CN104131179A - Method of directly reducing vanadium-titanium ore hot-pressing blocks in rotary hearth furnace and melting in electric furnace - Google Patents
Method of directly reducing vanadium-titanium ore hot-pressing blocks in rotary hearth furnace and melting in electric furnace Download PDFInfo
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Abstract
The invention belongs to the technical field of comprehensive utilization of metallurgical resources, and in particular relates to a comprehensive utilization method of directly reducing vanadium-titanium ore hot-pressing blocks in a rotary hearth furnace and melting in an electric furnace. The method comprises the following steps: (1) blending vanadium-titanium ore mineral powder with bituminous coal powder, heating mixed powder and carrying out hot-press molding so as to obtain the vanadium-titanium ore hot-pressing blocks; (2) putting the vanadium-titanium ore hot-pressing blocks into the rotary hearth furnace by covering multiple layers of materials on the vanadium-titanium ore hot-pressing blocks and carrying out direct reduction via thick material layers; (3) melting products obtained by reducing the vanadium-titanium ore hot-pressing blocks in the rotary hearth furnace so as to obtain vanadium-containing molten iron and titanium slag; and (4) carrying out vanadium blowing and steelmaking on the vanadium-containing molten iron so as to obtain vanadium slag and a steel ingot, wherein the vanadium slag can serve as a raw material for preparing titanium dioxide. The method which is used for preparing the vanadium-titanium ore hot-pressing blocks has the advantages of low production cost, high production efficiency, low energy consumption, good quality of the vanadium titanium ore hot-pressing blocks and the like. Thus, the economy of the process of directly reducing vanadium-titanium ores in the rotary hearth furnace and melting in the electric furnace is obviously improved.
Description
Technical field
The invention belongs to Metallurgical resources comprehensive utilization technique field, be specifically related to the method for molten point of comprehensive utilization of a kind of schreyerite hot wafering rotary hearth furnace direct-reduction-electric furnace.
Background technology
Mineral containing vanadium, titanium two metallic elements are universally acknowledged grand strategy resources, the important substance guarantee of the national economic development and national security containing vanadium, titanium metal, it is widely used in the fields such as chemical metallurgy, aerospace, national defense and military, vanadium titano-magnetite is the most important carrier of vanadium and titanium resources, be distributed widely in the ground such as the Pan Xi, Chengde, Hanzhong, Xiangyang of China, its reserves are abundant, only just exceed 10,000,000,000 tons in Panzhihua Region.But, the grade requirement for existing processing and utilization industrial flow to desired raw material, these vanadium titano-magnetites all belong to low grade ore, and valuable mineral is of a great variety, compose and deposit the very fine and each other closely symbiosis of yardstick.Compared with common iron ore deposit, mineral are processed and are utilized difficulty large, and iron, vanadium, titanium resource comprehensive utilization ratio are always in lower level.Therefore, how to strengthen the high-efficiency comprehensive utilization to vanadium titano-magnetite, significant to the sound development of China's steel industry.
Present Domestic has multiple to the method for comprehensive utilization of v-ti magnetite ore resources, be mainly divided into blast furnace-converter flow process and rotary hearth furnace-electric furnace flow process, wherein present stage blast furnace-converter flow process occupy schreyerite smelt ascendancy.In the middle of the fast development at present of rotary hearth furnace-electric furnace flow process.
For schreyerite rotary hearth furnace-electrosmelting flow process, domestic research institution and production unit have proposed a lot of methods.Described in patent CN1264993C, agglomeration after v-ti magnetite breeze, reductive agent, additive and binding agent are mixed, then the ball piece of moulding is dry at 80～90 DEG C, after dry, being packed into rotary hearth furnace reduces and obtains metallized product, then metallized product is carried out to molten point of electric furnace and obtain molten iron and vanadium titanium slag, further can carry out vanadium extraction to vanadium titanium slag and carry titanium, finally realize the comprehensive utilization of vanadium titano-magnetite.
Described in patent CN101619371, after being cold-pressed into piece, v-ti magnetite breeze, coal dust and binding agent mixing enter rotary hearth furnace reduction, reduction is obtained to metallized product to be carried out molten point of electric furnace and obtains vanadium-bearing hot metal and titanium slag, vanadium-bearing hot metal blows vanadium and obtains vanadium slag the most at last, and titanium slag can be used as the raw material that extracts titanium.
