CN117512246A - Method for efficiently utilizing vanadium titano-magnetite with low carbon - Google Patents
Method for efficiently utilizing vanadium titano-magnetite with low carbon Download PDFInfo
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- CN117512246A CN117512246A CN202210904511.0A CN202210904511A CN117512246A CN 117512246 A CN117512246 A CN 117512246A CN 202210904511 A CN202210904511 A CN 202210904511A CN 117512246 A CN117512246 A CN 117512246A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 206
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 196
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 238000000034 method Methods 0.000 title claims abstract description 94
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000008188 pellet Substances 0.000 claims abstract description 115
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 114
- 239000001257 hydrogen Substances 0.000 claims abstract description 114
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052742 iron Inorganic materials 0.000 claims abstract description 69
- 230000008569 process Effects 0.000 claims abstract description 54
- 239000007789 gas Substances 0.000 claims abstract description 52
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 51
- 239000010936 titanium Substances 0.000 claims abstract description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000012141 concentrate Substances 0.000 claims abstract description 39
- 239000000428 dust Substances 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 28
- 230000008018 melting Effects 0.000 claims abstract description 28
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 6
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 42
- 239000002893 slag Substances 0.000 claims description 40
- 230000009467 reduction Effects 0.000 claims description 33
- 238000007789 sealing Methods 0.000 claims description 31
- 239000011230 binding agent Substances 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 14
- 239000010959 steel Substances 0.000 claims description 14
- 239000003245 coal Substances 0.000 claims description 13
- 238000011946 reduction process Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010309 melting process Methods 0.000 claims description 9
- 238000001465 metallisation Methods 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002006 petroleum coke Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 abstract description 13
- 238000001816 cooling Methods 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000010310 metallurgical process Methods 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000004939 coking Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000010215 titanium dioxide Nutrition 0.000 description 5
- 239000003034 coal gas Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- -1 titanium metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention discloses a method for efficiently utilizing vanadium titano-magnetite with low carbon, which adopts a process of roasting by a belt type machine, prereducing by a hydrogen-based shaft furnace and melting by an electric furnace, firstly, mixing vanadium titano-magnetite concentrate with top dust and mud of the hydrogen-based shaft furnace to prepare pellets, oxidizing and roasting the pellets by the belt type machine, eliminating the cooling process of the traditional pellets, loading the pellets into the hydrogen-based shaft furnace at high temperature, and rapidly reducing the pellets at high temperature by using the introduced hydrogen or hydrogen-rich gas; and then the obtained pre-reduced pellets are hot-filled into an electric furnace, and fuel and reducing agent with low carbon emission are adopted, so that repeated heating-cooling links in the metallurgical process are reduced, carbon emission in the smelting process of the vanadium titano-magnetite is greatly reduced, and the low-carbon and high-efficiency utilization of iron, vanadium, titanium and other elements in the vanadium titano-magnetite is realized.
Description
Technical Field
The invention belongs to the technical field of ferrous metallurgy, and particularly relates to a method for efficiently utilizing vanadium titano-magnetite with low carbon.
Background
Vanadium titano-magnetite is a multi-element symbiotic iron ore mainly containing iron, vanadium and titanium elements and other useful elements such as cobalt, nickel, chromium, scandium, gallium and the like, and has high comprehensive utilization value. Because vanadium titano-magnetite is difficult to reduce, titanium is easy to form titanium nitride and titanium carbide under strong reducing atmosphere, so that the viscosity of molten iron is high, slag-iron separation is difficult, the smelting technology is greatly different from that of common iron ore, and the vanadium titano-magnetite is considered as 'dead ore' by some foreign experts, and the comprehensive utilization of iron, vanadium and titanium resources belongs to the world problem.
Vanadium titano-magnetite is mainly classified into a blast furnace method and a non-blast furnace method. The technology of climbing steel and bearing steel is advanced in the smelting aspect of a vanadium-titanium ore blast furnace, and 2000m of steel is completely mastered by adding about 30 percent of common ore 3 Left and right blast furnace vanadium-titanium ore smelting technology, the utilization coefficient reaches 2.5 t/(m) 3 D) fuel ratio of 530-550kg/tHM, coal ratio of about 100kg, iron grade in furnace of 52%, ti content in molten iron of 0.2%, slag ratio of 550-600kg, tiO in slag 2 About 22%. In the blast furnace smelting process, 80% of vanadium is fed into molten iron, and in the steelmaking process, oxygen is blown to obtain vanadium slag and comprehensive utilization is carried out; about 25% of titanium enters molten iron in the form of titanium nitride or titanium carbide, and the rest of titanium enters blast furnace slag, and because of TiO in the slag 2 Low content and exists in a perovskite form which is difficult to use, so that the perovskite form cannot be used well; the recycling rates of iron, vanadium and titanium in the vanadium-titanium magnetite concentrates treated by the blast furnace method are respectively 90%, 80% and 0%.
In the aspect of vanadium titanium ore non-blast furnace metallurgy, various researches and practices are also carried out by enterprises and research institutions at home and abroad. The new zealand iron and steel company utilizes the direct reduction-electric furnace process of sea sand ore to produce vanadium-containing molten iron and vanadium slag, adopts concentrate, coal and limestone to mix and then enter a multi-hearth furnace for heating, then enters a rotary kiln for reduction, and then enters a rectangular electric furnace for melting and separating, so that the iron and vanadium are well utilized, and the slag contains 30 percent of titanium dioxide and is not recycled. The south Africa Haifer steel vanadium company also adopts a rotary kiln-electric furnace process, iron and vanadium are well utilized, titanium is not recycled, and the technical problem that the rotary kiln is easy to form rings in the production process of the process exists. The Pan-steel and Dragon-shikim group has developed a great deal of work in the aspect of the pre-reduction of the vanadium-titanium ore rotary hearth furnace and the melting of the electric furnace; the iron, vanadium and titanium can be well utilized in the small test; because of the complexity of the technology and various problems encountered in the industrialization process, pilot plant test work is intermittent, and the test is stopped. In the field of conventional direct reduction of iron ores, gas-based shaft furnaces account for up to 75%, and are dominant. Many research institutions put forward to replace rotary kiln to conduct pre-reduction test research on vanadium titano-magnetite by using a shaft furnace, and the obtained reduction product enters an electric furnace to conduct melt separation to obtain titanium slag and vanadium-containing molten iron, and vanadium is extracted in the converter steelmaking process; the students of the university of south China and the university of northeast China develop a great deal of researches, the recovery rate of iron and vanadium is high, and the recovery rate of titanium is over 80 percent, but the researches are basically in laboratory scale, and no full-process verification in industrial scale exists.
