CN105087916A - Method for preparing oxide pellets through high-iron manganese ore - Google Patents
Method for preparing oxide pellets through high-iron manganese ore Download PDFInfo
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Abstract
The invention discloses a method for preparing oxide pellets through high-iron manganese ore. According to the method, after being crushed and ground, the high-iron manganese ore is evenly mixed with humic acid modified bentonite and carbonaceous reductant for pelletizing; and obtained raw pellets are dried, preheated, roasted and cooled, and then the high-iron manganese ore finished product pellets are obtained. According to the method, by using humic acid modified bentonite as binding agents, the strength of the raw pellets and the roasted pellets can be effectively improved; and meanwhile by using the carbonaceous reductant, the roasting temperature can be lowered, and the strength of the roasted pellets is further improved. Besides, the preparation method using the modified bentonite has the beneficial effects of being simple in technology, low in energy consumption and low in cost, raw material sources are wide, and industrial production can be achieved easily.
Description
Technical field
The present invention relates to a kind of method that ferric manganese ore concentrate prepares oxide pellet, belong to metallurgical engineering field of material preparation.
Background technology
Manganese is a kind of important strategic resource, and the manganese of 90% is consumed in steel industry as the reductor of molten steel and sweetening agent and alloying element, and 10% for other relevant industries.It is 64,351 ten thousand t that China's manganese ore adds up proven reserve, and retained reserve 59,204 ten thousand t, is mainly distributed in the provinces and regions such as Guangxi, Hunan, Guizhou, Sichuan, Liaoning, Yunnan, accounts for 90% of national manganese resource total reserves.
At present, along with the high speed development of economy and industrial expansion, particularly steel industry, the demand of market to manganese ore is increasing.Thus, the breach between the consumption of Chinese manganese ore and Ore Yield strengthens year by year, and the manganese ore amount of China's dependence on import in 2014 is up to 6,470,000 t.Cause the major cause of this situation to be that China's manganese ore grade is low, the rich manganese resource of higher-grade high-quality does not almost have, and the manganese ore 100% producing medium-low carbon ferromanganese depends on import.The average grade of China's manganese ore is about 20%, and generally containing higher Si, Fe, P, what wherein Fe content was above standard (Mn/Fe<7) accounts for 73%, and the overwhelming majority belongs to ferric manganese ore and Ferromanganese Ore, and SiO in ore
2content up to more than 10%, utilize the manganese ore of this type to need to carry out ore dressing and pyrogenic attack.
The ore dressing of manganese ore has the techniques such as gravity treatment, high intensity magnetic separation, weight-magnetic separation, strong magnetic-flotation, some gangue minerals can be removed by ore dressing, improve manganese grade, but due to the tight symbiosis of ferrimanganic in China's ferric manganese ore and Ferromanganese Ore resource, disseminated grain size is thin, be difficult to realize ferromanganese by means of only ore-dressing technique be separated, the high ferro manganic concerntrate obtained must enter blast-furnace smelting Mn-rich slag again and realize separation between iron and manganese after agglomeration, or carries out electrosmelting high carbon ferromanganese.The composition of feed stock for blast furnace and granularity are the important factors affecting matallurgical products grade and technico-economical comparison.Fine ore enters the ventilation property that stove can reduce furnace charge greatly, worsens the distribution of furnace gas, causes charge level flame to raise and flue dust loss increases and material suspension phenomenon, and thorn serious in causing producing is fiery, collapse material.Therefore, Ferromanganese Ore agglomeration is the very important link of comprehensive utilization realizing ferric manganese ore resource.
Ferromanganese Ore agglomeration mainly comprises Ferromanganese Ore powder sintering and the preparation of manganese beneficiation concentrate acidity, fluxed pellets etc.Because natural manganese ore quality is soft, crystal water content is high, scaling loss is large, suitable liquid phase and turnout is restive causes solid burnup needed for Ferromanganese Ore powder mine sintering high, the problem of environmental pollution caused thus is remarkable.Along with the dilution day by day of Ferromanganese Ore fine ore, the ratio that ferrimanganic beneficiation concentrate occupies is more and more higher, and therefore Ferromanganese Ore concentrate is prepared acid pellet and become more and more important.But, because Ferromanganese Ore concentrate exists following defect preparing in pelletizing process: 1) balling property is poor, causes bentonite adhesive consumption high; 2) baking property is poor, cause the problems such as maturing temperature is high, pellet strength is poor large, mainly because suitable pelletizing consolidation is difficult to generate mutually, Chinese scholars joins the fluxed manganese oxide ore pelletizing of carbon explained hereafter in adopting, although its metallurgical performance is obviously better than manganese sinter, but the intensity of this type of fluxed pellets is poor, the use of small blast furnace can only be met.
