CN105969981B - A kind of technique of vanadium titano-magnetite comprehensive utilization - Google Patents
A kind of technique of vanadium titano-magnetite comprehensive utilization Download PDFInfo
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- CN105969981B CN105969981B CN201610287438.1A CN201610287438A CN105969981B CN 105969981 B CN105969981 B CN 105969981B CN 201610287438 A CN201610287438 A CN 201610287438A CN 105969981 B CN105969981 B CN 105969981B
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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 present invention relates to a kind of technique for handling vanadium titano-magnetite comprehensive utilization, it is characterised in that comprises the following steps：(1) v-ti magnetite green ore obtains ilmenite concentrate and high vanadium ferroalloy concentrate after broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, separation by shaking table；(2) high vanadium ferroalloy fine powder supplying binding agent is mixed after pelletizing, drying, mixed with coal dust or coke powder, through cloth, enter to exercise the controlling reduction that V is not reduced in coal base shaft furnace and obtain sponge iron, the reducing agent consumption such as coal dust accounts for the 30%~70% of high vanadium ferroalloy fine powder weight, 850 DEG C~1060 DEG C of reduction temperature, the 18h of recovery time 10 obtains sponge iron；(3) sponge iron obtained is heated after 0.5 1.0h in intermediate frequency/main frequency furnace of weak reducing atmosphere in 1050 DEG C of Inner, is warming up to more than 1500 DEG C molten point, vanadium enters in slag, obtains high grade vanadium slag and high-purity molten iron.The present invention realizes efficiently separating and high value added utilization for a variety of valuable elements of vanadium titano-magnetite.
Description
Technical field
The present invention relates to a kind of technique of vanadium titano-magnetite comprehensive utilization.
Background technology
At present containing the non-blast furnace processing method of vanadium titano-magnetite approximately as：
Molten point of coal gas fluid bed reduction+electric furnace, such as Application No. CN201110027410.1 patent discloses one kind
The method that coal system reduces gas fluid bed reduction v-ti magnetite miberal powder, the coal gas of high temperature of coal system also Primordial Qi system production is with carrying out autoreduction
The gas mixing of weary gas cleaning system turns into reducing gas, sequentially enters three-level, two grades and one-level reduction fluid bed；After preheating
V-ti magnetite miberal powder sequentially enters one-level, two grades and three-level reduction fluid bed, it is reverse and on reducing gas in the presence of, it is real
Reduction reaction is concurrently given birth in existing fluidization；Obtained DRI compound stalk forming simultaneously removes titanium slag, extracted after vanadium slag, produces conjunction
Lattice molten steel.
Molten point of gas-based shaft kiln reduction+electric furnace：Patent such as Application No. CN201310216599.8 discloses one
The technique for planting molten point of vanadium titano-magnetite of gas-based shaft kiln directly reduced-electric furnace, comprises the following steps：A. manufactured goods pelletizing；B. will be into
Product vanadium-titanium ore pellets load in direct-reduction shaft furnace as raw material, and are passed through into shaft furnace also Primordial Qi, and reducting pellet ore deposit obtains heat
State DRI；C. hot direct reduced iron is heat-fed to molten point of electric furnace and carries out molten point of reduction, isolated titanium slag and contained
Vanadium-containing molten iron；D. vanadium-bearing hot metal is transported in converter and blown, isolate vanadium slag and half steel.And Publication No.
The method that CN201210377607.2 patent discloses a kind of molten point of comprehensive utilization of V-Ti magnetite of use reduction shaft furnace-electric furnace,
Vanadium titano-magnetite concentrate and binding agent are mixed and made into acid pellet, temperature be 900~1200 DEG C, pressure be 0.2~0.3MPa
Gas-based shaft kiln in reduction 4~6 hours, also Primordial Qi H2+CO >=90%, H2 and CO mol ratios is 1~3, goes back original product feeding electricity
Stove is melted and slag sluicing system, obtains titanium containing vanadium in molten iron and slag, slag, for vanadium extraction and carries titanium.Can be had titanium
The extraction and application of effect；Without coke, coking coal is not consumed, alleviates the situation being becoming tight coking coal resource day.
Tunnel kiln reduction+mill choosing separation：As Application No. CN201110367255.8 patents disclose a kind of from vanadium titanium magnetic
The method that iron and vanadium titanium are separated in iron ore, comprises the following steps：A, dispensing：By weight ratio by 100 parts of vanadium titano-magnetite, with adding
Plus 15~25 parts of mixings of 15~20 parts of agent and carbonaceous reducing agent, wherein, described additive is sodium chloride, sodium sulphate, sodium carbonate
At least one of；B, charging, reduction：Mixture after being mixed in a steps is fed, and then heating-up temperature is extremely in tunnel cave
920~980 DEG C and 5~60h of insulation, obtain reducing ingot；C, separation：Reduction ingot is broken, magnetic separation separation, obtains reduced iron powder and richness
Vanadium titanium material.
