CN103962223B - Utilize the method that v-ti magnetite concentrate is selected in calcining, alkali leaching, classification again - Google Patents

Utilize the method that v-ti magnetite concentrate is selected in calcining, alkali leaching, classification again Download PDF

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CN103962223B
CN103962223B CN201410164285.2A CN201410164285A CN103962223B CN 103962223 B CN103962223 B CN 103962223B CN 201410164285 A CN201410164285 A CN 201410164285A CN 103962223 B CN103962223 B CN 103962223B
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concentrate
alkali leaching
classification
calcining
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CN103962223A (en
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鞠洪钢
文孝廉
刘炳宇
赵亮
陈巍
王忠红
刘晓明
宋仁峰
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Angang Group Mining Co Ltd
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Abstract

A kind of method utilizing calcining, alkali leaching, classification to select v-ti magnetite concentrate again of disclosure, comprise the steps: by concentrated ilmenite by weight 1:0.1~0.2 ratio add CaO, at the temperature of 800 DEG C~1400 DEG C, carry out calcining 20~60 minutes, form calcination product A;Product A is placed in aqueous slkali, alkali leaching reaction 0.5~5 hour at the temperature of 300 DEG C~370 DEG C, filter, obtain filtrate and alkali leaching cake B, B is added water and is configured to ore pulp and feeds cyclone and carry out classification, classification goes out sand setting C and overflow D, described sand setting C to be TFe content is the final iron ore concentrate of 60%~68%, and described overflow D concentration is TiO2Content is the ilmenite concentrate of 35%~50%.The invention have the advantage that and reduce NaOH or KOH consumption, it is achieved that v-ti magnetite concentrate is efficiently sorted, alkaline consumption is low, reduce impurity contents such as entering blast furnace Al and Si, improve the capacity factor of a blast furnace, reduce ironmaking cost, improve titanium resource comprehensive utilization ratio simultaneously.

Description

Utilize the method that v-ti magnetite concentrate is selected in calcining, alkali leaching, classification again
Technical field
The present invention relates to the ore-dressing technique of a kind of v-ti magnetite concentrate, particularly relate to a kind of method utilizing calcining, alkali leaching, classification to select v-ti magnetite concentrate again.
Background technology
Vanadium titano-magnetite is the grandidierite of a kind of multiple metallic element, be based on iron content, vanadium, titanium the magnetic iron ore of symbiosis.And one of v-ti magnetite concentrate product that to be vanadium titano-magnetite obtain through ore dressing, wherein vanadium is composed with isomorph and is stored in titanomagnetite, replaces ferric ion.Titanomagnetite is oikocryst mineral (Fe3O4) and chadacryst ore deposit [ulvite 2FeO TiO2, ilmenite FeO TiO2, aluminum-spinel (Mg, Fe) (Al, Fe)2O4] complex that formed.Such as, China's Panzhihua Region Midi Concentrator v-ti magnetite green ore and the v-ti magnetite concentrate chemistry multielement analysis result after selecting ferrum in Table 1, v-ti magnetite green ore and vanadium titano-magnetite concentrate material phase analysis result respectively in Table 2 and table 3.
Table 1 China's Panzhihua Region Midi Concentrator raw ore and v-ti magnetite concentrate chemistry multielement analysis result
Element TFe FeO mFe S Fe2O3 TiO2 V2O5
Raw ore 29.53 21.36 20.20 0.631 17.70 10.54 0.278
Concentrate 54.01 32.42 51.16 0.574 40.97 12.67 0.61
Element SiO2 Al2O3 CaO MgO Co P As
Raw ore 22.80 7.65 6.36 7.23 0.02 0.015 <0.01
Concentrate 3.21 3.30 0.98 2.90 0.02 0.008 <0.010
Table 2 China Panzhihua Region Midi Concentrator v-ti magnetite green ore titanium, ferrum chemical phase analysis result
Table 3 China Panzhihua Region Midi Concentrator vanadium titano-magnetite concentrate titanium, ferrum chemical phase analysis result
Vanadium titano-magnetite aboundresources in the world, whole world reserves reach more than 40,000,000,000 tons, and reserves in China reaches 98.3 hundred million tons.In v-ti magnetite Ore, ferrum is mainly composed and is stored in titanomagnetite, the TiO in Ore2Main tax is stored in granular ilmenite and titanomagnetite.Generally, the titanium of about 57% is composed and is stored in titanomagnetite (mFeTiO3·nFe3O4) in, the titanium of about 40% is composed and is stored in ilmenite (FeTiO3) in, due to vanadium titano-magnetite Ore composition complexity, character is special, thus the comprehensive utilization of this kind of Ore is the international a great problem always thoroughly not solved.This occurrence characteristics of vanadium titano-magnetite mineral determines and adopts physical upgrading method cannot realize titanium, the efficiently separating of ferrum from the source of Ore, cause v-ti magnetite Ore after physical upgrading, iron concentrate grade low (TFe < 55%), the titanium in iron ore concentrate at ironmaking processes completely into blast furnace slag (TiO2Content reaches more than 22%) form vitreous body, TiO2Lose activity and cannot economic recovery, meanwhile, titanium recovery rate is low by only 18%.Therefore with the beneficiation method of physics sort titanium iron ore greatly reduce titanium and ferrum individually with value.