Described in patent CN102277462A, after being mixed, schreyerite powder flux, binding agent and reductive agent be cold-pressed into piece, packing the agglomerate of moulding into rotary hearth furnace reduces and obtains titanium slag and pearl iron, the titanium slag of reduction gained is carried out to magnetic separation with pearl iron to be separated, carry out vanadium extraction processing to separating the titanium slag obtaining, the higher-grade titanium slag obtaining can be used as producing the high quality raw material of titanium white.
Described in patent CN103526051A, after schreyerite, sodium sulfate, reductive agent and binding agent are mixed, be pressed into pit coal pelletizing juxtaposition reduces in rotary hearth furnace, the metallized pellet that reduction is obtained carries out fragmentation, then the product after fragmentation is placed in to leach liquor and carries out leaching repeatedly, and extract is carried out to magnetic separation separation, finally obtain being rich in leach liquor and rich titanium material and the rich iron charge of vanadium.
Described in patent CN101157984B, by adding carbonaceous reducing agent to grind into pelletizing with profit after binding agent after schreyerite fragmentation, then prepared pelletizing is placed in to tunnel furnace and reduces, obtain degree of metalization and exceed 90% metallized pellet.
Described in patent CN101117660A, by after the fragmentation of vanadium ilmenite concentrate powder, profit mill, adding carbonaceous reducing agent to make pelletizing is placed in rotary hearth furnace and reduces, reduzate is carried out obtaining iron powder and mine tailing through magnetic separation and gravity treatment after fragmentation, after mine tailing is carried out multistep and leaches processing, finally obtain Vanadium Pentoxide in FLAKES product.
Described in patent CN100564558C, by water logging vanadium extraction after vanadium titano-magnetite sodium roasting, the vanadium product of leach liquor system, and the residue obtaining enters rotary hearth furnace reduction after joining carbon, and reduzate is carried out to molten point of electric furnace, obtain molten iron and titanium slag, molten iron can be used for steel-making, and titanium slag can be produced titanium white by sulfate process titanium dioxide technique.
Described in patent CN102690921A, by v-ti magnetite concentrate powder, go back and after raw coal and binding agent mix, be cold-pressed into pelletizing and be placed in rotary hearth furnace and reduce, obtained reduzate is sent into the molten point of stove of regenerative gas that does fuel by coal gas to be melted point, obtain vanadium-bearing hot metal and titanium slag, wherein vanadium-bearing hot metal can blow and obtain vanadium slag and half steel, and titanium slag can be used as producing the raw material of titanium white.
Described in patent CN102690944A, first sodium salt or calcium salt will be added in vanadium titano-magnetite, then after rotary hearth furnace roasting, leach processing, the leach liquor obtaining can be used for producing vanadium product, and the residue obtaining is by making reductibility pelletizing with addition of carbon containing reducer, then reductibility pelletizing is placed in to gas furnace or electric furnace and melts and point obtain molten iron and titanium slag, titanium slag can be used as the raw material of producing titanium white.
But mainly there is following problem in these above methods: (1) is prepared in vanadium titanium titanium pelletizing process and added a large amount of binding agents, because binding agent is expensive, make overall production cost high; (2) by adding the preparation-obtained vanadium-titanium ore pellets of binding agent, under hot conditions, its intensity is very low, therefore in the process that enters rotary hearth furnace reduction, generally can only adopt individual layer cloth and can not use multilayer cloth, this just greatly reduces the production efficiency of rotary hearth furnace reduction process; (3) additive and binding agent etc. will be brought a large amount of detrimental impurity elements into, and such as S, P, Na etc., this endangers greatly to the mass formation of molten iron; (4) owing to having added binding agent, reduction process energy consumption will raise in a large number, simultaneously increase the quantity of slag in the molten point process of electric furnace, and making electric furnace melt energy consumption and cost in division technique increases greatly; (5) in the schreyerite treating processes after a large amount of use acid leaching solutions are to sodium roasting, will produce a large amount of contaminating fluid, this class contaminating fluid is difficult, and carrying capacity of environment is large, the furnace lining of sodium salt corrosion simultaneously, and it is unfavorable that production unit is safeguarded.