Patent CN102424876A and patent CN103451419A introduce a method for reducing vanadium titano-magnetite by using coal gas prepared from non-coking coal as a reducing agent, so that the dependence of the traditional process on coking coal is greatly reduced, the diversification of smelting energy is realized, the comprehensive recovery of iron, vanadium and titanium metals is realized, and the smelting of all-vanadium titano-magnetite in a furnace is realized.
Patent CN110484720A describes a process for comprehensively utilizing vanadium titanomagnetite by roasting in a grate, prereducing in a gas-based shaft furnace and deeply reducing in an electric furnace, so that the reduction degradation rate of oxidized pellets is greatly reduced, and the reduction requirement of the subsequent shaft furnace can be met, thereby realizing the efficient clean utilization of iron, vanadium and titanium, reducing the cost and improving the production efficiency.
Patent CN102899435a describes a method for comprehensively utilizing vanadium titano-magnetite by shaft furnace reduction-electric furnace melting, which can effectively utilize titanium metal in the vanadium titano-magnetite, does not need coke and consume coking coal, and can relieve the situation that the coking coal supply is increasingly tense.
Patent CN103667572A describes a gas-based shaft furnace direct reduction smelting method of high-chromium vanadium titano-magnetite, 100% of high-chromium vanadium titano-magnetite is taken as a raw material, and the smelting is carried out by a shaft furnace reduction and high-frequency induction furnace, so that the obtained pig iron has iron grade and yield of more than 90%, the vanadium and chromium yields are both higher than 85%, and TiO in high-titanium slag is obtained 2 The grade is about 40 percent, and the titanium metal yield is 85 to 90 percent.
The technology is a patent of the whole flow of vanadium-titanium ore gas-based prereduction-electric furnace melting separation, and the emphasis and the technical innovation point are different; patent CN102424876A and patent CN103451419A focus on gas-based reduction and electric furnace melting and titanium slag utilization, and use non-coking coal gas as a reducing agent, so that dependence of a traditional process on coking coal is reduced, and diversity of smelting energy is realized, but energy consumption and wastewater discharge in the coal gas process are relatively large. The patent CN110484720A is used for pellet preparation, gas-based reduction and slag adjustment, the scheme adopts a grate for pellet preparation, the thickness of a grate material layer is generally 200-300mm, the material layer is low, so that heat is underutilized and passes through the material layer, and the energy consumption is high; the patent CN102899435A is gas-based reduction+electric furnace melting and vanadium-titanium slag utilization, wherein vanadium and titanium both enter slag, and the subsequent process utilization difficulty is higher because the vanadium content in the slag is lower; patent CN103667572a aims at high chromium type vanadium titanium ore, an induction furnace is used as melting equipment, and a large amount of slag cannot generate heat in the furnace by induction due to large slag quantity, so that slag-iron separation is difficult. The heating and reducing gases of the technology adopt blast furnace gas, coke oven gas or coal gas and the like, the process carbon emission is high, and the technology does not accord with the prospect of carbon neutralization.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for utilizing vanadium titanomagnetite with low carbon and high efficiency, which adopts a process of belt type machine roasting-hydrogen-based shaft furnace prereduction-electric furnace melting separation, vanadium titanomagnetite concentrate and top dust mud of the hydrogen-based shaft furnace are firstly prepared into pellets, the belt type machine is utilized to oxidize and roast the pellets, the cooling process of the traditional pellets is eliminated, the hydrogen-based shaft furnace is filled with high temperature heat, and the introduced hydrogen or hydrogen-rich gas and the pellets are utilized to realize high-temperature rapid reduction; and then the obtained pre-reduced pellets are hot-filled into an electric furnace, and fuel and reducing agent with low carbon emission are adopted, so that repeated heating-cooling links in the metallurgical process are reduced, carbon emission in the smelting process of the vanadium titano-magnetite is greatly reduced, and the low-carbon and high-efficiency utilization of iron, vanadium, titanium and other elements in the vanadium titano-magnetite is realized.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a method for efficiently utilizing vanadium titano-magnetite with low carbon, which comprises the following steps:
s1, roasting by a belt type machine, respectively carrying out surface modification on vanadium-titanium magnetite concentrate and hydrogen-based shaft furnace top dust mud, and uniformly mixing the surface modified vanadium-titanium magnetite concentrate, binder and water to obtain vanadium-titanium magnetite green pellets; the raw pellets of the vanadium titano-magnetite enter a belt conveyor to be dried, preheated and roasted to obtain oxidized pellets of the vanadium titano-magnetite;
s2, pre-reducing the hydrogen-based shaft furnace, and thermally loading the vanadium titano-magnetite oxidized pellets into the hydrogen-based shaft furnace for pre-reducing to obtain vanadium titano-magnetite pre-reduced pellets;
s3, melting in an electric furnace, namely, hot charging the vanadium titano-magnetite pre-reduced pellets into the electric furnace, adding a flux and low ash coal or low sulfur petroleum coke, and carrying out deep reduction, melting and slag-iron separation to obtain vanadium-containing molten iron and titanium-containing slag; the vanadium-containing molten iron is subjected to oxygen blowing refining to obtain molten steel and vanadium slag; the titanium-containing slag is used as a raw material of titanium dioxide.