China is first country comprehensively extracting ferrum, vanadium, titanium with commercial scale from complicated vanadium titano-magnetite in the world, but due to general physical method can not fundamentally change ferrum, characteristic is deposited in the tax of titanium densification symbiosis, therefore, adopt the physical upgrading methods such as common gravity separation method, magnetic method, floatation to carry out titanium, ferrum separates, efficiency is low, is difficult to select of high grade and ilmenite concentrate that impurity is few or iron ore concentrate;Meanwhile, TiO2Organic efficiency is not high, v-ti magnetite green ore after Mineral separation, the TiO of about 54%2Enter iron ore concentrate, these TiO2After blast furnace process, almost fully enter slag phase, form TiO2The blast furnace slag of content 20~24%;Further, since the impurity contents such as S, Si, Al in iron ore concentrate are also too high, above-mentioned reason not only causes that steelmaking furnace usage factor is low, energy consumption big, titanium resource waste, and amount of slag is big, environmental pollution is serious.
CN2011100879566 discloses " beneficiation method of a kind of ilmenite ", is by the v-ti magnetite green ore method that magnetic separation obtains ilmenite concentrate and iron ore concentrate after ore grinding, alkaline pretreatment, filtration, again ore grinding.The method is by iron content 32.16% with containing TiO2The v-ti magnetite green ore of 12.11% is processed by magnetic separation after ore grinding, alkaline pretreatment, filtration, again ore grinding, defines iron content 59.30% iron ore concentrate and containing TiO2The ilmenite concentrate of 20.15%.Owing to the method is for ilmenite raw ore, raw ore SiO2、Al2O3, the gangue mineral content such as CaO, MgO high, the process of alkali leaching will preferentially occur at SiO2、Al2O3With mineral, defining compound after the alkali similar to titanium soaks in the dipped journey of alkali, the NaOH alkali number of alkali leaching ferrotianium raw ore consumption is 469Kg/t raw ore, and cost is high;And the titanium compound formed after the leaching of ferrotianium raw ore alkali, with the compound of silicon formed after the gangue mineral alkali leaching such as quartz, it is very difficult for wanting to realize efficiently separating in follow-up magnetic separation, and this also constrains the raising of iron concentrate grade and ilmenite concentrate grade after ferrotianium raw ore alkali soaks.Meanwhile, the method adopts twice grinding process to change mineral surfaces physicochemical properties, adds complexity and the process cost of the method.In a word, by this kind of procedure complexity, and in processing procedure, quantity of alkali consumption is big, cost is high;Simultaneously, it is impossible to obtain more high-grade iron ore concentrate and ilmenite concentrate.
CN201310183580.8 discloses " a kind of method that wet treatment sefstromite concentrate prepares titanium liquid ", it is proposed that by the method for salt pickling separation ferrotianium.This invention is the method that wet treatment v-ti magnetite concentrate prepares titanium liquid, the processes such as titanium liquid are obtained including v-ti magnetite concentrate hydrochloric acid leaching, fused salt reaction, pickling again, sulfuric acid solution, filtration etc., the method is primarily directed to extraction ilmenite concentrate, its complex technical process, hydrochloric acid leaching process needs react with ferrum and vanadium with hydrochloric acid to dissolve in filtrate, consuming a large amount of hydrochloric acid, cost is high;Meanwhile, fused salt process consumes alkali with NaOH with titanium and pasc reaction.Further, since employ hydrochloric acid in the method leaching process, in hydrochloric acid, chloride ion is big to equipment corrosion, not easily industrialized production.The method is primarily adapted for use in the low lean v-ti magnetite concentrate of high vanadium low iron content the recycling of titanium.
