CN103962223A - Method for recleaning of vanadium-titanium magnetite concentrates through calcination, alkaline leaching and classification - Google Patents
Method for recleaning of vanadium-titanium magnetite concentrates through calcination, alkaline leaching and classification Download PDFInfo
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Abstract
The invention discloses a method for recleaning of vanadium-titanium magnetite concentrates through calcination, alkaline leaching and classification. The method comprises the following steps that CaO is added to titaniferous iron concentrates according to the weight ratio of 1: 0.1 to 0.2, the mixture is calcined for 20 to 60 minutes at the temperature ranging from 800 DEG C to 1400 DEG C, and therefore a calcined product A is formed; the product A is placed in an alkaline solution, an alkaline leaching reaction is conducted for 0.5 to 5 hours at the temperature ranging from 300 DEG C to 370 DEG C, and filtrate and an alkaline leaching filter cake B are obtained through filtration; water is added to the alkaline leaching filter cake B, so that ore pulp is prepared and fed into a hydrocyclone for classification, and settling sand C and overflow D are obtained through classification; the settling sand C is final iron ore concentrates with the TFe content ranging from 60% to 68%, and the overflow D is concentrated to be titanium concentrates with the TiO2 content ranging from 35% to 50%. The method has the advantages that consumption of NaOH or KOH is reduced, the vanadium-titanium magnetite concentrates are efficiently screened, alkali consumption is low, the content of impurities such as Al and Si which enter a blast furnace is reduced, the blast furnace use coefficient is increased, iron manufacture cost is reduced, and meanwhile the comprehensive use rate of titanium resources is improved.
Description
Technical field
The present invention relates to a kind of ore-dressing technique of v-ti magnetite concentrate, relate in particular to a kind of method that calcining, alkali soak, v-ti magnetite concentrate is selected in classification again of utilizing.
Background technology
Vanadium titano-magnetite is a kind of grandidierite of multiple metallic element, is the magnetic iron ore taking iron content, vanadium, titanium as main symbiosis.And v-ti magnetite concentrate is one of product of vanadium titano-magnetite process ore dressing acquisition, wherein vanadium is composed and is stored in titanomagnetite with isomorph, displacement high price iron ion.Titanomagnetite is oikocryst mineral (Fe
3o
4) and chadacryst ore deposit [ulvite 2FeOTiO
2, ilmenite FeOTiO
2, aluminum-spinel (Mg, Fe) (Al, Fe)
2o
4] form complex.For example, Chinese Panzhihua Region Midi Concentrator v-ti magnetite green ore and select v-ti magnetite concentrate after iron chemistry multielement analysis to the results are shown in Table 1, v-ti magnetite green ore and vanadium titano-magnetite concentrate material phase analysis result are respectively in table 2 and table 3.
The Chinese Panzhihua Region of table 1 Midi Concentrator raw ore and v-ti magnetite concentrate chemistry multielement analysis result
| Element | TFe | FeO | mFe | S | Fe 2O 3 | TiO 2 | V 2O 5 |
| 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 | SiO 2 | Al 2O 3 | 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 |
The Chinese Panzhihua Region of table 2 Midi Concentrator v-ti magnetite green ore titanium, iron chemical phase analysis result
The Chinese Panzhihua Region of table 3 Midi Concentrator vanadium titano-magnetite concentrate titanium, iron 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, iron is mainly composed and is stored in titanomagnetite, the TiO in ore
2main tax is stored in granular ilmenite and titanomagnetite.Generally, approximately 57% titanium is composed and is stored in titanomagnetite (mFeTiO
3nFe
3o
4) in, approximately 40% titanium is composed and is stored in ilmenite (FeTiO
3) in, because vanadium titano-magnetite ore composition is complicated, character is special, thereby the comprehensive utilization of this class ore is the international a great problem always thoroughly not solving.This occurrence characteristics of vanadium titano-magnetite mineral has determined to adopt physical upgrading method cannot realize from the source of ore effective separation of titanium, iron, cause v-ti magnetite ore after physical upgrading, iron concentrate grade low (TFe<55%), the titanium in iron ore concentrate enters blast furnace slag (TiO completely at ironmaking processes
2content reaches more than 22%) formation vitreum, TiO
2lost actively and cannot economic recovery, meanwhile, titanium recovery rate is low only has 18%.Therefore sort titanium iron ore by the beneficiation method of physics and greatly reduce titanium and the iron value of utilization separately.