Many scholars have carried out alta-mud modification research, with the technical barrier solving current difficult pelletizing, acid pellet prepared by difficult roasting material.Research shows that humic acids modified alta-mud can the balling property of effective modification difficulty pelletizing material, patent documentation " a kind of method for preparing modified bentonite and application thereof for bentonite modified method (application number: 201410430843.5) " discloses a kind of Whote-wet method method for preparing modified bentonite and application thereof, preparation method is after being ground by natural calcium base bentonite, join reacting by heating in the sodium hydroxide solution containing Sodium salts humic acids, after having reacted, filtering separation, gained filtration cakes torrefaction, to grind, obtain modified alta-mud.Obtained modified alta-mud is used for the intensity that iron concentrate pelletization obviously can improve green-ball.But, bentonitic Whote-wet method modification, long flow path, modified product filters, dry energy consumption is high, the time is long, to the large-scale industrial application of this product and energy-conserving and environment-protective unfavorable.
The consolidation of ferrimanganic concentrate acid pellet is different from conventional iron ore and manganese oxide ore pelletizing, and because its Mn-Fe ratio is low, ferrimanganic symbiosis is tight, impurity (SiO
2, Al
2o
3) content is high, Binder Phase suitable in oxidizing roasting process and rational pellet microtexture is caused to be difficult to control, therefore, according to Present Domestic manganese resource feature, carry out pelletizing and the baking property research of ferrimanganic concentrate, realize Ferromanganese Ore resource high-efficiency, rationally, on a large scale utilize, further raising manganeseirom furnace charge quality, reduce fuel consumption, the discharge of decreasing pollution thing, is of great significance the sustainable development tool of nation manganese industry.
Summary of the invention
There is balling property for Ferromanganese Ore concentrate pelletizing in prior art poor, cause bentonite adhesive consumption high; And baking property is poor, cause the problems such as maturing temperature is high, pellet strength is poor, the object of the invention is to be to provide a kind of method utilizing special humic acid modified wilkinite to prepare ferric manganese ore concentrate acid pellet as binding agent, the method can improve green ball strength and roasting ball intensity effectively.
In order to realize technical purpose of the present invention, the invention provides a kind of method that ferric manganese ore concentrate prepares oxide pellet, the method is that ferric manganese ore is broken and after grinding, with humic acids modified alta-mud and carbonaceous reductant in mass ratio 100:0.5 ~ 1.5:0.5 ~ 2.0 mix, pelletizing; Gained green-ball, through super-dry, preheating, roasting and cooling, obtains ferric manganese ore finished product oxide pellet;
Described humic acids modified alta-mud prepares by the following method: Sodium salts humic acids and organic quaternary ammonium salt mixing solutions are sprayed onto after in natural calcium base bentonite, pressure group is shaping, gained agglomerate through ageing, oven dry, fragmentation and grinding, obtains humic acids modified alta-mud successively; Wherein, the butt mass ratio of Sodium salts humic acids, organic quaternary ammonium salt and calcium-base bentonite three is 5 ~ 30:1 ~ 5:100.
Technical scheme of the present invention is used for Ferromanganese Ore pellet formation by the humic acids modified alta-mud using special methods obtained as binding agent, effectively can improve the intensity of green-ball and agglomerates, and hinge structure greatly reduces the usage quantity of Peng Run great soil group binding agent.Meanwhile, Ferromanganese Ore pelletizing can be regulated and controled by using carbonaceous reductant in roasting process, generate suitable manganese iron axinite and knebelite consolidation phase, relatively not add reductive agent and can reduce maturing temperature more than 50 DEG C, pellet strength is improved further.
Humic acid modified bentonite adhesive in technical scheme of the present invention is carried out common modification by Sodium salts humic acids and organic quaternary ammonium salt pair natural calcium base bentonite and is obtained.Na in pressure group and ageing process
+part Ca is replaced with capable can the entering in ca-montmorillonite crystal layer of quaternary ammonium cation
2+, organic quaternary ammonium salt can insert in the lamella of montmorillonite smoothly, will cover the support of flake interlamellar spacing greatly, is conducive to promoting carrying out smoothly further of sodium modification; Particularly carry out chemical bonding between organic quaternary ammonium salt and the functional group of humic acids, all define organic phase in montmorillonite lamella and outside and be connected, be conducive to the organic modification of calcium-base bentonite.This humic acid modified bentonite adhesive can be used for Ferromanganese Ore pelletizing, not only improves green ball strength and roasting ball intensity, and greatly reduces binding agent usage quantity.