Summary of the invention
In order to overcome the deficiency of above-mentioned beneficiation method, the technical problem to be solved is on the basis that physics and chemical mineral processing method effectively combine, there is provided that a kind of cost is low, it is high to reclaim quality and efficiency and the method utilizing calcining, alkali leaching, classification to select v-ti magnetite concentrate again of good operability, achieve and titanium, ferrum in v-ti magnetite concentrate are carried out high efficiency separation, improve into stokehold Iron grade, reduce and enter blast furnace TiO2, the impurity such as S, Si, Al content, improve the capacity factor of a blast furnace, reduce the discharge capacity of blast furnace slag, reduce ironmaking cost, improve TiO2Comprehensive resource utilization rate, reduces NaOH or KOH consumption simultaneously, decreases environmental pollution.
In order to realize the purpose of the present invention, the technical scheme is that and be achieved in that:
A kind of method utilizing calcining, alkali leaching, classification to select v-ti magnetite concentrate again of the present invention, it is characterised in that comprise the steps:
1) calcining
It is 50%~55% by TFe content range, TiO2Content range is 10%~15%, SiO2Content is 3%~6%, Al2O3Content is 3%~6%, S content > 0.5% the ratio of v-ti magnetite concentrate 1:0.1~0.2 by weight add CaO, at the temperature of 800 DEG C~1400 DEG C, carry out calcining 20~60 minutes, form calcination product A;
2) alkali leaching
By step 1) in calcination product A be placed in the aqueous slkali that mass concentration is 5%~52%, alkali leaching reaction 0.5~5 hour at the temperature of 300 DEG C~370 DEG C, being filtered by reactant, obtain filtrate and alkali leaching cake B, described filtrate feeds recovery and processing system;
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp of formation mass concentration 20%~25% feeds cyclone and carries out classification, classification goes out sand setting C and overflow D, described sand setting C to be TFe content range is the final iron ore concentrate of 60%~68%, and described overflow D concentration is TiO2Content range is the ilmenite concentrate of 35%~50%.
Described aqueous slkali is any one in NaOH or KOH aqueous solution, NaOH and KOH mixed aqueous solution.
The invention have the advantage that
The method that v-ti magnetite concentrate is selected in the method integrated use calcining of the present invention, alkali leaching, classification again, it is achieved that titanium, ferrum high efficiency separation in v-ti magnetite concentrate;In the iron ore concentrate concurrently separated out, S content is greatly reduced, and is decreased to less than 0.10% by more than 0.50%, SiO2Content is down to less than 3% by 3%~6%, Al2O3Content is down to less than 3% by 3%~6%, creates better condition for subsequent smelting.
Calcination utilizes CaO part to replace alkali liquor consumption in the dipped journey of alkali, decreases the consumption 20%~30% of NaOH or KOH in subsequent alkaline leaching operation;Owing to CaO price is NaOH price 1/5~1/6, it is the 1/20 of KOH price, therefore can be substantially reduced production cost.
The elements such as Ti, S, Si, Al in v-ti magnetite concentrate have been carried out chemical reaction by the process of alkali leaching, define corresponding salt.With v-ti magnetite concentrate the difference is that, SiO in ilmenite raw ore2Content (> 20%) and Al2O3Content (> 7%) it is significantly larger than in v-ti magnetite concentrate SiO2Content (< 6%) and Al2O3Content (< 6%), soak in ilmenite raw ore process at alkali, owing to the process of alkali leaching will preferentially occur at SiO2、Al2O3Deng on mineral so that it is less that alkali leaching v-ti magnetite concentrate soaks ferrotianium raw ore alkali consumption than alkali, better effects if.Such as, after calcining, when soaking with NaOH alkali, the alkali number that the present invention consumes is less than 60kg/t concentrate, and the alkali number 469kg/t raw ore soaking raw ore consumption than alkali reduces more than 7 times.
Granularity and the gravity grading of mineral pressed by cyclone, and the titanium compound generated after alkali leaching is than the fine size of iron mineral, and proportion is little, titanium, ferrum difference of specific gravity bigger, it is achieved that titanium, the efficiently separating of ferrum.Make iron concentrate grade be brought up to 60%~68% by 50%~55% plus classification, iron ore concentrate is measured less than 0.1% containing S, SiO simultaneously2And Al2O3Content is respectively less than 3%, TiO2Content is down to less than 6% by 12.91%;At the same time it can also be obtain TiO2Content is the ilmenite concentrate of 35%~50%.Employing the method achieves and titanium, ferrum is effectively separated, and reduces and enters blast furnace TiO2, the impurity such as S, Si, Al content, improve the capacity factor of a blast furnace, reduce the discharge capacity of blast furnace slag, reduce ironmaking cost, improve titanium resource comprehensive utilization ratio simultaneously.