China is that first comprehensively extracts the country of iron, vanadium, titanium from complicated vanadium titano-magnetite with commercial scale in the world, but characteristic is deposited in the tax that can not fundamentally change iron, the fine and close symbiosis of titanium due to general physical method, therefore, adopt the physical upgrading methods such as common gravity separation method, magnetic method, floatation to carry out titanium, iron separation, efficiency is low, is difficult to select ilmenite concentrate of high grade and that impurity is few or iron ore concentrate; Meanwhile, TiO
2organic efficiency is not high, v-ti magnetite green ore after Mineral separation, approximately 54% TiO
2enter iron ore concentrate, these TiO
2after blast furnace process, almost all enter slag phase, form TiO
2the blast furnace slag of content 20～24%; In addition, because the impurity contents such as the S in iron ore concentrate, Si, Al are also too high, above-mentioned reason not only causes that steelmaking furnace usage factor is low, energy consumption is large, titanium resource waste, and amount of slag is large, environmental pollution is serious.
CN2011100879566 discloses " a kind of beneficiation method of ilmenite ", be by v-ti magnetite green ore through ore grinding, alkali soak pretreatment, filtration, magnetic separation obtains the method for ilmenite concentrate and iron ore concentrate after ore grinding again.The method is by iron content 32.16% with containing TiO
212.11% v-ti magnetite green ore soaks pretreatment, filtration, magnetic separation processing after ore grinding again by ore grinding, alkali, has formed iron content 59.30% iron ore concentrate and containing TiO
220.15% ilmenite concentrate.Because the method is for ilmenite raw ore, raw ore SiO
2, Al
2o
3, the gangue mineral content such as CaO, MgO is high, the process that alkali soaks will preferentially occur in SiO
2, Al
2o
3with it mineral, alkali soaks and in process, has formed the alkali similar to titanium and soak rear compound, and the NaOH alkali number that alkali soaks the consumption of ferrotianium raw ore is 469Kg/t raw ore, and cost is high; And ferrotianium raw ore alkali soaks the titanium compound of rear formation, soak the compound of the silicon of rear formation with gangue mineral alkali such as quartz, want in follow-up magnetic separation to realize that effectively to separate be very difficult, this has also restricted ferrotianium raw ore alkali and has soaked the raising of rear iron concentrate grade and ilmenite concentrate grade.Meanwhile, the method adopts twice grinding process to change mineral surfaces physicochemical properties, has increased 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 large, cost is high; Meanwhile, cannot obtain more high-grade iron ore concentrate and ilmenite concentrate.
CN201310183580.8 discloses " a kind of wet-treating sefstromite concentrate is prepared the method for titanium liquid ", has proposed the method with salt pickling separating titanium iron.This invention is the method that wet-treating v-ti magnetite concentrate is prepared titanium liquid, comprise that v-ti magnetite concentrate hydrochloric acid leaching, molten salt react ion, pickling again, sulfuric acid solution, filtration etc. obtain the processes such as titanium liquid, the method is mainly for extracting ilmenite concentrate, its complex technical process, in hydrochloric acid leaching process, need to react and dissolve in filtrate with iron and vanadium with hydrochloric acid, consume a large amount of hydrochloric acid, cost is high; Meanwhile, in fused salt process, use NaOH and titanium and pasc reaction to consume alkali.In addition, owing to having used hydrochloric acid in the method leaching process, in hydrochloric acid, chlorion is large to equipment corrosion, is difficult for suitability for industrialized production.The method is mainly applicable to the recycling of titanium in the low poor v-ti magnetite concentrate of high vanadium low iron content.