The humic acids method for preparing modified bentonite adopted in technical scheme of the present invention has simple to operate, that less energy consumption, cost are low advantage, and raw material sources are wide, are easy to realize suitability for industrialized production.
The method that ferric manganese ore concentrate of the present invention prepares oxide pellet also comprises following preferred version:
In preferred scheme, ferric manganese ore is broken, be ground to the mass percentage content that granularity meets-200 order grades is not less than 80%, and specific surface area is not less than 1500cm
2/ g.In preferred scheme, the mass percentage content that carbonaceous reductant granularity meets-200 order grades is not less than 95%.In preferred scheme, the mass percent that humic acids bentone soil granularity meets-200 order grades is not less than 99%.The Task-size Controlling of humic acids modified alta-mud, carbonaceous reductant and carbon containing iron dust containing is conducive to pelletizing in certain limit.
In preferred scheme, reductive agent is at least one in coke powder, hard coal, blue charcoal, biomass charcoal.These carbonaceous reductants preferred effectively can reduce maturing temperature, thus improve the phenomenon of the pellet strength reduction caused by high-temperature roasting.
In preferred scheme, described preheating is under temperature is the condition of 950 DEG C ~ 1040 DEG C, insulation 6min ~ 10min.
In preferred scheme, roasting is under temperature is the condition of 1240 DEG C ~ 1300 DEG C, insulation 8min ~ 12min.
In preferred scheme, after broken for natural calcium base bentonite, the levigate mass percentage content meeting-1mm grade to granularity is not less than 90%, in the natural calcium base bentonite after levigate, add Sodium salts humic acids and organic quaternary ammonium mixed salt solution by spray pattern, then it is shaping to press down group at 15 ~ 25MPa pressure condition; The ageing of gained agglomerate is after 3 ~ 10 days, and drying, fragmentation and grinding, obtain humic acids modified alta-mud.Preferred humic acids modified alta-mud preparation method has the advantage that flow process is short, simple to operate, energy consumption is low.The humic acids modified alta-mud particularly prepared, for high ferrous manganese ore pelletizing, effectively can improve the intensity of green-ball and agglomerates, and hinge structure greatly reduces the usage quantity of Peng Run great soil group binding agent.
In preferred scheme, the moisture content controlling natural calcium base bentonite and sodium humate solution mixture in pressure group moulding process is 20 ~ 50wt%.Suitable moisture content can make ca-montmorillonite expand, and ca-montmorillonite lattice spacing becomes large, is conducive to ion-exchange, carries out modification to it.
In preferred scheme, described organic quaternary ammonium salt is at least one in dimethyldioctadecylammonium ammonium chloride, trimethyloctadecyl ammonium chloride and trimethylammonium hexadecyl brometo de amonio.Preferred organic quaternary ammonium salt at least containing the relatively large chain alkyl of molecular weight and quaternary ammonium cationic groups, quaternary ammonium cation can with Sodium salts humic acids acid ion bonding, and chain alkyl can be organically-modified to natural calcium base bentonite inside.
Sodium salts humic acids of the present invention and organic quaternary ammonium mixed salt solution are commercially available Sodium salts humic acids and organic quaternary ammonium salt is water-soluble obtains.
In preferred scheme, drying temperature is not higher than 80 DEG C.
Hinge structure, the Advantageous Effects that technical scheme of the present invention is brought:
1) a kind of humic acids modified alta-mud is obtained by method that is simple, low cost;
2) humic acids modified alta-mud is used for Ferromanganese Ore pellet formation as binding agent, effectively can improve the intensity of green-ball and agglomerates, and hinge structure greatly reduces the usage quantity of Peng Run great soil group binding agent.
3) allocate carbonaceous reductant into and carry out pelletizing, Ferromanganese Ore pelletizing can be regulated and controled in roasting process, generate suitable manganese iron axinite and knebelite consolidation phase, with not with addition of reductive agent Ferromanganese Ore pelletizing compared with, its maturing temperature can reduce by more than 50 DEG C.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of the protection domain of restriction the claims in the present invention.