Preferably, in the step S1:
the vanadium-titanium magnetite concentrate and the top dust mud of the hydrogen-based shaft furnace are subjected to surface modification treatment by fine grinding and high-pressure roller grinding; and/or
The surface modification treatment of the vanadium-titanium magnetite concentrate and the hydrogen-based shaft furnace top dust mud shows that the specific surface area is 1500-2000 cm 2 /g; and/or
In the vanadium-titanium magnetite concentrate, the TFe content is more than or equal to 52 weight percent, and the titanium content isMore than or equal to 9 weight percent, the vanadium content is 0.3 to 1.5 weight percent, and the SiO content is equal to or more than 2 The content is 2.5 to 3.5 weight percent; and/or
In the top dust mud of the hydrogen-based shaft furnace, the TFe content is more than or equal to 60wt percent, V 2 O 5 ≥0.3wt％，TiO 2 More than or equal to 10wt%; and/or
More than 70% of the vanadium-titanium magnetite concentrates have the granularity of-0.074 mm; more than 70% of the top dust mud of the hydrogen-based shaft furnace has a granularity of-0.074 mm; and/or
After the surface modification treatment of the vanadium-titanium magnetite concentrate and the hydrogen-based shaft furnace top dust mud, the specific surface area is more than or equal to 1500cm 2 /g; and/or
The top dust mud of the hydrogen-based shaft furnace accounts for 1.0-3.0 wt% of the total materials; the binder accounts for 0.5 to 1.5 weight percent of the total materials; the water accounts for 6.0 to 9.0 weight percent of the total materials; and/or
The binder is one or more selected from bentonite, an organic binder and a composite binder; and/or
The diameter of the raw pellet of the vanadium titano-magnetite is 8-12 mm.
Preferably, in the step S1, TFe content is more than or equal to 55wt%, titanium content is more than or equal to 10wt%, and SiO in the vanadium-titanium magnetite concentrate 2 The content is 2.5 to 3.0 weight percent.
Preferably, in the step S1:
the belt conveyor adopts one or more of hydrogen, natural gas, coke oven gas or biomass pyrolysis gas as fuel; the thickness of the material layer in the belt conveyor is 400-600 mm; and/or
In the drying process, the drying temperature is 180-400 ℃; and/or
In the preheating process, the preheating temperature is 900-1050 ℃; and/or
In the roasting process, the roasting temperature is 1000-1200 ℃ and the roasting time is 20-60 min; and/or
In the roasting process of the belt conveyor, the oxygen content in the hot air is 15-19 wt%; and/or
The compressive strength of the vanadium titano-magnetite oxidized pellet is 1700-2000N/pellet.
Preferably, in the step S1:
in the roasting process, the roasting temperature is 1050-1150 ℃ and the roasting time is 25-40 min; and/or
In the roasting process of the belt conveyor, the oxygen content in the hot air is 16-18 wt%.
Preferably, in the step S2, the specific process of prereduction in the hydrogen-based shaft furnace is as follows:
the vanadium titano-magnetite oxidized pellet is thermally filled into an upper sealing tank at the top of a hydrogen-based vertical furnace, and N is arranged in the upper sealing tank 2 The high-temperature purging and deoxidizing process is completed by water vapor or high-temperature flue gas, so that the oxygen content in the gas of the upper sealed tank is less than or equal to 1wt%; then the hot vanadium titano-magnetite oxidized pellets enter a lower sealing tank, and hydrogen or hydrogen-rich gas is adopted to pressurize the lower sealing tank, wherein the pressure reaches 0.2-0.5 MPa; and then, thermally loading the pellets into a hydrogen-based shaft furnace, and pre-reducing the pellets by taking hydrogen or hydrogen-rich gas as reducing gas to obtain the vanadium titano-magnetite pre-reduced pellets.
Preferably, in the step S2:
the temperature of the vanadium titano-magnetite oxidized pellet hot-charged into the upper sealing tank of the hydrogen-based shaft furnace is 900-1150 ℃; and/or
In the pre-reduction process, the molar ratio of hydrogen in the reducing gas is more than or equal to 60%, and the temperature of the reducing gas is 600-1000 ℃; and/or
In the pre-reduction process, the reduction time of the vanadium titano-magnetite oxidized pellet in the hydrogen-based shaft furnace is 1-3 h; and/or
In the pre-reduction process, the metallization rate of the vanadium titano-magnetite pre-reduced pellet is 70-90%.
Preferably, in the step S2:
the temperature of the vanadium titano-magnetite oxidized pellet hot-charged into the upper sealing tank of the hydrogen-based shaft furnace is 1000-1150 ℃; and/or
In the pre-reduction process, the metallization rate of the vanadium titano-magnetite pre-reduced pellet is 82-90%.
Preferably, in the step S3:
the temperature of the vanadium titano-magnetite pre-reduced pellets is 500-700 ℃ when the pellets are hot-charged into the electric furnace; and/or
In the melting process of the electric furnace, the melting temperature is 1550-1700 ℃; and/or
In the melting process of the electric furnace, tiO in the titanium-containing slag 2 The content of (2) is more than or equal to 40wt%; and/or
The vanadium-containing molten iron comprises the following components: TFe: > 92%, C: 2-5%, V: 0.2% or more, si: less than or equal to 1.2 percent, and the balance is unavoidable impurities in percentage by mass.
Preferably, in the step S3:
in the melting process of the electric furnace, the melting temperature is 1580-1650 ℃; and/or
In the melting process of the electric furnace, tiO in the titanium-containing slag 2 The content of (C) is 45-49 wt%.
