CN105969981A - Process for comprehensively utilizing vanadium-titanium magnetite - Google Patents
Process for comprehensively utilizing vanadium-titanium magnetite Download PDFInfo
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- CN105969981A CN105969981A CN201610287438.1A CN201610287438A CN105969981A CN 105969981 A CN105969981 A CN 105969981A CN 201610287438 A CN201610287438 A CN 201610287438A CN 105969981 A CN105969981 A CN 105969981A
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- vanadium
- magnetite
- slag
- iron
- reduction
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/006—Starting from ores containing non ferrous metallic oxides
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/02—Making spongy iron or liquid steel, by direct processes in shaft furnaces
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
Abstract
The invention relates to a process for treating and comprehensively utilizing a vanadium-titanium magnetite. The process is characterized by comprising the following steps: (1) treating a raw vanadium-titanium magnetite by crushing, tailings discarding, fine grinding, low-intensity magnetic separating, high-intensity magnetic separating, and separating by a shaking table, so as to obtain a titanium concentrate and a high-vanadium-ferrum concentrate; (2) adding an adhesive to the high-vanadium-ferrum concentrate; uniformly mixing and pelletizing; drying; uniformly mixing with pulverized coal or coke powder; distributing; performing controlled reduction that V is not reduced through a coal based shaft furnace so as to obtain sponge iron, wherein the amount of used reducing agents such as the pulverized coal is 30 to 70% of the weight of high-vanadium-ferrum concentrate powder, and the reduction is performed for 10 to 18 hours at the temperature of 850 to 1060 DEG C; (3) heating the obtained sponge iron for 0.5 to 1.0 hour at the temperature less than 1050 DEG C through an intermediate frequency/ main frequency furnace under a weak reduction atmosphere; then heating until the temperature is more than 1500 DEG C; performing melt separation to enable vanadium to enter slag, thus obtaining high-grade vanadium slag and high-purity molten iron. With the adoption of the process, a plurality of valuable elements in the vanadium-titanium magnetite can be effectively separated and utilized with high additional value.
Description
Technical field
The technique that the present invention relates to the comprehensive utilization of a kind of vanadium titano-magnetite.
Background technology
At present containing vanadium titano-magnetite non-blast furnace processing method approximately as:
Molten point of coal gas fluid bed reduction+electric furnace, such as the patent of Application No. CN201110027410.1
A kind of method disclosing coal reducing gases fluid bed reduction v-ti magnetite breeze, coal reducing gases system
The coal gas of high temperature produced is mixed into reducing gas, sequentially with the gas carrying out autoreduction weary gas cleaning system
Enter three grades, two grades and one-level reduction fluid bed；V-ti magnetite breeze after preheating sequentially enter one-level,
Two grades and three grades of reduction fluid beds, reverse and on reducing gas effect under, realize fluidization concurrent
Raw reduction reaction；The DRI compound stalk forming that obtains after removing titanium slag, extracting vanadium slag, produces
Qualified molten steel.
Molten point of gas-based shaft kiln reduction+electric furnace: the patent such as Application No. CN201310216599.8 is open
Disclosing a kind of gas-based shaft kiln directly reduced electric furnace melts the technique of point vanadium titano-magnetite, including following
Step: a. manufactured goods pelletizing；B. finished product vanadium-titanium ore pellets is loaded direct-reduction shaft furnace as raw material
In, and in shaft furnace, it being passed through reducing gases, reducting pellet ore deposit obtains hot direct reduced iron；C. by hot directly
Connect reduced iron heat to deliver to a molten point of electric furnace and carry out molten point of reduction, isolate titanium slag and obtain vanadium-bearing hot metal；D. will
Vanadium-bearing hot metal blows in being transported to converter, isolates vanadium slag and half steel.And publication number
Patent for CN201210377607.2 discloses molten point of comprehensive utilization vanadium of one reduction shaft furnace-electric furnace
The method of titanomagnetite, vanadium titano-magnetite concentrate and binding agent are mixed and made into acid pellet, in temperature are
900～1200 DEG C, pressure be 0.2～0.3MPa gas-based shaft kiln in reduction 4～6 hours, reducing gases
H2+CO >=90%, H2 Yu CO mol ratio is 1～3, goes back original product feeding electric furnace and carries out fusing and slag ferrum
Separating, obtain molten iron and slag, the titanium Han vanadium in slag, for vanadium extraction with carry titanium.Titanium can be made to obtain effectively
Extraction and application；Without coke, do not consume coking coal, alleviate the situation being becoming tight coking coal resource day.