Rotary hearth furnace reduction+gas furnace melting：Patent such as Application No. CN201210208871.3 discloses one kind and turns bottom
The method of molten point of comprehensive utilization of V-Ti magnetite of stove reduction-combustion gas smelting furnace, first by vanadium titano-magnetite, reduction coal and binding agent
Pelletizing is pressed into after mixing, loads after drying and 1150~1350 DEG C is heated in rotary hearth furnace, reduce 30~40 minutes；Obtained high temperature
Metallized pellet, which is sent directly into, to be made molten point of stove of regenerative gas of fuel with coal gas and carries out fusing separation, and control combustion gas is molten to divide a furnace temperature
Degree obtains vanadium-bearing hot metal and titanium slag at 1500-1620 DEG C；Titanium slag is used for the raw material for producing titanium dioxide, or by floatation process life
Produce rich-titanium material；Vanadium-bearing hot metal enters oxygen blast in converter and obtains vanadium slag and half steel, removes half steel after vanadium slag and continues to smelt into molten steel.
The method for summarizing reduction vanadium titano-magnetite at present, is broadly divided into gas base method and coal base method, gas base method is needed to use
Expensive natural gas resource, is not suitable for China's national situation；And natural gas is substituted using coal gas and is used as also Primordial Qi, although China has largely
Coal resource, but coal gas be used as also Primordial Qi there is many technical barriers, can not realize in a short time industrialization large-scale production,
And production cost is high, only one cost of coal gas is accomplished by 950 yuan/tDRI.Coal base fado uses rotary hearth furnace or tunnel cave, turns bottom
Stove is relatively thin due to the bed of material, and production capacity is restricted, especially, within Carbon-bearing briquette be raw material, reducing agent ash content enters product, causes
Resultant metal rate is low, high (＞ 0.10%) containing S.And tunnel cave tunnel furnace method is low because of the thermal efficiency, high energy consumption (consumption coal about 1t/t,
Wherein reduction 450~550kg/t of coal, heating 400~550kg/t of coal), production cycle length (48~76 hours)；Pollution is tight
Weight (solid waste such as reduction coal ash, useless reductive jar is more, and dust is more), the problems such as single machine production ability is small can not possibly turn into from now on
Handle the main flow direction of vanadium titano-magnetite.
Generally there are two kinds of processing modes by reducing obtained metallized pellet, one kind is molten point of electric furnace, and one kind is mill choosing
Separation.Melt and be divided to and be divided into two kinds, one kind is vanadium and titanium while entering clinker；Another is that titanium enters clinker, and most of vanadium enters
Molten iron, then carry out vanadium extraction from hot metal production vanadium slag.Molten timesharing need to add fluxing agent and slag former, CaO, SiO2Enter simultaneously with vanadium titanium
Content of vanadium relative reduction in clinker, slag, currently without economically viable technology path, in the experimental study stage.And molten iron is carried
Vanadium causes heating element in the loss of iron, half steel to reduce and temperature reduction when producing vanadium slag, bring adverse effect to steel-making, simultaneously
CaO, SiO in vanadium slag2Content is high, it is impossible to produce high grade vanadium slag, the production to next step vanadic anhydride brings difficulty.
The content of the invention
The purpose of the present invention in view of the shortcomings of the prior art, proposes a kind of technique for handling vanadium titano-magnetite comprehensive utilization,
The problem of solution vanadium titano-magnetite economy, high added value, extensive industrialization are utilized.The present invention is carried out to vanadium titano-magnetite first
Sorting obtains high vanadium ferroalloy fine powder, then being controlled property of high vanadium ferroalloy fine powder (making V not be reduced) reduction is obtained using coal base shaft furnace
Sponge iron, obtained sponge iron progress electric furnace, which melts, gets high-purity molten iron and high grade vanadium slag, and realizing that vanadium titano-magnetite is a variety of has
Valency element is efficiently separated and high value added utilization.
The present invention solve the above problems the technical scheme that uses for：
A kind of technique for handling vanadium titano-magnetite comprehensive utilization, it is characterised in that comprise the following steps：
(1) v-ti magnetite green ore obtains ilmenite concentrate after broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, separation by shaking table
With high vanadium ferroalloy concentrate；
(2) high vanadium ferroalloy fine powder is incorporated 1-3% binding agent and mixed after pelletizing, drying, is mixed with coal dust or coke powder, through cloth,
Enter to exercise the controlling reduction that V is not reduced in coal base shaft furnace and obtain sponge iron, coal dust or coke powder consumption account for high vanadium ferroalloy fine powder
The 30%~70% of weight, 850 DEG C~1060 DEG C of reduction temperature, recovery time 10-18h obtains sponge iron.