Preferably, in the method for efficiently utilizing vanadium titano-magnetite with low carbon, the utilization rate of iron in the vanadium titano-magnetite is more than 90%, the utilization rate of vanadium is more than 75%, and the utilization rate of titanium is more than 70%.
The method for efficiently utilizing vanadium titano-magnetite with low carbon provided by the invention has the following beneficial effects:
1. the invention relates to a method for efficiently utilizing vanadium titano-magnetite with low carbon, which adopts a process of belt type machine oxidative roasting, hydrogen-based shaft furnace prereduction and electric furnace melting separation, firstly vanadium titano-magnetite concentrate and hydrogen-based shaft furnace top dust mud are prepared into pellets, and the belt type machine is utilized for oxidative roasting of the pellets; by utilizing the characteristic of high material layer height of the belt roasting machine, the heat energy utilization rate can be improved, and the service life of the grate bars can be prolonged; the cooling process of the traditional pellets is canceled, the pellets are filled into a hydrogen-based shaft furnace at high temperature, and the introduced hydrogen or hydrogen-rich gas and the pellets are quickly reduced at high temperature; the obtained pre-reduced pellets are hot-charged into an electric furnace, and fuel with low carbon emission and a reducing agent are adopted, so that repeated heating-cooling links in the metallurgical process are reduced, carbon emission in the smelting process of vanadium titano-magnetite is greatly reduced, and low carbon and high efficiency utilization of iron, vanadium, titanium and other elements in the vanadium titano-magnetite is realized;
2. according to the method for efficiently utilizing vanadium titanomagnetite with low carbon, disclosed by the invention, vanadium titanomagnetite concentrate and hydrogen-based shaft furnace top dust mud are cooperatively treated, and the heat release in the oxidizing roasting process of metallic iron and FeO in the hydrogen-based shaft furnace top dust mud is utilized, so that the roasting temperature is reduced, and the pellet strength is improved; in addition, the sphericity of the vanadium-titanium magnetite concentrate and the top dust mud of the hydrogen-based shaft furnace is optimized through the surface modification treatment, so that the addition of a binder is reduced as much as possible;
3. according to the method for efficiently utilizing vanadium titano-magnetite with low carbon, disclosed by the invention, the belt type machine oxidation roasting and the hydrogen-based shaft furnace pre-reduction are organically combined, the pellet cooling and the temperature raising process of directly reducing the pellets are eliminated, the flow is simpler, and the energy utilization efficiency is improved;
4. according to the method for efficiently utilizing the vanadium titano-magnetite with low carbon, the physical heat of the vanadium titano-magnetite oxidized pellets is utilized, so that the heat required by hydrogen reduction and gas heating in the pre-reduction process of the hydrogen-based shaft furnace is met, the thermodynamic condition of hydrogen reduction is more reasonable, and the hydrogen utilization rate can be greatly improved;
5. the method for efficiently utilizing vanadium titanomagnetite with low carbon utilizes pure hydrogen or hydrogen-rich gas for cooling reduction, can realize the production of pre-reduced pellets by a carbon-free or low-carbon process, can greatly reduce carbon emission in the smelting process, is more environment-friendly, and can reduce the carbon emission by 10-70% compared with the traditional blast furnace process for producing vanadium-containing molten iron.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a process flow diagram of the method for efficiently utilizing vanadium titano-magnetite with low carbon.
Detailed Description
In order to better understand the above technical solution of the present invention, the technical solution of the present invention is further described below with reference to examples.
With reference to FIG. 1, the method for efficiently utilizing vanadium titano-magnetite with low carbon provided by the invention comprises the following steps:
s1, roasting by a belt type machine, respectively carrying out surface modification on vanadium-titanium magnetite concentrate and hydrogen-based shaft furnace top dust mud, and uniformly mixing the surface modified vanadium-titanium magnetite concentrate, binder and water to obtain vanadium-titanium magnetite green pellets; the raw pellets of the vanadium titano-magnetite enter a belt conveyor to be dried, preheated and roasted to obtain oxidized pellets of the vanadium titano-magnetite;
specifically, the first step is to prepare vanadium titano-magnetite green pellets, and surface modification is carried out on vanadium titano-magnetite concentrate and hydrogen-based shaft furnace top dust mud through fine grinding and high-pressure roller grinding respectively, so that the specific surface area of the vanadium titano-magnetite concentrate and the hydrogen-based shaft furnace top dust mud is more than or equal to 1500cm 2 In a further preferred embodiment, the surface of the vanadium-titanium magnetite concentrate and the top dust mud of the hydrogen-based shaft furnace is modified so that the specific surface area of the vanadium-titanium magnetite concentrate and the top dust mud is 1500-2000 cm 2 /g; the surface properties of vanadium-titanium magnetite concentrate and hydrogen-based shaft furnace top dust mud are activated and improved through surface modification, and the sphericity is optimized, so that the addition of a binder is reduced as much as possible; and uniformly mixing the modified vanadium-titanium magnetite concentrate, the hydrogen-based shaft furnace top dust mud, a binder and water, and pelletizing to obtain the vanadium-titanium magnetite green pellets with the diameter of 8-12 mm.