For the problems referred to above, be necessary the molten separating method of schreyerite rotary hearth furnace direct-reduction-electric furnace to carry out technical renovation or improvement.Hot wafering is a kind of novel high-quality iron-smelting raw material that utilizes the thermoplasticity of coal and prepare, and has the advantages such as hot strength is high, reduction rate is fast, adaptability to raw material is strong.Adopt in addition heat pressing process without adding any binding agent, effectively eliminated owing to adding binding agent and caused the drawback that the quantity of slag is large, energy consumption is large, and greatly reduced production cost.Therefore, the smelting technology that exploitation schreyerite hot wafering rotary hearth furnace direct-reduction-electric furnace is molten point, can reduce the production cost in agglomeration process on the one hand, can utilize on the other hand hot strength and the reducing property of hot wafering excellence, be multilayer cloth by the innovation of rotary hearth furnace individual layer cloth, again in conjunction with rotary hearth furnace direct-reduction and molten point of advantage having respectively of electric furnace, make iron, vanadium, titanium is realized high efficiency separation, this is for developing the abundant schreyerite resource of China's reserves, improving and improve the molten point smelting technology of existing schreyerite rotary hearth furnace direct-reduction-electric furnace has great importance.
Summary of the invention
For above problem, the invention provides the method for molten point of comprehensive utilization of a kind of schreyerite hot wafering rotary hearth furnace direct-reduction-electric furnace.Specifically comprise the following steps:
1. schreyerite, two kinds of materials of bituminous coal are carried out to crushing and screening, wherein: schreyerite breeze is not less than 40% by its all iron content of mass percent; Select pulverized bituminous coal, the fixed carbon content in coal dust by mass percent be not less than 50%, ash content not higher than 15%, volatile matter is no more than 35%, plastometer indice is not less than 10; The granularity of schreyerite powder and coal dust is all not more than 0.15mm.The ratio that is 60%～80%, 20%～40% in mass percent by the schreyerite powder after crushing and screening, two kinds of materials of coal dust is calculated batching, by the fully mixed uniform compound of composition that makes of mixer for the raw material preparing;
2. pair compound preparing carries out heat temperature raising, in the time that temperature reaches 250～500 DEG C, be pressed into the schreyerite hot wafering of elliposoidal with hot-press arrangement, hot pressing pressure is 35～45Mpa, schreyerite hot wafering is of a size of the particle of (20～40) × (15～30) × (10～20) mm, its carbon-to-oxygen ratio is 0.8～1.4, and the schreyerite hot wafering ultimate compression strength of making is not less than 1000N/, and dropping strength is not less than 5 times/; While using hot pressing pair roller ball press to suppress the compound preparing, the linear pressure of its equipment is not less than 3.0t/cm.
3. schreyerite hot wafering is arranged on rotary hearth furnace siege by distributor, carry out multilayer cloth, rotary hearth furnace heats by Sweet natural gas or coal gas, and the reduction temperature in stove is between 1300～1450 DEG C, recovery time is 15～45min, obtains the metallized pellet that degree of metalization is greater than 90%.
4. the metallization reduzate that vanadium titano-magnetite hot wafering obtains through rotary hearth furnace direct-reduction enters electric furnace and melts point, obtains pig iron containing vanadium and titanium slag.The molten point atmosphere of general control is neutrality or reducing atmosphere, and a molten point temperature is not less than 1600 DEG C, and the vanadium-bearing hot metal temperature obtaining is not less than 1400 DEG C, and titanium slag temperature is not less than 1450 DEG C, and the molten subset of electric furnace can be electric arc furnace or induction furnace.
5. by blowing vanadium steel-making through molten point of vanadium-bearing hot metal obtaining of electric furnace, obtain vanadium slag and steel ingot or molten steel, wherein enter converter vanadium-bearing hot metal temperature and be not less than 1300 DEG C.
6. through molten point of its TiO of titanium slag obtaining of electric furnace
2grade is 45%～55%, can be used as sulfuric acid process and produces the raw material of titanium white and be used.