Summary of the invention
In order to overcome the deficiency of above-mentioned beneficiation method, technical problem to be solved by this invention is on the basis of the effective combination of physics and chemistry beneficiation method, provide a kind of cost low, reclaim quality and efficiency is high and utilization calcining, the alkali of good operability soak, v-ti magnetite concentrate is selected in classification again method, realize titanium, iron in v-ti magnetite concentrate have efficiently been separated, improve and entered stokehold iron grade, reduced and enter blast furnace TiO
2, the impurity such as S, Si, Al content, improve the capacity factor of a blast furnace, reduce the discharge capacity of blast furnace slag, reduced ironmaking cost, improved TiO
2comprehensive utilization of resources rate has reduced NaOH or KOH consumption simultaneously, has reduced environmental pollution.
In order to realize object of the present invention, technical scheme of the present invention is achieved in that
A kind of method that calcining, alkali soak, v-ti magnetite concentrate is selected in classification again of utilizing of the present invention, is characterized in that comprising the steps:
1) calcining
Be 50%～55%, TiO by TFe content range
2content range is 10%～15%, SiO
2content is 3%～6%, Al
2o
3content is 3%～6%, the v-ti magnetite concentrate of S content >0.5% by weight the ratio of 1:0.1～0.2 add CaO, at the temperature of 800 DEG C～1400 DEG C, calcine 20～60 minutes, form calcination product A;
2) alkali soaks
By step 1) in calcination product A to be placed in mass concentration be 5%～52% aqueous slkali, at the temperature of 300 DEG C～370 DEG C, alkali soaks reaction 0.5～5 hour, reactant is filtered, 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 that forms mass concentration 20%～25% feeds cyclone and carries out classification, classification goes out sand setting C and overflow D, and described sand setting C is that TFe content range is 60%～68% final iron ore concentrate, described overflow D simmer down to TiO
2content range is 35%～50% ilmenite concentrate.
Described aqueous slkali is any one in NaOH or the KOH aqueous solution, NaOH and KOH mixed aqueous solution.
Advantage of the present invention is:
Method synthesis of the present invention uses calcining, alkali soaks, v-ti magnetite concentrate is selected in classification again method, has realized titanium in v-ti magnetite concentrate, iron efficiently separates; In isolated iron ore concentrate, S content significantly reduces simultaneously, by more than 0.50% being down to and being less than 0.10%, SiO
2content is down to below 3% by 3%～6%, Al
2o
3content is down to below 3% by 3%～6%, for subsequent smelting has been created better condition.
Calcination process utilizes CaO part to replace alkali to soak alkali lye consumption in process, has reduced follow-up alkali and soak the consumption 20%～30% of NaOH in operation or KOH; Because CaO price is 1/5～1/6 of NaOH price, be 1/20 of KOH price, therefore can greatly reduce production costs.
The process that alkali soaks has been carried out chemical reaction to elements such as Ti, S, Si, Al in v-ti magnetite concentrate, has formed corresponding salt.Different from v-ti magnetite concentrate, SiO in ilmenite raw ore
2content (>20%) and Al
2o
3content (>7%) is far away higher than SiO in v-ti magnetite concentrate
2content (<6%) and Al
2o
3content (<6%), soaks in ilmenite raw ore process at alkali, and the process of soaking due to alkali will preferentially occur in SiO
2, Al
2o
3on mineral, make alkali soak v-ti magnetite concentrate and soak ferrotianium raw ore alkali consumption still less than alkali, better effects if.For example, after calcining, while 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 that soaks raw ore consumption than alkali has reduced more than 7 times.
Cyclone is pressed granularity and the gravity grading of mineral, and alkali soaks the titanium compound of rear generation than the fine size of iron mineral, and proportion is little, the difference of specific gravity of titanium, iron is larger, has realized effective separation of titanium, iron.Add that classification makes iron concentrate grade bring up to 60%～68% by 50%～55%, in iron ore concentrate, be less than 0.1%, SiO containing S amount simultaneously
2and Al
2o
3content is all less than 3%, TiO
2content is down to below 6% by 12.91%; Meanwhile, can also obtain TiO
2content is 35%～50% ilmenite concentrate.Adopt the method to realize titanium, iron are effectively separated, reduce and enter blast furnace TiO
2, the impurity such as S, Si, Al content, improve the capacity factor of a blast furnace, reduce the discharge capacity of blast furnace slag, reduced ironmaking cost, improve titanium resource comprehensive utilization ratio simultaneously.