Tunnel kiln reduction+mill choosing separates: as Application No. CN201110367255.8 patent discloses one
Plant ferrum and the method for vanadium titanium of separating from vanadium titano-magnetite, comprise the steps: a, dispensing: by weight
Proportioning by vanadium titano-magnetite 100 parts, and additive 15～20 parts and carbonaceous reducing agent 15～25 parts of mixings,
Wherein, described additive is at least one in sodium chloride, sodium sulfate, sodium carbonate；B, feed, also
Former: in a step, the mixture after mixing feeds, then in tunnel cave heating-up temperature to 920～
980 DEG C and be incubated 5～60h, obtain reducing ingot；C, separation: reduction ingot is broken, magnetic separation separates, and is gone back
Former iron powder and rich vanadium titanium material.
Rotary hearth furnace reduction+gas furnace melting: the patent such as Application No. CN201210208871.3 is open
The method that a kind of rotary hearth furnace reduction-combustion gas smelting furnace melts point comprehensive utilization of V-Ti magnetite, first by vanadium
It is pressed into pelletizing after titanomagnetite, reduction coal and binding agent mixing, is heated in dried loading rotary hearth furnace
1150～1350 DEG C, reduce 30～40 minutes；The high-temperature metal pellet obtained is sent directly into uses coal gas
The molten point stove of regenerative gas making fuel carries out fusing separation, controls the molten point furnace temperature of combustion gas and exists
1500-1620 DEG C, obtain vanadium-bearing hot metal and titanium slag；Titanium slag is for producing the raw material of titanium dioxide, or passes through floating
Technique is selected to produce rich-titanium material；Vanadium-bearing hot metal enters oxygen blast in converter and obtains vanadium slag and half steel, after removing vanadium slag
Half steel continues to smelt into molten steel.
The method summing up reduction vanadium titano-magnetite at present, is broadly divided into gas base method and coal base method, gas base method
Need to use expensive natural gas resource, be not suitable for China's national situation；And substitute natural gas with coal gas and make
For reducing gases, although there is substantial amounts of coal resource in China, but coal gas is used as reducing gases and there is many skills
An art difficult problem, cannot realize industrialization large-scale production in a short time, and production cost is high, only coal gas one
Item cost is accomplished by 950 yuan/tDRI.Coal base fado uses rotary hearth furnace or tunnel cave, and rotary hearth furnace is due to material
Layer relatively thin, production capacity is restricted, especially, within Carbon-bearing briquette be raw material, reducing agent ash enter
Product, causes resultant metal rate low, high (＞ 0.10%) containing S.And tunnel cave tunnel furnace method because of
The thermal efficiency is low, energy consumption high (consumption coal about 1t/t, wherein reduction coal 450～550kg/t, heating coal
400～550kg/t), production cycle length (48～76 hours)；Seriously polluted (reduction coal ash, useless
The solid waste such as reductive jar are many, and dust is many), the problems such as single machine production ability is little can not become modern
The main flow direction of post processing vanadium titano-magnetite.
The metallized pellet obtained by reduction generally has two kinds of processing modes, and one is molten point of electric furnace,
One is that mill choosing separates.Molten point is divided into again two kinds, and one is vanadium and titanium simultaneously enters slag；Another kind of
Being that titanium enters slag, major part vanadium enters molten iron, then carries out vanadium extraction from hot metal production vanadium slag.Molten timesharing needs
Add flux and slag former, CaO, SiO2Simultaneously entering slag with vanadium titanium, in slag, content of vanadium is relative
Reduce, currently without economically viable technology path, be in the experimental study stage.And vanadium extraction from hot metal is raw
Cause heating element in the loss of ferrum, half steel to reduce when producing vanadium slag and temperature reduces, bring not to steel-making
Profit impact, CaO, SiO in vanadium slag simultaneously2Content is high, it is impossible to produce high grade vanadium slag, to next step
The production of vanadic anhydride brings difficulty.