The invention has the advantages that:
(1) vanadium titano-magnetite hot wafering relies on the thermoplasticity of coal, adopts bituminous coal as binding agent, does not use any organic binder bond, and adaptability to raw material is strong, and production cost is low, and hot pressing temperature is 250～500 DEG C of left and right, and energy consumption is relatively low;
(2) compared with cold fixed vanadium titanium carbonaceous pelletizing, schreyerite hot wafering does not use additive, and production cost is low, and hot strength is high, and reduction rate is fast, has the smelting direct motion that utilizes rotary hearth furnace, reduces smelting cost;
(3) the good reducing property of high temperature bond schreyerite hot wafering of rotary hearth furnace, completes whole reduction process fast, and the recovery time is 15～45min, and other techniques of comparing are smelted flow process and greatly shortened, and production efficiency is improved;
(4) rotary hearth furnace direct-reduction has been realized multilayer cloth, greatly improve production efficiency, in this external smelting process, rotary furnace bottom is relative static state with material, in addition the good hot strength of schreyerite hot wafering, reduces schreyerite hot wafering efflorescence percentage of damage in reduction process greatly;
(5) metallized pellet obtains vanadium-bearing hot metal and titanium slag through molten point of electric furnace, further vanadium-bearing hot metal is blown and obtained vanadium slag and molten steel, good separation and the enrichment of iron, vanadium, titanium are successfully realized, in the present invention, the rate of recovery of iron reaches more than 97%, the rate of recovery of vanadium and titanium reaches respectively more than 85% and 95%, has greatly improved the comprehensive utilization that has valency constituent element in vanadium titano-magnetite.Therefore, it is high that the present invention has production efficiency, and environmental pollution is little, Social benefit and economic benefit outstanding feature, this will contribute to improve the smelting level of China's vanadium titano-magnetite, has important realistic meaning for the smelting cost that reduces vanadium titano-magnetite, has wide market prospects for commercial application.
Body embodiment
Further describe the present invention below in conjunction with specific embodiment, advantage and disadvantage of the present invention can manifest more clearly in description, but these embodiment are only exemplary, scope of the present invention are not formed to any restriction.
Embodiment 1
The schreyerite breeze using taking certain company is raw material, by its full iron TFe content of mass percent be 53.15%, V
2o
5content be 0.712%, TiO
2content is 11.06%, and its chemical composition is by mass percent in table 1, and the granularity of breeze is all not more than 0.15mm.
The main chemical compositions of table 1 schreyerite
The pulverized bituminous coal using using certain company is as carbon raw material, its fixed carbon content is 50.94%, ash content and volatile content are respectively 14.00% and 34.70%, this gum layer of soft coal index is 11, chemical composition sees the following form 2 and table 3 by mass percent, and the granularity of pulverized bituminous coal is all not more than 0.15mm.
The chemical composition (/ %) of certain bituminous coal of table 2
The chemical composition of table 3 bituminous coal ash content
By above-mentioned two kinds of raw materials in the mass percent of schreyerite breeze and pulverized bituminous coal 77.77% and 22.23% the ratio of being respectively prepare burden, mix, heating and hot pressing.
In hot pressing, hot pressing temperature is 250 DEG C, and hot pressing pressure is 40MPa, and the composition of the schreyerite hot wafering that compacting obtains is by mass percent in table 4, and vanadium titanium hot wafering ultimate compression strength is 1038N/, and dropping strength is 5.4 times/.
The main chemical compositions of table 4 vanadium titano-magnetite hot wafering
The schreyerite hot wafering of compression moulding is entered to rotary hearth furnace burner hearth by material distributing machine, carry out double-layer cloth, the reduction temperature of controlling rotary hearth furnace is 1350 DEG C, and the time of whole reduction process is 40 min, and the degree of metalization that obtains metallized pellet is 91.4%.
The metallized pellet that rotary hearth furnace direct-reduction is obtained is sent into electric arc furnace and is joined molten point of carbon, and controlling molten point atmosphere is neutral atmosphere, and molten point temperature is 1650 DEG C, and in the molten point later stage, controlling vanadium-bearing hot metal temperature is 1410 DEG C, and titanium slag temperature is 1450 DEG C.
The titanium slag obtaining can be used as the raw material of sulfuric acid process extraction titanium white, and vanadium-bearing hot metal is further blown to vanadium steel-making, obtains vanadium slag and steel ingot.In whole flow process, the rate of recovery of iron is 97.2%, and the rate of recovery of titanium is 95.2%, and the rate of recovery of vanadium is 85.2%.
Embodiment 2
Still taking breeze listed in embodiment 1 and coal dust as raw material.