Accompanying drawing explanation
Fig. 1 is present invention process flow chart.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further:
As shown in Figure 1.
Embodiment 1:
1) calcining
It is 51.3% by TFe content, TiO2Content is 14.0%, SiO2Content is 3.66%, Al2O3Content is 4.42%, the v-ti magnetite concentrate of S content 0.55%, and the ratio of 1:0.1 adds CaO by weight, carries out calcining 30 minutes at the temperature of 1200 DEG C, forms calcination product A, and its chemical equation is:
2) alkali leaching
By step 1) in calcination product A be placed in the NaOH aqueous slkali that mass concentration is 20%, alkali leaching reaction 3.0 hours at the temperature of 300 DEG C, reactant is filtered, obtain filtrate and alkali leaching cake B, NaOH consumption 47kg/t is to ore deposit, described filtrate feeds recovery and processing system, and its chemical equation is:
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp forming mass concentration 20% feeds cyclone and carries out classification, and classification goes out the final iron ore concentrate (SiO that sand setting C and overflow D, sand setting C are TFe content 60.8%2Content is 0.83%, Al2O3Content is 1.55%, S content is 0.02%), overflow D concentration is TiO2Content is the final ilmenite concentrate of 39.8%.
Embodiment 2:
1) calcining
It is 53.5% by TFe content, TiO2Content is 11.3%, SiO2Content is 3.56%, Al2O3Content is 5.50%, the v-ti magnetite concentrate of S content 0.72%, and the ratio of 1:0.11 adds CaO by weight, carries out calcining 45 minutes at the temperature of 1000 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali leaching
By step 1) in calcination product A be placed in the NaOH aqueous slkali that mass concentration is 10%, alkali leaching reaction 3.0 hours at the temperature of 315 DEG C, reactant is filtered, obtain filtrate and alkali leaching cake B, NaOH consumption 45kg/t is to ore deposit, described filtrate feeds recovery and processing system, and its chemical equation is with embodiment 1.
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp forming mass concentration 21% feeds cyclone and carries out classification, and classification goes out the final iron ore concentrate (SiO that sand setting C and overflow D, sand setting C are TFe content 63.5%2Content is 0.67%, Al2O3Content is 1.44%, S content is 0.02%), overflow D concentration is TiO2Content is the final ilmenite concentrate of 36.8%.
Embodiment 3:
1) calcining
It is 53.4% by TFe content, TiO2Content is 13.2%, SiO2Content is 3.45%, Al2O3Content is 5.08%, the v-ti magnetite concentrate of S content 0.60%, and the ratio of 1:0.1 adds CaO by weight, carries out calcining 50 minutes at the temperature of 900 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali leaching
By step 1) in calcination product A be placed in the NaOH aqueous slkali that mass concentration is 28%, alkali leaching reaction 2.5 hours at the temperature of 305 DEG C, reactant is filtered, obtain filtrate and alkali leaching cake B, NaOH consumption 47.5kg/t is to ore deposit, described filtrate feeds recovery and processing system, and its chemical equation is with embodiment 1.
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp forming mass concentration 22% feeds cyclone and carries out classification, and classification goes out the final iron ore concentrate (SiO that sand setting C and overflow D, sand setting C are TFe content 64.7%2Content is 0.54%, Al2O3Content is 1.40%, S content is 0.02%), overflow D concentration is TiO2Content is the final ilmenite concentrate of 35.9%.
Embodiment 4:
1) calcining
It is 54.8% by TFe content, TiO2Content is 10.9%, SiO2Content is 3.50%, Al2O3Content is 5.20%, the v-ti magnetite concentrate of S content 0.66%, and the ratio of 1:0.12 adds CaO by weight, carries out calcining 30 minutes at the temperature of 1300 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali leaching
By step 1) in calcination product A be placed in the NaOH aqueous slkali that mass concentration is 49%, alkali leaching reaction 2.0 hours at the temperature of 370 DEG C, reactant is filtered, obtain filtrate and alkali leaching cake B, NaOH consumption 45.0kg/t is to ore deposit, described filtrate feeds recovery and processing system, and its chemical equation is with embodiment 1.
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp forming mass concentration 23% feeds cyclone and carries out classification, and classification goes out the final iron ore concentrate (SiO that sand setting C and overflow D, sand setting C are TFe content 67.5%2Content is 0.61%, Al2O3Content is 1.30%, S content is 0.01%), overflow D concentration is TiO2Content is the final ilmenite concentrate of 46.1%.