Summary of the invention
The purpose of the present invention, for the deficiencies in the prior art, proposes one and processes vanadium titano-magnetite comprehensive utilization
Technique, solve vanadium titano-magnetite economy, high added value, extensive industrialization utilize problem.
First the present invention carries out sorting and obtains high vanadium ferroalloy fine powder vanadium titano-magnetite, then uses coal base shaft furnace to height
Vanadium iron being controlled property of fine powder (making V not be reduced) reduction obtains sponge iron, and the sponge iron obtained enters
Row electric furnace is molten gets high-purity molten iron and high grade vanadium slag, it is achieved the multiple valuable element of vanadium titano-magnetite
Efficiently separate and high value added utilization.
The present invention solves the technical scheme of the problems referred to above employing:
A kind of technique processing vanadium titano-magnetite comprehensive utilization, it is characterised in that comprise the following steps:
(1) v-ti magnetite green ore divides through broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, shaking table
Ilmenite concentrate and high vanadium ferroalloy concentrate is obtained after choosing；
(2) high vanadium ferroalloy fine powder allocates 1 3% binding agent mixing pelletizing, dried, with coal dust or Jiao into
Powder mixes, and through cloth, the controlling reduction carrying out making V not be reduced in coal base shaft furnace obtains sponge
Ferrum, coal dust or coke powder consumption account for the 30%～70% of high vanadium ferroalloy fine powder weight, reduction temperature 850 DEG C
～1060 DEG C, recovery time 10-18h, obtain sponge iron.
(3) sponge iron obtained carries out heating in weak reducing atmosphere in intermediate frequency/main frequency furnace, in
1050 DEG C of heating 0.5-1.0h, are warming up to more than 1500 DEG C molten point, and vanadium enters in slag, obtains Gao Pin
Level vanadium slag and high-purity molten iron, Fe reaches more than 99%, the V response rate more than 99%).
Present invention additionally comprises: vanadium slag is used for vanadium extraction, high-purity molten iron be further used for producing high-purity iron block,
Atomized iron powder or steel-making.
Described binding agent is mixed by 0.5-0.8:0.5-0.2 by starch and cellulose.
The ilmenite concentrate sub-elected is for producing titanium white further.
The principle of the invention: 1) vanadium titano-magnetite is sorted, obtain high vanadium ferroalloy fine ore；2) exist
The interior coal dust of coal base shaft furnace or coke powder etc. reduce as being controlled property of reducing agent, at reduction temperature
The sponge iron degree of metalization obtained that reduces at 850～1060 DEG C is high, reaches more than 90%, vanadium after molten point
The response rate high, reach more than 99%；Can accurately control reduction temperature exist simultaneously as coal base is perpendicular
Within 850～1060 DEG C, can effective reduced iron, suppress simultaneously Si, Mn, Ca, Mg, Al, V,
The reduction of Cr, B, has been effectively ensured degree of purity and the recovery rate of vanadium of molten iron after molten point.3) control is used
Property processed heating (weak reducing atmosphere heats, and prevents sponge iron oxidation when heating) and molten point of intensification,
After molten point, non-reduzate enters slag, forms vanadium slag, and ferrum enters molten iron, and the vanadium slag grade obtained is high,
The molten steel quality formed is pure, and Fe reaches more than 99%, the V response rate more than 99%, it is achieved that having of ferrum and vanadium
Effect separates and high value added utilization.