(3) sponge iron obtained carries out heating in weak reducing atmosphere in intermediate frequency/main frequency furnace, in 1050 DEG C of Inner heating
0.5-1.0h, is warming up to more than 1500 DEG C molten point, vanadium enters in slag, obtains high grade vanadium slag and high-purity molten iron, Fe up to 99% with
On, the V rate of recovery more than 99%).
Present invention additionally comprises：Vanadium slag is used for vanadium extraction, and high-purity molten iron is further used for producing high-purity iron block, atomized iron powder or refining
Steel.
Described binding agent presses 0.5-0.8 by starch and cellulose：0.5-0.2 is mixed.
The ilmenite concentrate sub-elected is used to further produce titanium white.
The principle of the invention：1) vanadium titano-magnetite is sorted, obtains high vanadium ferroalloy fine ore；2) coal is used in coal base shaft furnace
Powder or coke powder etc. are reduced as being controlled property of reducing agent, and obtained sponge ferrous metal is reduced at 850~1060 DEG C of reduction temperature
Rate is high, reaches more than 90%, melts the rate of recovery height of point rear vanadium, reaches more than 99%；Can accurately it be controlled simultaneously as coal base is perpendicular
Reduction temperature processed within 850~1060 DEG C, can effective reduced iron, while suppress Si, Mn, Ca, Mg, Al, V, Cr, B reduction,
The degree of purity and the recovery rate of vanadium of molten iron after molten point has been effectively ensured.3) using controlling heating, (weak reducing atmosphere is heated, and is prevented
Only sponge iron is aoxidized when heating) and molten point of heating, melt non-reduzate after dividing and enter slag, form vanadium slag, iron enters molten iron, obtained
The vanadium slag grade that arrives is high, and the molten steel quality of formation is pure, and Fe is up to more than 99%, the V rate of recovery more than 99%, and realize iron and vanadium has
Effect separation and high value added utilization.
Beneficial effects of the present invention：Solve the following technical barrier in existing process：1) formed after molten point of prior art
Si, Mn, V high molten iron, vanadium is difficult to the technical barrier efficiently separated, and this method realizes iron, vanadium and efficiently separated and high value
Utilize；2) solve molten point of the current existing non-blast furnace process-electric furnace of vanadium titano-magnetite and be difficult to scale, industrialization, low cost
The problem of production, this method production cost is low, and energy consumption is low, can scale, industrialized production；3) existing metallized pellet has been cast out
Molten point forms vanadium-bearing hot metal, then the complicated technology that vanadium extraction obtains vanadium slag is carried out to molten iron.The molten point step of electric furnace produces high grade
Vanadium slag and high-purity molten iron, improve the economic value that vanadium titano-magnetite is utilized.This method has the advantages that simultaneously：1)
Vanadium titano-magnetite is handled using coal base shaft furnace, domestic abundant coal resources are made full use of, the thermal efficiency is high, low production cost,
Technology maturation, easily realizes extensive, industrialized production；Compared with rotary hearth furnace, rotary hearth furnace is relatively thin due to the bed of material, and production capacity is limited
System, especially within Carbon-bearing briquette be raw material, reducing agent ash content enters product, cause resultant metal rate low (less than 85%),
It is high (＞ 0.10%) containing S；Compared with tunnel cave, the tunnel furnace method thermal efficiency is low, high energy consumption (consumption coal about 1t/t, wherein reduction coal
450~550kg/t, heating 400~550kg/t of coal), production cycle length (48~76 hours)；Seriously polluted (reduction coal ash,
The solid waste such as useless reductive jar are more, and dust is more), single machine production ability is small, and floor space is big.2) this method is not to v-ti magnetite
Ore deposit is handled in carrying out with carbon so that the sponge iron degree of metalization that reduction is obtained is high, and S contents are low, the molten hot metal purifying degree got
Height, quality better.3) vanadium slag CaO, SiO that directly molten point (being not added with slag former) obtains2Content is low, and grade is high, good in economic efficiency, raw
Production is with low cost.4) this method reduction process need not use the additive of costliness, effectively reduce production cost, be beneficial to simultaneously
Improve furnace life.5) this method production good product quality, vanadium slag grade is high, and good in economic efficiency, hot metal purifying degree is high, and (Fe reaches
More than 99%, the V rate of recovery more than 99%), the exploitation available for high value added product.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Embodiment
Coal base shaft furnace of the present invention uses Patent No. ZL200620095509. × structure, technological process such as Fig. 1
It is shown.