Embodiment 5:
1) calcining
It is 53.8% by TFe content, TiO2Content is 12.9%, SiO2Content is 3.67%, Al2O3Content is 5.01%, the v-ti magnetite concentrate of S content 0.75%, and the ratio of 1:0.15 adds CaO by weight, carries out calcining 20 minutes at the temperature of 1400 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali leaching
By step 1) in calcination product A be placed in the KOH aqueous slkali that mass concentration is 15%, alkali leaching reaction 2.0 hours at the temperature of 310 DEG C, reactant is filtered, obtain filtrate and alkali leaching cake B, KOH consumption 45.0kg/t is to ore deposit, described filtrate feeds recovery and processing system, and its chemical equation is:
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp forming mass concentration 24% feeds cyclone and carries out classification, and classification goes out the final iron ore concentrate (SiO that sand setting C and overflow D, sand setting C are TFe content 66.4%2Content is 0.61%, Al2O3Content is 1.30%, S content is 0.01%), overflow D concentration is TiO2Content is the final ilmenite concentrate of 45.8%.
Embodiment 6:
1) calcining
It is 53.6% by TFe content, TiO2Content is 11.9%, SiO2Content is 3.82%, Al2O3Content is 4.62%, the v-ti magnetite concentrate of S content 0.55%, and the ratio of 1:0.2 adds CaO by weight, carries out calcining 60 minutes at the temperature of 800 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali leaching
By step 1) in calcination product A be placed in the KOH aqueous slkali that mass concentration is 25%, alkali leaching reaction 4.0 hours at the temperature of 320 DEG C, reactant is filtered, obtain filtrate and alkali leaching cake B, KOH consumption 57kg/t is to ore deposit, described filtrate feeds recovery and processing system, and its chemical equation is with embodiment 5.
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp forming mass concentration 25% feeds cyclone and carries out classification, and classification goes out the final iron ore concentrate (SiO that sand setting C and overflow D, sand setting C are TFe content 67.2%2Content is 0.31%, Al2O3Content is 1.38%, S content is 0.01%), overflow D concentration is TiO2Content is the final ilmenite concentrate of 49.5%.
Embodiment 7:
1) calcining
It is 54.0% by TFe content, TiO2Content is 12.3%, SiO2Content is 3.80%, Al2O3Content is 4.60%, the v-ti magnetite concentrate of S content 0.55%, and the ratio of 1:0.2 adds CaO by weight, carries out calcining 25 minutes at the temperature of 1350 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali leaching
By step 1) in calcination product A be placed in NaOH mass concentration be 20%, KOH mass concentration be 6% aqueous slkali in, alkali leaching reaction 4.0 hours at the temperature of 330 DEG C, reactant is filtered, obtain filtrate and alkali leaching cake B, NaOH consumption 20kg/t is to ore deposit, KOH consumption 25kg/t is to ore deposit, and described filtrate feeds recovery and processing system, embodiment 1 and embodiment 5.
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp forming mass concentration 25% feeds cyclone and carries out classification, and classification goes out the final iron ore concentrate (SiO that sand setting C and overflow D, sand setting C are TFe content 66.8%2Content is 0.25%, Al2O3Content is 1.11%, S content is 0.01%), overflow D concentration is TiO2Content is the final ilmenite concentrate of 48.9%.

Claims (1)

1. one kind utilizes the method that v-ti magnetite concentrate is selected in calcining, alkali leaching, classification again, it is characterised in that comprise the steps:
1) calcining
It is 50%~55% by TFe content range, TiO2Content range is 10%~15%, SiO2Content is 3%~6%, Al2O3Content is 3%~6%, S content > 0.5% the ratio of v-ti magnetite concentrate 1:0.1~0.2 by weight add CaO, at the temperature of 800 DEG C~1400 DEG C, carry out calcining 20~60 minutes, form calcination product A;
2) alkali leaching
By step 1) in calcination product A be placed in the aqueous slkali that mass concentration is 5%~52%, described aqueous slkali is any one in NaOH or KOH aqueous solution, NaOH and KOH mixed aqueous solution, alkali leaching reaction 0.5~5 hour at the temperature of 300 DEG C~370 DEG C, reactant is filtered, obtaining filtrate and alkali leaching cake B, described filtrate feeds recovery and processing system;
3) classification
By step 2) in alkali leaching cake B add water, the ore pulp of formation mass concentration 20%~25% feeds cyclone and carries out classification, classification goes out sand setting C and overflow D, described sand setting C to be TFe content range is the final iron ore concentrate of 60%~68%, and described overflow D concentration is TiO2Content range is the ilmenite concentrate of 35%~50%.
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