In the materials, the granularity of the vanadium-titanium magnetite concentrate and the top dust mud of the hydrogen-based shaft furnace is required to be-0.074 mm to be more than 70%; in the vanadium-titanium magnetite concentrate, the TFe content is more than or equal to 52wt%, the titanium content is more than or equal to 9wt%, the vanadium content is 0.3-1.5 wt%, and the SiO content is higher than or equal to 9wt% 2 The content is 2.5 to 3.5 weight percent, in a further preferred scheme, the TFe content is more than or equal to 55 weight percent, the titanium content is more than or equal to 10 weight percent, the vanadium content is 0.3 to 1.5 weight percent, and the SiO content is more than or equal to 2 The content is 2.5 to 3.0 weight percent; in the top dust mud of the hydrogen-based shaft furnace, the TFe content is more than or equal to 60wt percent, V 2 O 5 ≥0.3wt％，TiO 2 ≥10wt％。
The hydrogen-based shaft furnace top dust mud accounts for 1.0 to 3.0 weight percent of all materials (all materials comprise vanadium-titanium magnetite concentrate, hydrogen-based shaft furnace top dust mud, binder and water), and the binder accounts for 0.5 to 1.5 weight percent of all materials based on total consumption; the binder is selected from one or more of bentonite, organic binder and composite binder. The water accounts for 6.0 to 9.0 weight percent of the total materials.
Roasting the vanadium titano-magnetite green pellets by a belt conveyor, and drying, preheating and roasting the prepared vanadium titano-magnetite green pellets in the belt conveyor to finally obtain vanadium titano-magnetite oxidized pellets; in the process, the belt conveyor adopts one or more of hydrogen, natural gas, coke oven gas or biomass pyrolysis gas as fuel to provide the required high temperature for the roasting of the belt conveyor; the thickness of a material layer (namely vanadium titano-magnetite green pellets) in the belt conveyor is 400-600 mm; in the drying process, controlling the drying temperature to be 180-400 ℃; in the preheating process, the preheating temperature is controlled to be 900-1050 ℃; in the roasting process, the roasting temperature is controlled to be 1000-1200 ℃, the roasting time is controlled to be 20-60 min, and in a further preferred scheme, the roasting temperature is 1050-1150 ℃ and the roasting time is controlled to be 25-40 min; in the roasting process of the belt conveyor, the air-fuel ratio condition of the hydrogen-rich gas can be controlled to ensure that the oxygen content in the hot air is 15-19 wt percent so as to ensure that FeO and metallic iron in the vanadium titano-magnetite are oxidized and released, and in a further preferred scheme, the oxygen content in the hot air is 16-18 wt percent. The compressive strength of the vanadium titano-magnetite oxidized pellet is 1700-2000N/pellet.
S2, pre-reducing the hydrogen-based shaft furnace, and thermally loading the vanadium titano-magnetite oxidized pellets into the hydrogen-based shaft furnace for pre-reducing to obtain vanadium titano-magnetite pre-reduced pellets;
specifically, firstly, vanadium titano-magnetite oxidized pellets are thermally loaded into an upper sealing tank at the top of a hydrogen-based vertical furnace, and N is used for the upper sealing tank 2 The high-temperature purging and deoxidizing process is completed by water vapor or high-temperature flue gas, so that the oxygen content in the gas of the upper sealing tank is less than or equal to 1wt%; then the hot vanadium titano-magnetite oxidized pellets enter a lower sealing tank, and hydrogen or hydrogen-rich gas is adopted in the lower sealing tank for pressurization, wherein the pressure reaches 0.2-0.5 MPa; and then the pellets are thermally filled into a hydrogen-based shaft furnace, and the pre-reduction is carried out by adopting hydrogen or hydrogen-rich gas as reducing gas to obtain vanadium titano-magnetite pre-reduced pellets. Wherein the temperature of the upper sealing tank of the hydrogen-based shaft furnace, which is filled with vanadium titano-magnetite oxidized pellets, is 900-1150 ℃, and in a further preferred scheme, the temperature of the upper sealing tank of the hydrogen-based shaft furnace, which is filled with vanadium titano-magnetite oxidized pellets, is 1000-1150 ℃; in the pre-reduction process, the molar ratio of hydrogen in the reducing gas is more than or equal to 60 percent, the temperature of the reducing gas is 600-1000 ℃, and the vanadium titano-magnetite oxidized pellets are in a hydrogen-based shaft furnaceThe reduction time of (2) is 1-3 h. The metallization rate of the finally obtained vanadium titano-magnetite pre-reduced pellet is 70-90%, and in a further preferred scheme, the metallization rate of the vanadium titano-magnetite pre-reduced pellet is 82-90%.
S3, melting in an electric furnace, namely, hot charging the vanadium titano-magnetite pre-reduced pellets into the electric furnace, adding a flux and low ash coal or low sulfur petroleum coke, and carrying out deep reduction, melting and slag-iron separation to obtain vanadium-containing molten iron and titanium-containing slag; the vanadium-containing molten iron is subjected to oxygen blowing refining to obtain molten steel and vanadium slag; the titanium-containing slag is used as a raw material of titanium white.
Specifically, the vanadium titano-magnetite pre-reduced pellets obtained in the step S2 are hot-charged into an electric furnace, and a small amount of flux and low ash coal or low sulfur petroleum coke are added for deep reduction, melting and slag-iron separation, so that vanadium-containing molten iron and titanium-containing slag are finally obtained; wherein the temperature of the vanadium titano-magnetite pre-reduced pellet is 500-700 ℃ when the pellet is hot-charged into an electric furnace; in the melting process of the electric furnace, the melting temperature is controlled to be 1550-1700 ℃, and in a further preferred scheme, the melting temperature is controlled to be 1580-1650 ℃. The obtained vanadium-containing molten iron comprises the following components: > 92%, C: 2-5%, V: 0.2% or more, si: less than or equal to 1.2 percent, and the balance being unavoidable impurities in percentage by mass; the vanadium-containing molten iron can be further refined into molten steel and vanadium slag by oxygen blowing. TiO in titanium-containing furnace charge 2 In a further preferred embodiment, the titanium-containing charge contains TiO at a level of greater than or equal to 40 wt.% 2 The content of (C) is 45-49 wt%.