Beneficial effects of the present invention: solve the following technical barrier in existing technique: 1) prior art
Forming the high molten iron of Si, Mn, V after molten point, vanadium is difficult to the technical barrier of high efficiency separation, and this method is real
Show ferrum, the high efficiency separation of vanadium and high value to utilize；2) current existing vanadium titano-magnetite is solved non-
Blast furnace process electric furnace melts point difficult problem being difficult to scale, industrialization, low-cost production, and this method is raw
Producing low cost, energy consumption is low, can scale, industrialized production；3) cast out existing metallized pellet to melt
Point formed vanadium-bearing hot metal, then molten iron is carried out vanadium extraction obtain vanadium slag complicated technology.Molten point one of electric furnace
Step produces high grade vanadium slag and high-purity molten iron, improves the economic worth that vanadium titano-magnetite utilizes.With
Time this method have the advantages that 1) use coal base shaft furnace process vanadium titano-magnetite, make full use of
Domestic abundant coal resources, the thermal efficiency is high, low production cost, technology maturation, easily realizes big rule
Mould, industrialized production；Compared with rotary hearth furnace, rotary hearth furnace is relatively thin due to the bed of material, and production capacity is restricted,
Within especially, Carbon-bearing briquette is raw material, and reducing agent ash enters product, causes resultant metal rate low
(less than 85%), the height containing S (＞ 0.10%)；Compared with tunnel cave, the tunnel furnace method thermal efficiency is low,
Energy consumption high (consumption coal about 1t/t, wherein reduction coal 450～550kg/t, heating coal 400～550kg/t),
Production cycle length (48～76 hours)；Seriously polluted (the solid waste such as reduction coal ash, useless reductive jar
Thing is many, and dust is many), single machine production ability is little, and floor space is big.2) this method is not to v-ti magnetite
Ore deposit is joined carbon and is processed in carrying out so that the sponge iron degree of metalization that reduction obtains is high, and S content is low, molten point
The hot metal purifying degree obtained is high, quality better.3) the most molten point of vanadium slag that (being not added with slag former) obtains
CaO、SiO2Content is low, and grade is high, good in economic efficiency, low production cost.4) this method reduction
Process need not use expensive additive, effectively reduces production cost, is of value to raising stove simultaneously
Life-span.5) this method produces good product quality, and vanadium slag grade is high, good in economic efficiency, hot metal purifying degree
High (Fe reaches more than 99%, the V response rate more than 99%), can be used for the exploitation of high value added product.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Coal base shaft furnace of the present invention uses Patent No. ZL200620095509. × structure, technique
Flow process is as shown in Figure 1.
Embodiment one: the method for high value added utilization vanadium titano-magnetite, the steps include:
(1) v-ti magnetite green ore divides through broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, shaking table
High vanadium ferroalloy concentrate is obtained after choosing；
(2) high vanadium ferroalloy fine powder allocates 2.0% binding agent (starch and the cellulose accounting for high vanadium ferroalloy fine powder weight into
Mix in 0.7:0.3 ratio) mix pelletizing, air-dry, allocate into outward and account for the 40% of high vanadium ferroalloy fine powder weight
Mixing material is erected furnace reduction through cloth at coal base and obtains sponge iron, reduction temperature by coal blending (3)
880 DEG C, recovery time 18h, reduzate degree of metalization 90%；
(4) sponge iron obtained heats 0.5h in 1000 DEG C in the main frequency furnace of weak reducing atmosphere
After be warming up to more than 1500 DEG C molten point, vanadium enters in slag and obtains high grade vanadium slag and high-purity molten iron, wherein
Vanadium recovery 99%, high-purity molten iron iron content 99%；
(5) vanadium slag is used for vanadium extraction, and high-purity molten iron is refined for producing atomized iron powder.
Embodiment two: the method for high value added utilization vanadium titano-magnetite, the steps include:
(1) v-ti magnetite green ore divides through broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, shaking table
High vanadium ferroalloy concentrate is obtained after choosing；
(2) high vanadium ferroalloy fine powder allocates 1.5% binding agent (starch and the cellulose accounting for high vanadium ferroalloy fine powder weight into
Mix in 0.5:0.5 ratio) mix pelletizing, air-dry, allocate into outward and account for the 30% of high vanadium ferroalloy fine powder weight
Coal blending；
(3) mixing material is erected furnace reduction through cloth at coal base and obtain sponge iron, reduction temperature 1000 DEG C,
Recovery time 15h, reduzate degree of metalization 91.3%；
(4) sponge iron obtained heats 40 points in 1000 DEG C in the middle frequency furnace of weak reducing atmosphere
Being warming up to more than 1500 DEG C molten point after clock, vanadium enters in slag and obtains high grade vanadium slag and high-purity molten iron, its
Middle vanadium recovery 99.5%, high-purity molten iron iron content 99.3%.