Brief description of the drawings
Fig. 1 is process chart of the present invention.
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
Be 51.3%, TiO by TFe content
2content is 14.0%, SiO
2content is 3.66%, Al
2o
3content is 4.42%, the v-ti magnetite concentrate of S content 0.55%, and the ratio of 1:0.1 adds CaO by weight, calcines 30 minutes at the temperature of 1200 DEG C, forms calcination product A, and its chemical equation is:
2) alkali soaks
By step 1) in calcination product A to be placed in mass concentration be 20% NaOH aqueous slkali, at the temperature of 300 DEG C, alkali soaks reaction 3.0 hours, 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, form the ore pulp of mass concentration 20% and feed cyclone and carry out classification, classification goes out sand setting C and overflow D, sand setting C is the final iron ore concentrate (SiO of TFe content 60.8%
2content is 0.83%, Al
2o
3content is 1.55%, S content is 0.02%), overflow D simmer down to TiO
2content is 39.8% final ilmenite concentrate.
Embodiment 2:
1) calcining
Be 53.5%, TiO by TFe content
2content is 11.3%, SiO
2content is 3.56%, Al
2o
3content is 5.50%, the v-ti magnetite concentrate of S content 0.72%, and the ratio of 1:0.11 adds CaO by weight, calcines 45 minutes at the temperature of 1000 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali soaks
By step 1) in calcination product A to be placed in mass concentration be 10% NaOH aqueous slkali, at the temperature of 315 DEG C, alkali soaks reaction 3.0 hours, 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, form the ore pulp of mass concentration 21% and feed cyclone and carry out classification, classification goes out sand setting C and overflow D, sand setting C is the final iron ore concentrate (SiO of TFe content 63.5%
2content is 0.67%, Al
2o
3content is 1.44%, S content is 0.02%), overflow D simmer down to TiO
2content is 36.8% final ilmenite concentrate.
Embodiment 3:
1) calcining
Be 53.4%, TiO by TFe content
2content is 13.2%, SiO
2content is 3.45%, Al
2o
3content is 5.08%, the v-ti magnetite concentrate of S content 0.60%, and the ratio of 1:0.1 adds CaO by weight, calcines 50 minutes at the temperature of 900 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali soaks
By step 1) in calcination product A to be placed in mass concentration be 28% NaOH aqueous slkali, at the temperature of 305 DEG C, alkali soaks reaction 2.5 hours, 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, form the ore pulp of mass concentration 22% and feed cyclone and carry out classification, classification goes out sand setting C and overflow D, sand setting C is the final iron ore concentrate (SiO of TFe content 64.7%
2content is 0.54%, Al
2o
3content is 1.40%, S content is 0.02%), overflow D simmer down to TiO
2content is 35.9% final ilmenite concentrate.
Embodiment 4:
1) calcining
Be 54.8%, TiO by TFe content
2content is 10.9%, SiO
2content is 3.50%, Al
2o
3content is 5.20%, the v-ti magnetite concentrate of S content 0.66%, and the ratio of 1:0.12 adds CaO by weight, calcines 30 minutes at the temperature of 1300 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali soaks
By step 1) in calcination product A to be placed in mass concentration be 49% NaOH aqueous slkali, at the temperature of 370 DEG C, alkali soaks reaction 2.0 hours, 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, form the ore pulp of mass concentration 23% and feed cyclone and carry out classification, classification goes out sand setting C and overflow D, sand setting C is the final iron ore concentrate (SiO of TFe content 67.5%
2content is 0.61%, Al
2o
3content is 1.30%, S content is 0.01%), overflow D simmer down to TiO
2content is 46.1% final ilmenite concentrate.
Embodiment 5:
1) calcining
Be 53.8%, TiO by TFe content
2content is 12.9%, SiO
2content is 3.67%, Al
2o
3content is 5.01%, the v-ti magnetite concentrate of S content 0.75%, and the ratio of 1:0.15 adds CaO by weight, calcines 20 minutes at the temperature of 1400 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali soaks
By step 1) in calcination product A to be placed in mass concentration be 15% KOH aqueous slkali, at the temperature of 310 DEG C, alkali soaks reaction 2.0 hours, 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, form the ore pulp of mass concentration 24% and feed cyclone and carry out classification, classification goes out sand setting C and overflow D, sand setting C is the final iron ore concentrate (SiO of TFe content 66.4%
2content is 0.61%, Al
2o
3content is 1.30%, S content is 0.01%), overflow D simmer down to TiO
2content is 45.8% final ilmenite concentrate.