By above-mentioned two kinds of raw materials in the mass percent of schreyerite breeze and pulverized bituminous coal 74.46% and 25.54% the ratio of being respectively prepare burden, mix, heating and hot pressing.
In heat pressing process, hot pressing temperature is 300 DEG C, and hot pressing pressure is 40MPa, and the composition of the schreyerite hot wafering that compacting obtains is by mass percent in table 5, and vanadium titanium hot wafering ultimate compression strength is 1224N, and dropping strength is 6.2 times/.
The main chemical compositions of table 5 vanadium titano-magnetite hot wafering
The schreyerite hot wafering of compression moulding is entered to rotary hearth furnace burner hearth by material distributing machine, carry out 3 layers of cloth, the reduction temperature control of rotary hearth furnace is 1400 DEG C, and the time of whole reduction process is 35 min, and the degree of metalization of the metallized pellet obtaining is 93.2%.
The metallized pellet that rotary hearth furnace direct-reduction is obtained is sent into electric arc furnace and is melted point, and controlling molten point atmosphere is reducing atmosphere, and the highest to melt point temperature be 1650 DEG C, and the vanadium-bearing hot metal temperature obtaining is 1400 DEG C, and titanium slag temperature is 1500 DEG C.
The titanium slag obtaining can be used as the raw material of sulfuric acid process extraction titanium white.Vanadium-bearing hot metal is further blown to vanadium steel-making, obtain vanadium slag and steel ingot.In whole flow process, the rate of recovery of iron reaches for 97.6.%, and the rate of recovery of titanium reaches 96.2%, and the rate of recovery of vanadium reaches 86.0%.
Embodiment 3
Still taking breeze listed in embodiment 1 and coal dust as raw material.
By above-mentioned two kinds of raw materials in the mass percent of schreyerite breeze and pulverized bituminous coal 71.42% and 28.58% the ratio of being respectively prepare burden, mix, heating and hot pressing.
In heat pressing process, hot pressing temperature and hot pressing pressure are respectively 350 DEG C and 45MPa, and the schreyerite hot wafering composition that final compacting obtains is in table 6, and vanadium titanium hot wafering ultimate compression strength is 1482N, and dropping strength is 8 times/.
The main chemical compositions of table 6 vanadium titano-magnetite hot wafering
The schreyerite hot wafering of compression moulding is entered to rotary furnace bottom by material distributing machine, carry out multilayer cloth, bed thickness is 3-6 layer, the reduction temperature of controlling rotary hearth furnace is not less than 1450 DEG C, the time of whole reduction process was controlled in 30 minutes, and the degree of metalization of the metallized pellet obtaining is 94.2%.The metallized pellet that rotary hearth furnace direct-reduction is obtained is sent into electric arc furnace and is melted point, controlling molten point atmosphere is neutrality or reducing atmosphere, molten point temperature is 1650 DEG C, the vanadium-bearing hot metal temperature obtaining is 1400～1450 DEG C, titanium slag temperature is not less than 1480 DEG C, and the titanium slag obtaining can be used as the raw material of sulfuric acid process extraction titanium white.Vanadium-bearing hot metal is further blown to vanadium steel-making, obtain vanadium slag and steel ingot.In whole flow process, the rate of recovery of iron is 98.2%, and the rate of recovery of titanium is 96.4%, and the rate of recovery of vanadium is 86.8%.