Embodiment 1
During the modification of natural calcium base bentonite, first by commercially available for 5g Sodium salts humic acids and 2g commercially available trimethyloctadecyl ammonium chloride 30mL water dissolution, then be sprayed in 100g calcium-base bentonite, at 25MPa pressure block after mixing.The ageing of gained agglomerate was dried after 10 days at 80 DEG C.Again by the agglomerates of drying and to be ground to mass percentage shared by-200 order grades be 100%, namely obtain humic acids modified alta-mud.When adopting this humic acids modified alta-mud to carry out pelletizing, be that the ferric manganese ore concentrate of 80% is for raw material with granularity mass percentage shared by-200 order grades, add mass ratio 1.0% humic acids modified alta-mud and 1.0% hard coal after mixing, pelletizing, gained shatter strength of green pellet is 15.0 times/0.5m, and ultimate compression strength is 24N/; Preheating temperature 1000 DEG C, warm up time 8min, maturing temperature 1260 DEG C, during roasting time 10min, the ultimate compression strength of roasting ball is 2530N/.
Embodiment 2
During the modification of natural calcium base bentonite, first by commercially available for 30g Sodium salts humic acids and 1g commercially available trimethylammonium hexadecyl brometo de amonio 60mL water dissolution, then be sprayed in 100g calcium-base bentonite, at 20MPa pressure block after mixing.The ageing of gained agglomerate was dried after 5 days at 80 DEG C.Again by dried agglomerates, to be ground to mass percentage shared by-200 order grades be 99%, namely obtains humic acids modified alta-mud.When adopting humic acids modified alta-mud to carry out pelletizing, be that the ferric manganese ore concentrate of 90% is for raw material with mass percentage shared by-200 order grades, add mass ratio 1.5% humic acids modified alta-mud and 1.5% coke powder after mixing, pelletizing, gained shatter strength of green pellet is 20.0 times/0.5m, and ultimate compression strength is 30N/; Preheating temperature 1000 DEG C, warm up time 8min, maturing temperature 1275 DEG C, during roasting time 12min, the ultimate compression strength of roasting ball is 2790N/.
Embodiment 3
During the modification of natural calcium base bentonite, first by commercially available for 20g Sodium salts humic acids and 5g commercially available dimethyldioctadecylammonium ammonium chloride 50mL water dissolution, then be sprayed in 100g calcium-base bentonite, at 15MPa pressure block after mixing.The ageing of gained agglomerate was dried after 10 days at 80 DEG C.Again by dried agglomerates, to be ground to mass percentage shared by-200 order grades be 100%, namely obtains humic acids modified alta-mud.When adopting humic acids modified alta-mud to carry out pelletizing, with mass percentage shared by-200 order grades be 88%, specific surface area is for 1500cm
2the ferric manganese ore concentrate of/g is raw material, add mass ratio 1.5% humic acids modified alta-mud and 1.0% biomass carbon after mixing, pelletizing, gained shatter strength of green pellet is 18.0 times/0.5m, and ultimate compression strength is 28N/; Preheating temperature 1040 DEG C, warm up time 6min, maturing temperature 1300 DEG C, during roasting time 8min, the ultimate compression strength of roasting ball is 2675N/.
Comparative example 1
Natural calcium base bentonite (unmodified) is adopted to be binding agent:
With natural calcium base bentonite for binding agent carries out pelletizing, with mass percentage shared by-200 order grades be 85%, specific surface area is for 1550cm
2the ferrimanganic concentrate of/g is raw material, add mass ratio 2.0% natural calcium base bentonite and 1.5% hard coal after mixing, pelletizing, gained shatter strength of green pellet is 6.0 times/0.5m, and ultimate compression strength is 15N/; Preheating temperature 1000 DEG C, warm up time 8min, maturing temperature 1265 DEG C, during roasting time 10min, the ultimate compression strength of roasting ball is only 1860N/.
Comparative example 2
Pelletizing is not carried out with addition of reductive agent:
During the modification of natural calcium base bentonite, first by commercially available for 15g Sodium salts humic acids 40mL water dissolution, then will wherein add 100g calcium-base bentonite, at the pressure block of 20MPa after mixing.The ageing of gained nodulizing was dried after 10 days at 80 DEG C.Again by the agglomerates of drying, to be ground to mass percentage shared by-200 order grades be 100%, namely obtains humic acids modified alta-mud.When adopting humic acids modified alta-mud to carry out pelletizing, with mass percentage shared by-200 order grades be 90%, specific surface area is for 1730cm
2the ferrimanganic concentrate of/g is raw material, mixing after the humic acids modified alta-mud of interpolation mass ratio 1.5%, pelletizing, and gained shatter strength of green pellet is 18.0 times/0.5m, and ultimate compression strength is 25N/; Preheating temperature 1000 DEG C, warm up time 8min, maturing temperature 1270 DEG C, during roasting time 12min, the ultimate compression strength of roasting ball is 2050N/, is starkly lower than the ultimate compression strength with addition of agglomerates during reductive agent.When maturing temperature is increased to 1345 DEG C, when roasting time is 10min, the ultimate compression strength of roasting ball can reach 2700N/, with in embodiment 2 with addition of the coke powder of 1.5% and maturing temperature for the intensity of the roasting ball obtained when 1275 DEG C is suitable.