Embodiment 6:
1) calcining
Be 53.6%, TiO by TFe content
2content is 11.9%, SiO
2content is 3.82%, Al
2o
3content is 4.62%, the v-ti magnetite concentrate of S content 0.55%, and the ratio of 1:0.2 adds CaO by weight, calcines 60 minutes at the temperature of 800 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali soaks
By step 1) in calcination product A to be placed in mass concentration be 25% KOH aqueous slkali, at the temperature of 320 DEG C, alkali soaks reaction 4.0 hours, 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, form the ore pulp of mass concentration 25% and feed cyclone and carry out classification, classification goes out sand setting C and overflow D, sand setting C is the final iron ore concentrate (SiO of TFe content 67.2%
2content is 0.31%, Al
2o
3content is 1.38%, S content is 0.01%), overflow D simmer down to TiO
2content is 49.5% final ilmenite concentrate.
Embodiment 7:
1) calcining
Be 54.0%, TiO by TFe content
2content is 12.3%, SiO
2content is 3.80%, Al
2o
3content is 4.60%, the v-ti magnetite concentrate of S content 0.55%, and the ratio of 1:0.2 adds CaO by weight, calcines 25 minutes at the temperature of 1350 DEG C, forms calcination product A, and its chemical equation is with embodiment 1.
2) alkali soaks
By step 1) in calcination product A be placed in the aqueous slkali that NaOH mass concentration is 20%, KOH mass concentration is 6%, at the temperature of 330 DEG C, alkali soaks reaction 4.0 hours, 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, form the ore pulp of mass concentration 25% and feed cyclone and carry out classification, classification goes out sand setting C and overflow D, sand setting C is the final iron ore concentrate (SiO of TFe content 66.8%
2content is 0.25%, Al
2o
3content is 1.11%, S content is 0.01%), overflow D simmer down to TiO
2content is 48.9% final ilmenite concentrate.
Claims (2)
1. utilize the method that calcining, alkali soak, v-ti magnetite concentrate is selected in classification again, it is characterized in that comprising the steps:
1) calcining
Be 50%～55%, TiO by TFe content range
2content range is 10%～15%, SiO
2content is 3%～6%, Al
2o
3content is 3%～6%, the v-ti magnetite concentrate of S content >0.5% by weight the ratio of 1:0.1～0.2 add CaO, at the temperature of 800 DEG C～1400 DEG C, calcine 20～60 minutes, form calcination product A;
2) alkali soaks
By step 1) in calcination product A to be placed in mass concentration be 5%～52% aqueous slkali, at the temperature of 300 DEG C～370 DEG C, alkali soaks reaction 0.5～5 hour, reactant is filtered, 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 that forms mass concentration 20%～25% feeds cyclone and carries out classification, classification goes out sand setting C and overflow D, and described sand setting C is that TFe content range is 60%～68% final iron ore concentrate, described overflow D simmer down to TiO
2content range is 35%～50% ilmenite concentrate.
2. a kind of method that alkali soaks, v-ti magnetite concentrate is selected in classification again of utilizing according to claim 1, is characterized in that described aqueous slkali is any one in NaOH or the KOH aqueous solution, NaOH and KOH mixed aqueous solution.
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Cited By (1)
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|---|---|---|---|---|
| CN104984817A (en) * | 2015-06-12 | 2015-10-21 | 鞍钢集团矿业公司 | Method of separating vanadium-titanium magnetite concentrate by using calcining, oxidation and alkaline leaching, desliming and gravity separation |
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Address after: 114001 Anshan District, Liaoning, No. 219 Road, No. 39, Tiedong Patentee after: Anshan Iron and Steel Group Mining Co., Ltd. Address before: 114001 Anshan District, Liaoning, No. 219 Road, No. 39, Tiedong Patentee before: Anshan Iron & Steel Group Mining Co., Ltd. |