Claims (5)
1. the molten separating method of schreyerite hot wafering rotary hearth furnace direct-reduction-electric furnace, is characterized in that whole technical process comprises:
(1) schreyerite, two kinds of materials of bituminous coal are carried out to crushing and screening, wherein: schreyerite breeze is not less than 40% by its all iron content of mass percent; Select pulverized bituminous coal, the fixed carbon content in coal dust by mass percent be not less than 50%, ash content not higher than 15%, volatile matter is no more than 35%, plastometer indice is not less than 10; The granularity of schreyerite powder and coal dust is all not more than 0.15mm, the ratio that is 60%～80%, 20%～40% in mass percent by the schreyerite powder after crushing and screening, two kinds of materials of coal dust is calculated batching, by the fully mixed uniform compound of composition that makes of mixer for the raw material preparing;
(2) compound preparing is carried out to heat temperature raising, in the time that temperature reaches 250～500 DEG C, be pressed into the schreyerite hot wafering of elliposoidal with hot-press arrangement, hot pressing pressure is 35～45Mpa, schreyerite hot wafering is of a size of the particle of (20～40) × (15～30) × (10～20) mm, its carbon-to-oxygen ratio is 0.8～1.4, and the schreyerite hot wafering ultimate compression strength of making is not less than 1000N/, and dropping strength is not less than 5 times/; While using hot pressing pair roller ball press to suppress the compound preparing, the linear pressure of its equipment is not less than 3.0t/cm;
(3) schreyerite hot wafering is arranged on rotary hearth furnace siege by distributor, rotary hearth furnace heats by Sweet natural gas or coal gas, reduction temperature in stove is between 1300～1450 DEG C, and the recovery time is 15～45min, obtains the metallized pellet that degree of metalization is greater than 90%;
(4) the metallization reduzate that vanadium titano-magnetite hot wafering obtains through rotary hearth furnace direct-reduction enters the molten subset of electric furnace and melts point, obtains pig iron containing vanadium and titanium slag.
2. the molten separating method of schreyerite hot wafering rotary hearth furnace direct-reduction-electric furnace according to claim 1, is characterized in that: when schreyerite hot wafering enters rotary hearth furnace direct-reduction, adopt distributor multilayer cloth to carry out high gentle and kind bed of material direct-reduction.
3. the molten separating method of schreyerite hot wafering rotary hearth furnace-electric furnace according to claim 1, it is characterized in that the high metallized pellet that rotary hearth furnace direct-reduction is obtained is sent into melts timesharing in electric furnace, its molten point atmosphere of general control is neutrality or reducing atmosphere, a molten point temperature is not less than 1600 DEG C, the vanadium-bearing hot metal temperature obtaining is not less than 1400 DEG C, titanium slag temperature is not less than 1450 DEG C, and the molten subset of electric furnace can be electric arc furnace or induction furnace.
4. the molten separating method of vanadium titano-magnetite hot wafering rotary hearth furnace direct-reduction-electric furnace according to claim 1, is characterized in that: molten point of vanadium-bearing hot metal obtaining of electric furnace further carried out to oxygen blast smelting and obtain vanadium slag and steel ingot or molten steel.
5. the molten separating method of vanadium titano-magnetite hot wafering rotary hearth furnace direct-reduction-electric furnace according to claim 1, is characterized in that: through molten point of its TiO of titanium slag obtaining of electric furnace
2grade is 45%～55%, can be used as sulfuric acid process and produces the raw material of titanium white and use.
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| CN104498711A (en) * | 2015-01-21 | 2015-04-08 | 东北大学 | Method for using stainless steel dust to produce chrome, nickel and iron alloy |
| CN105039626A (en) * | 2015-09-14 | 2015-11-11 | 北京科技大学 | Vanadium slag preparation method |
| CN105087961A (en) * | 2015-08-10 | 2015-11-25 | 中冶南方工程技术有限公司 | Method for efficiently recycling vanadium, iron and titanium in vanadium-titanium metallized pellet through electric arc furnace |
| CN105734266A (en) * | 2016-02-25 | 2016-07-06 | 钢研晟华工程技术有限公司 | Comprehensive recovery process for vanadium titanium iron ore concentrate directly processed by sodium treatment |
| CN106636515A (en) * | 2016-10-31 | 2017-05-10 | 攀枝花学院 | Method for reinforcing vanadium-titanium-iron concentrate direct reduction-melting separation process by using magnesium oxide |
| CN106702064A (en) * | 2016-12-13 | 2017-05-24 | 昆明理工大学 | Method for preparing high-grade titanium slag by taking vanadium titano-magnetite as raw material |
| CN108950224A (en) * | 2018-06-08 | 2018-12-07 | 河北工程大学 | A kind of method of valuable constituent element comprehensive reutilization in vanadium slag |
| CN110592314A (en) * | 2019-10-16 | 2019-12-20 | 中冶赛迪工程技术股份有限公司 | Method for producing vanadium-rich slag by using electric furnace |
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| CN110592314A (en) * | 2019-10-16 | 2019-12-20 | 中冶赛迪工程技术股份有限公司 | Method for producing vanadium-rich slag by using electric furnace |
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