After the method for efficiently utilizing the vanadium titano-magnetite with low carbon is adopted, the utilization rate of iron in the vanadium titano-magnetite reaches more than 90 percent, the utilization rate of vanadium reaches more than 75 percent, and the utilization rate of titanium reaches more than 70 percent. If all electricity in the flow adopts green electricity, the carbon emission is less than or equal to 0.80t/t vanadium-containing molten iron, and is reduced by more than 50% compared with the carbon emission of the existing blast furnace flow.
The method for efficiently utilizing vanadium titano-magnetite with low carbon of the present invention is further described below with reference to specific examples. The vanadium-titanium magnetite concentrates used in the following examples 1-2 have the following main chemical composition contents: TFe:55.28%, feO:28.40%, siO 2 ：3.35％，V 2 O 5 ：0.56％，TiO 2 :11.50%, S:0.39%; in the vanadium-titanium magnetite concentrate, the proportion of the fraction of-0.074 mm is 75 percent; the main chemical composition content of the top dust mud of the hydrogen-based shaft furnace is as follows: MFe:22.02%, TFe:62.91%, feO:52.57%, siO 2 ：3.81％，V 2 O 5 ：0.64％，TiO 2 :12.88%, S:0.04%; the proportion of-0.074 mm size fraction in the top dust mud of the hydrogen-based shaft furnace was 72wt%.
Reference example
The vanadium titano-magnetite in this reference example was used as follows:
the main chemical components of the vanadium titano-magnetite are as follows: TFe:54%, siO 2 ：3.5％，V 2 O 5 ：0.65％，TiO 2 :11%, adding 70% vanadium titano-magnetite into 30% common iron concentrate, adding limestone, coke powder and water, mixing, sintering at high temperature to obtain sintered ore, adding blast furnace together with coke from the top, spraying coal at tuyere, coke ratio 450kg and coal ratio 100kg to obtain vanadium-containing molten iron with iron content 94% and V content 0.35%, and TiO 2 The iron recovery rate of the blast furnace slag with the content of 21 percent is 90 percent, the vanadium recovery rate is 80 percent, the titanium recovery rate is 0 percent, and the carbon emission of each ton of vanadium-containing molten iron is 1.58t.
Example 1
The method for efficiently utilizing vanadium titano-magnetite with low carbon in the embodiment comprises the following specific processes:
(1) Preparing oxidized pellets: the surface modification of vanadium titano-magnetite and hydrogen-based shaft furnace top dust mud is carried out by a high-pressure roller mill to ensure that the specific surface areas reach 1880cm respectively 2 /g、1910cm 2 Uniformly mixing vanadium titano-magnetite concentrate (dry basis), shaft furnace dust mud (dry basis), binder (dry basis) and water according to the mass percentage of 89.05:1.84:1.1:8, pelletizing, drying, preheating and roasting the obtained vanadium titano-magnetite green pellets in a belt conveyor at the drying temperature of 220-300 ℃ for 5min, the preheating temperature of 900-1000 ℃ for 10min, the roasting temperature of 1100 ℃ and the roasting time of 30min, wherein the oxygen content in hot air is 17.5-18%, and the compressive strength of the vanadium titano-magnetite oxidized pellets is 1780N/g, and the chemical components are as follows: TFe:53.44%, feO:0.50%, siO 2 ：3.70％，V 2 O 5 ：0.54％，TiO 2 ：11.10％，S：0.04％；
(2) Pre-reduction of hydrogen-based shaft furnace: the vanadium titano-magnetite oxidized pellet is thermally filled into an upper sealing tank at the top of a hydrogen-based vertical furnace, and N is introduced into the upper sealing tank 2 The high-temperature purging and deoxidizing process is completed by water vapor or high-temperature flue gas, so that the oxygen content in the gas of the upper sealing tank is less than or equal to 1wt%; then the hot vanadium titano-magnetite oxidized pellets enter a lower sealing tank, and hydrogen or hydrogen-rich gas is adopted in the lower sealing tank for pressurization, wherein the pressure reaches 0.2-0.5 MPa; and then the pellets are thermally filled into a hydrogen-based shaft furnace, and the pre-reduction is carried out by adopting hydrogen or hydrogen-rich gas as reducing gas to obtain vanadium titano-magnetite pre-reduced pellets. Wherein the temperature of the vanadium titano-magnetite oxidized pellet hot-charged into the upper sealing tank of the hydrogen-based shaft furnace is 1000-1150 ℃; in the pre-reduction process, the molar ratio of hydrogen in the reducing gas is more than or equal to 60 percent, the temperature of the reducing gas is 800 ℃, and the reduction time of the vanadium titano-magnetite oxidized pellets in the hydrogen-based shaft furnace is 70 minutes. The metallization rate of the finally obtained vanadium titano-magnetite pre-reduced pellet is 85%.
(3) Melting and separating in an electric furnace: the obtained vanadium titano-magnetite pre-reduced pellets are hot charged into an electric furnace at 600-650 ℃, 70kg of petroleum coke is added into ton iron at 1600 ℃, deep reduction melting is carried out, the melting time is 40min, vanadium-containing molten iron and titanium-containing slag are obtained through separation, and the components of the vanadium-containing molten iron are as follows: [ Fe]94.95％，[C]3.51％，[V]0.48％，[Si]0.30%; tiO in titanium-containing slag 2 The mass percentage is 48.27%. Blowing oxygen into vanadium-containing molten iron to obtain molten steel and vanadium slag; the titanium slag is used as a raw material of titanium white for recycling.
In the whole process, the utilization rate of iron, vanadium and titanium reaches 92%,79% and 80%. The electricity used by the electric furnace is calculated according to the carbon emission factor of China, and the rest materials are calculated according to the greenhouse gas emission accounting method and report guidelines (trial) of China iron and steel production enterprises, so that the carbon emission of ton vanadium-containing molten iron is 1.42t/t, and the carbon emission of the process of the electric furnace is reduced by 10 percent.