Claims (10)
1. ferric manganese ore concentrate prepares a method for oxide pellet, it is characterized in that: by ferric manganese ore after broken and grinding, with humic acids modified alta-mud and carbonaceous reductant in mass ratio 100:0.5 ~ 1.5:0.5 ~ 2.0 mix, pelletizing; Gained green-ball, through super-dry, preheating, roasting and cooling, obtains ferric manganese ore oxide pellet;
Described humic acids modified alta-mud prepares by the following method: Sodium salts humic acids and organic quaternary ammonium salt mixing solutions are sprayed onto after in natural calcium base bentonite, pressure group is shaping, gained agglomerate through ageing, oven dry, fragmentation and grinding, obtains humic acids modified alta-mud successively; Wherein, the butt mass ratio of Sodium salts humic acids, organic quaternary ammonium salt and natural calcium base bentonite three is 5 ~ 30:1 ~ 5:100.
2. ferric manganese ore concentrate according to claim 1 prepares the method for oxide pellet, it is characterized in that: described ferric manganese ore is broken, be ground to the mass percentage content that granularity meets-200 order grades is not less than 80%, and specific surface area is not less than 1500cm
2/ g.
3. ferric manganese ore concentrate according to claim 1 prepares the method for oxide pellet, it is characterized in that: described carbonaceous reductant is at least one in coke powder, hard coal, blue charcoal, biomass charcoal.
4. ferric manganese ore concentrate according to claim 3 prepares the method for oxide pellet, it is characterized in that: the mass percentage content that described carbonaceous reductant granularity meets-200 order grades is not less than 95%.
5. ferric manganese ore concentrate according to claim 1 prepares the method for oxide pellet, it is characterized in that: described preheating is under temperature is the condition of 950 DEG C ~ 1040 DEG C, insulation 6min ~ 10min.
6. ferric manganese ore concentrate according to claim 1 prepares the method for oxide pellet, it is characterized in that: described roasting is under temperature is the condition of 1240 DEG C ~ 1300 DEG C, insulation 8min ~ 12min.
7. ferric manganese ore concentrate according to claim 1 prepares the method for oxide pellet, it is characterized in that: after broken for natural calcium base bentonite, the levigate mass percentage content meeting-1mm grade to granularity is not less than 90%, in the natural calcium base bentonite after levigate, add Sodium salts humic acids and organic quaternary ammonium mixed salt solution by spray pattern, then it is shaping to press down group at 15 ~ 25MPa pressure condition; The ageing of gained agglomerate is after 3 ~ 10 days, and drying, fragmentation and grinding, obtain humic acids modified alta-mud.
8. the ferric manganese ore concentrate according to claim 1 or 7 prepares the method for oxide pellet, it is characterized in that: the moisture content controlling natural calcium base bentonite and sodium humate solution mixture in pressure group moulding process is 20 ~ 50wt%.
9. the ferric manganese ore concentrate according to claim 1 or 7 prepares the method for oxide pellet, it is characterized in that: the mass percent that described humic acids bentone soil granularity meets-200 order grades is not less than 99%.
10. the ferric manganese ore concentrate according to claim 1 or 7 prepares the method for oxide pellet, it is characterized in that: described organic quaternary ammonium salt is at least one in dimethyldioctadecylammonium ammonium chloride, trimethyloctadecyl ammonium chloride and trimethylammonium hexadecyl brometo de amonio.
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| CN107557568A (en) * | 2017-09-11 | 2018-01-09 | 中南大学 | A kind of method that high lead-type promoter manganese takes off lead |
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| CN114574695B (en) * | 2022-01-19 | 2023-08-22 | 中南大学 | Sintering method of iron-manganese ore pellets |
| CN114574694B (en) * | 2022-01-19 | 2023-08-22 | 中南大学 | Novel method for sintering iron concentrate powder balls |
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