humate solution mixture to be 20~50wt%.
8. the method that ferric manganese ore concentrate according to claim 1 prepares oxide pellet, it is characterised in that：Described corruption
The mass percent that phytic acid bentone soil granularity meets -200 mesh grades is not less than 99%.
9. the method that ferric manganese ore concentrate according to claim 1 prepares oxide pellet, it is characterised in that：Described has
Machine quaternary ammonium salt is in dimethyldioctadecylammonium ammonium chloride, trimethyloctadecyl ammonium chloride and trimethyl cetyl ammonium bromide
At least one.
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| CN109251748A (en) * | 2018-10-26 | 2019-01-22 | 核工业西南勘察设计研究院有限公司 | A kind of radioactive pollution soil conditioner and preparation method thereof |
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| CN105714120A (en) * | 2016-04-12 | 2016-06-29 | 唐山市金岭工贸有限公司 | Comprehensive utilization method of low-quality ferromanganese ore slag and steel iron industrial waste |
| CN107400775B (en) * | 2016-05-20 | 2019-07-02 | 云南民族大学 | A kind of method of microwave heating biomass reduction pyrolusite |
| CN107557568B (en) * | 2017-09-11 | 2018-12-21 | 中南大学 | A kind of method that high lead-type promoter manganese takes off lead |
| CN107557567B (en) * | 2017-09-11 | 2018-11-20 | 中南大学 | A kind of method of high-phosphorus iron ore dephosphorization |
| CN114574694B (en) * | 2022-01-19 | 2023-08-22 | 中南大学 | Novel method for sintering iron concentrate powder balls |
| CN114574695B (en) * | 2022-01-19 | 2023-08-22 | 中南大学 | Sintering method of iron-manganese ore pellets |
| CN115261617B (en) * | 2022-07-22 | 2024-03-15 | 北京科技大学 | LF refining slag recycling technology and application thereof |
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| CN101671055B (en) * | 2009-09-24 | 2011-07-20 | 章仁荣 | Nanoscale sodium humate solution and production technology thereof |
| CN102417976B (en) * | 2011-11-16 | 2013-07-31 | 中南大学 | Method for preparing oxidated pellets from pure hematite concentrate |
| CN102399994B (en) * | 2011-11-18 | 2013-11-06 | 攀钢集团研究院有限公司 | Titanium slag smelting method |
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| CN102241068A (en) * | 2011-07-07 | 2011-11-16 | 浙江丰虹新材料股份有限公司 | Method for semi-continuous dry preparation of organic clay by screw extrusion type kneading machine |
| CN104229813A (en) * | 2014-08-28 | 2014-12-24 | 中南大学 | Preparation method and application of modified bentonite |
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| CN109251748A (en) * | 2018-10-26 | 2019-01-22 | 核工业西南勘察设计研究院有限公司 | A kind of radioactive pollution soil conditioner and preparation method thereof |
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