(5) vanadium slag is used for vanadium extraction, and high-purity molten iron is refined for producing high-purity iron block.
Embodiment three: the method for high value added utilization vanadium titano-magnetite, the steps include:
(1) v-ti magnetite green ore divides through broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, shaking table
High vanadium ferroalloy concentrate is obtained after choosing；
(2) high vanadium ferroalloy fine powder allocates 3.0% binding agent (starch and the cellulose accounting for high vanadium ferroalloy fine powder weight into
Mix in 0.8:0.2 ratio) mix pelletizing, air-dry, allocate into outward and account for the 55% of high vanadium ferroalloy fine powder weight
Coal blending；
(3) mixing material is erected furnace reduction through cloth at coal base and obtain sponge iron, reduction temperature 1060 DEG C,
Recovery time 13h, reduzate degree of metalization 92%；
(4) middle frequency furnace of the sponge iron weak reducing atmosphere obtained heats 30 minutes in 1050 DEG C
After be warming up to more than 1500 DEG C molten point molten point, vanadium enters in slag and obtains high grade vanadium slag and high-purity molten iron,
Wherein vanadium recovery 99.1%, high purity iron iron content 99.5%.
(5) vanadium slag is used for vanadium extraction, and high-purity molten iron is used for making steel.
Claims (3)
1. the technique processing vanadium titano-magnetite comprehensive utilization, it is characterised in that comprise the following steps:
(1) v-ti magnetite green ore divides through broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, shaking table
Ilmenite concentrate and high vanadium ferroalloy concentrate is obtained after choosing；
(2) high vanadium ferroalloy fine powder allocates 1 3% binding agent mixing pelletizing, dried, with coal dust or Jiao into
Powder mixes, and through cloth, the controlling reduction carrying out making V not be reduced in coal base shaft furnace obtains sponge
Ferrum, coal dust or coke powder consumption account for the 30%～70% of high vanadium ferroalloy fine powder weight, reduction temperature 850 DEG C
～1060 DEG C, recovery time 10-18h, obtain sponge iron.
(3) sponge iron obtained carries out heating in weak reducing atmosphere in intermediate frequency/main frequency furnace, in
1050 DEG C of heating 0.5-1.0h, are warming up to more than 1500 DEG C molten point, and vanadium enters in slag, obtains Gao Pin
Level vanadium slag and high-purity molten iron.
The technique of process vanadium titano-magnetite the most according to claim 1 comprehensive utilization, its feature exists
In also including: (4) vanadium slag is used for vanadium extraction, and high-purity molten iron is further used for producing high-purity iron block, atomization
Iron powder or steel-making.
The technique of process vanadium titano-magnetite the most according to claim 1 and 2 comprehensive utilization, it is special
Levy and be: described binding agent is mixed by 0.5-0.8:0.5-0.2 by starch and cellulose.
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| CN106755687A (en) * | 2016-11-24 | 2017-05-31 | 武汉科思瑞迪科技有限公司 | A kind of based shaft kiln directly reduced technique of coal |
| CN106868245A (en) * | 2017-03-13 | 2017-06-20 | 武汉科思瑞迪科技有限公司 | A kind of molten iron making processes of two-step method |
| CN106987731A (en) * | 2017-03-23 | 2017-07-28 | 江苏省冶金设计院有限公司 | The system and method for extracting vanadium from stone coal |
| CN107739819A (en) * | 2017-11-15 | 2018-02-27 | 武汉科思瑞迪科技有限公司 | A kind of method of coal base shaft furnace process processing iron content red mud |
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| CN110564906A (en) * | 2019-07-19 | 2019-12-13 | 陕西有色冶金矿业集团有限公司 | Method for separating and enriching vanadium from iron ore concentrate and producing pure iron |
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