Embodiment one：The method of high value added utilization vanadium titano-magnetite, its step is：
(1) v-ti magnetite green ore obtains high vanadium ferroalloy after broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, separation by shaking table
Concentrate；
(2) high vanadium ferroalloy fine powder supplying accounts for 2.0% binding agent of high vanadium ferroalloy fine powder weight (starch and cellulose is by 0.7：0.3
Ratio is mixed) mix pelletizing, air-dry, 40% coal blending (3) that outer supplying accounts for high vanadium ferroalloy fine powder weight will mix material through cloth
Furnace reduction, which is erected, in coal base obtains sponge iron, 880 DEG C of reduction temperature, recovery time 18h, reduzate degree of metalization 90%；
(4) sponge iron obtained is warming up to 1500 after heating 0.5h in 1000 DEG C in the main frequency furnace of weak reducing atmosphere
Melt and divide more than DEG C, vanadium, which enters in slag, 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 to be used to produce atomized iron powder.
Embodiment two：The method of high value added utilization vanadium titano-magnetite, its step is：
(1) v-ti magnetite green ore obtains high vanadium ferroalloy after broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, separation by shaking table
Concentrate；
(2) high vanadium ferroalloy fine powder supplying accounts for 1.5% binding agent of high vanadium ferroalloy fine powder weight (starch and cellulose is by 0.5：0.5
Ratio is mixed) mix pelletizing, air-dry, it is outer to be incorporated 30% coal blending for accounting for high vanadium ferroalloy fine powder weight；
(3) material will be mixed and obtain sponge iron, 1000 DEG C of reduction temperature, recovery time in the perpendicular furnace reduction of coal base through cloth
15h, reduzate degree of metalization 91.3%；
(4) sponge iron obtained is warming up to after being heated 40 minutes in 1000 DEG C in the middle frequency furnace of weak reducing atmosphere
More than 1500 DEG C molten point, vanadium, which enters in slag, obtains high grade vanadium slag and high-purity molten iron, wherein 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 to be used to produce high-purity iron block.
Embodiment three：The method of high value added utilization vanadium titano-magnetite, its step is：
(1) v-ti magnetite green ore obtains high vanadium ferroalloy after broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, separation by shaking table
Concentrate；
(2) high vanadium ferroalloy fine powder supplying accounts for 3.0% binding agent of high vanadium ferroalloy fine powder weight (starch and cellulose is by 0.8：0.2
Ratio is mixed) mix pelletizing, air-dry, it is outer to be incorporated 55% coal blending for accounting for high vanadium ferroalloy fine powder weight；
(3) material will be mixed and obtain sponge iron, 1060 DEG C of reduction temperature, recovery time in the perpendicular furnace reduction of coal base through cloth
13h, reduzate degree of metalization 92%；
(4) 1500 are warming up to after being heated 30 minutes in 1050 DEG C in the middle frequency furnace of the sponge iron weak reducing atmosphere obtained
Melted more than DEG C and divide molten point, vanadium, which enters in slag, 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 to make steel.
Claims (3)
1. a kind of technique for handling vanadium titano-magnetite comprehensive utilization, it is characterised in that comprise the following steps：
（1）V-ti magnetite green ore obtains ilmenite concentrate and height after broken, throwing tail, fine grinding, low intensity magnetic separation, high intensity magnetic separation, separation by shaking table
Vanadium iron concentrate；
（2）High vanadium ferroalloy fine powder is incorporated 1-3% binding agent and mixed after pelletizing, drying, is mixed with coal dust or coke powder, through cloth, in coal
Enter to exercise the controlling reduction that V is not reduced in base shaft furnace and obtain sponge iron, coal dust or coke powder consumption account for high vanadium ferroalloy fine powder weight
30% ~ 70%, 850 DEG C ~ 1060 DEG C of reduction temperature, recovery time 10-18h obtains sponge iron；
（3）Obtained sponge iron carries out heating in weak reducing atmosphere in intermediate frequency/main frequency furnace, in 1050 DEG C of Inner heating 0.5-
1.0h, is warming up to more than 1500 DEG C molten point, vanadium enters in slag, obtains high grade vanadium slag and high-purity molten iron.
2. the technique of processing vanadium titano-magnetite comprehensive utilization according to claim 1, it is characterised in that also include：（4）Vanadium
Slag is used for vanadium extraction, and high-purity molten iron is further used for producing high-purity iron block, atomized iron powder or steel-making.
3. the technique of the processing vanadium titano-magnetite comprehensive utilization according to claim 1 or 2, it is characterised in that：Described is viscous
Tie agent and 0.5-0.8 is pressed by starch and cellulose：0.5-0.2 is mixed.
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| 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 |
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| CN105969981A (en) | 2016-09-28 |
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