The whole electricity consumption in the process flow adopts green electricity, so that the carbon emission of each ton of vanadium-containing molten iron is 0.76t/t, and is reduced by 51.6% compared with the carbon emission of the existing blast furnace flow.
Example 2
The method for efficiently utilizing vanadium titano-magnetite with low carbon in the embodiment comprises the following specific processes:
(1) Preparing oxidized pellets: the vanadium titano-magnetite and the dust mud are subjected to surface modification by a high-pressure roller mill to ensure that the specific surface areas of the vanadium titano-magnetite and the dust mud reach 1570cm respectively 2 /g、1730cm 2 Uniformly mixing vanadium-titanium magnetite concentrate (dry basis), shaft furnace dust mud (dry basis), binder (dry basis) and water according to the mass percentage of 88.34:2.68:1.48:7.5, pelletizing, drying, preheating and roasting the obtained vanadium-titanium magnetite green pellets in a belt conveyor at the drying temperature of 240-310 ℃ for 4.5min, preheating at the preheating temperature of 950-1050 ℃ for 12min, roasting at the roasting temperature of 1150 ℃ for 25min, wherein the oxygen content in hot air is 16.5-17.5%, and obtaining vanadium-titanium magnetite oxidized pellets with the compression strength of 1930N/g and the chemical components of: TFe:53.23%, feO:0.45%, siO 2 ：3.96％，V 2 O 5 ：0.55％，TiO 2 ：1.03％，S：0.04％；
(2) Reduction of hydrogen-based shaft furnace: the vanadium titano-magnetite oxidized pellet is thermally filled into an upper sealing tank at the top of a hydrogen-based vertical furnace, and N is introduced into the upper sealing tank 2 The high-temperature purging and deoxidizing process is completed by water vapor or high-temperature flue gas, so that the oxygen content in the gas of the upper sealing tank is less than or equal to 1wt%; then the hot vanadium titano-magnetite oxidized pellets enter a lower sealing tank, and hydrogen or hydrogen-rich gas is adopted in the lower sealing tank for pressurization, wherein the pressure reaches 0.2-0.5 MPa; and then the pellets are thermally filled into a hydrogen-based shaft furnace, and the pre-reduction is carried out by adopting hydrogen or hydrogen-rich gas as reducing gas to obtain vanadium titano-magnetite pre-reduced pellets. Wherein the temperature of the vanadium titano-magnetite oxidized pellet hot-charged into the upper sealing tank of the hydrogen-based shaft furnace is 1050-1150 ℃; in the pre-reduction process, the molar ratio of hydrogen in the reducing gas is more than or equal to 80 percent, the temperature of the reducing gas is 900 ℃, and the reduction time of the vanadium titano-magnetite oxidized pellets in the hydrogen-based shaft furnace is 65 minutes. The metallization rate of the finally obtained vanadium titano-magnetite pre-reduced pellet is 88%.
(3) Melting and separating in an electric furnace: the obtained vanadium titano-magnetite pre-reduced pellet is hot charged into an electric furnace at 650-700 ℃ and ton iron is charged at 1600 DEG C60kg of petroleum coke and 25kg of fine quicklime, and carrying out deep reduction melting for 40min to obtain vanadium-containing molten iron and titanium-containing slag, wherein the vanadium-containing molten iron comprises the following components: [ Fe]95.12％，[C]3.23％，[V]0.49％，[Si]0.40%; tiO in titanium-containing slag 2 The mass percentage is 45.12%. Blowing oxygen into vanadium-containing molten iron to obtain molten steel and vanadium slag; the titanium slag is used as a raw material of titanium white for recycling.
In the whole process, the utilization rate of iron, vanadium and titanium reaches 91%,80% and 74%. The electricity used by the electric furnace is calculated according to the carbon emission factor of China, and the rest materials are calculated according to the greenhouse gas emission accounting method and report guidelines (trial) of China iron and steel production enterprises, so that the carbon emission of ton of vanadium-containing molten iron is 1.28t/t, and the carbon emission is reduced by 19.0% compared with the carbon emission of 1.58t/t of a blast furnace process.
The whole electricity consumption in the process flow adopts green electricity, so that the carbon emission of each ton of vanadium-containing molten iron is 0.62t/t, and is reduced by 60.8% compared with the carbon emission of the existing blast furnace flow.
It will be appreciated by persons skilled in the art that the above embodiments are provided for illustration only and not for limitation of the invention, and that variations and modifications of the above described embodiments are intended to fall within the scope of the claims of the invention as long as they fall within the true spirit of the invention.
Claims (11)
1. The method for efficiently utilizing vanadium titano-magnetite with low carbon is characterized by comprising the following steps of:
s1, roasting by a belt type machine, respectively carrying out surface modification on vanadium-titanium magnetite concentrate and hydrogen-based shaft furnace top dust mud, and uniformly mixing the surface modified vanadium-titanium magnetite concentrate, binder and water to obtain vanadium-titanium magnetite green pellets; the raw pellets of the vanadium titano-magnetite enter a belt conveyor to be dried, preheated and roasted to obtain oxidized pellets of the vanadium titano-magnetite;
s2, pre-reducing the hydrogen-based shaft furnace, and thermally loading the vanadium titano-magnetite oxidized pellets into the hydrogen-based shaft furnace for pre-reducing to obtain vanadium titano-magnetite pre-reduced pellets;
s3, melting in an electric furnace, namely, hot charging the vanadium titano-magnetite pre-reduced pellets into the electric furnace, adding a flux and low ash coal or low sulfur petroleum coke, and carrying out deep reduction, melting and slag-iron separation to obtain vanadium-containing molten iron and titanium-containing slag; the vanadium-containing molten iron is subjected to oxygen blowing refining to obtain molten steel and vanadium slag; the titanium-containing slag is used as a raw material of titanium dioxide.
2. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 1, wherein in step S1:
the vanadium-titanium magnetite concentrate and the top dust mud of the hydrogen-based shaft furnace are subjected to surface modification treatment by fine grinding and high-pressure roller grinding; and/or
The surface modification treatment of the vanadium-titanium magnetite concentrate and the hydrogen-based shaft furnace top dust mud shows that the specific surface area is 1500-2000 cm 2 /g; and/or
In the vanadium-titanium magnetite concentrate, the TFe content is more than or equal to 52wt%, the titanium content is more than or equal to 9wt%, the vanadium content is 0.3-1.5 wt%, and the SiO is 2 The content is 2.5 to 3.5 weight percent; and/or
In the top dust mud of the hydrogen-based shaft furnace, the TFe content is more than or equal to 60wt percent, V 2 O 5 ≥0.3wt％，TiO 2 More than or equal to 10wt%; and/or
More than 70% of the vanadium-titanium magnetite concentrates have the granularity of-0.074 mm; more than 70% of the top dust mud of the hydrogen-based shaft furnace has a granularity of-0.074 mm; and/or
After the surface modification treatment of the vanadium-titanium magnetite concentrate and the hydrogen-based shaft furnace top dust mud, the specific surface area is more than or equal to 1500cm 2 /g; and/or
The top dust mud of the hydrogen-based shaft furnace accounts for 1.0-3.0 wt% of the total materials; the binder accounts for 0.5 to 1.5 weight percent of the total materials; the water accounts for 6.0 to 9.0 weight percent of the total materials; and/or
The binder is one or more selected from bentonite, an organic binder and a composite binder; and/or
The diameter of the raw pellet of the vanadium titano-magnetite is 8-12 mm.
3. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 2, wherein in the step S1, the TFe content in the vanadium titano-magnetite concentrate is not less than 55wt%, titanium content is more than or equal to 10wt%, siO 2 The content is 2.5 to 3.0 weight percent.
4. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 1, wherein in step S1:
the belt conveyor adopts one or more of hydrogen, natural gas, coke oven gas or biomass pyrolysis gas as fuel; the thickness of the material layer in the belt conveyor is 400-600 mm; and/or
In the drying process, the drying temperature is 180-400 ℃; and/or
In the preheating process, the preheating temperature is 900-1050 ℃; and/or
In the roasting process, the roasting temperature is 1000-1200 ℃ and the roasting time is 20-60 min; and/or
In the roasting process of the belt conveyor, the oxygen content in the hot air is 15-19 wt%; and/or
The compressive strength of the vanadium titano-magnetite oxidized pellet is 1700-2000N/pellet.
5. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 4, wherein in step S1:
in the roasting process, the roasting temperature is 1050-1150 ℃ and the roasting time is 25-40 min; and/or
In the roasting process of the belt conveyor, the oxygen content in the hot air is 16-18 wt%.
6. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 1, wherein in the step S2, the specific procedure of pre-reduction of the hydrogen-based shaft furnace is as follows:
the vanadium titano-magnetite oxidized pellet is thermally filled into an upper sealing tank at the top of a hydrogen-based vertical furnace, and N is arranged in the upper sealing tank 2 The high-temperature purging and deoxidizing process is completed by water vapor or high-temperature flue gas, so that the oxygen content in the gas of the upper sealed tank is less than or equal to 1wt%; the hot vanadium titano-magnetite oxidized pellets then enter a lower sealing tank where they are sealedThe sealing tank is pressurized by adopting hydrogen or hydrogen-rich gas, and the pressure reaches 0.2-0.5 MPa; and then, thermally loading the pellets into a hydrogen-based shaft furnace, and pre-reducing the pellets by taking hydrogen or hydrogen-rich gas as reducing gas to obtain the vanadium titano-magnetite pre-reduced pellets.
7. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 6, wherein in step S2:
the temperature of the vanadium titano-magnetite oxidized pellet hot-charged into the upper sealing tank of the hydrogen-based shaft furnace is 900-1150 ℃; and/or
In the pre-reduction process, the molar ratio of hydrogen in the reducing gas is more than or equal to 60%, and the temperature of the reducing gas is 600-1000 ℃; and/or
In the pre-reduction process, the reduction time of the vanadium titano-magnetite oxidized pellet in the hydrogen-based shaft furnace is 1-3 h; and/or
In the pre-reduction process, the metallization rate of the vanadium titano-magnetite pre-reduced pellet is 70-90%.
8. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 7, wherein in step S2:
the temperature of the vanadium titano-magnetite oxidized pellet hot-charged into the upper sealing tank of the hydrogen-based shaft furnace is 1000-1150 ℃; and/or
In the pre-reduction process, the metallization rate of the vanadium titano-magnetite pre-reduced pellet is 82-90%.
9. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 1, wherein in step S3:
the temperature of the vanadium titano-magnetite pre-reduced pellets is 500-700 ℃ when the pellets are hot-charged into the electric furnace; and/or
In the melting process of the electric furnace, the melting temperature is 1550-1700 ℃; and/or
In the melting process of the electric furnace, tiO in the titanium-containing slag 2 The content of (2) is more than or equal to 40wt%; and/or
The vanadium-containing molten iron comprises the following components: TFe: > 92%, C: 2-5%, V: 0.2% or more, si: less than or equal to 1.2 percent, and the balance is unavoidable impurities in percentage by mass.
10. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to claim 9, wherein in step S3:
in the melting process of the electric furnace, the melting temperature is 1580-1650 ℃; and/or
In the melting process of the electric furnace, tiO in the titanium-containing slag 2 The content of (C) is 45-49 wt%.
11. The method for low-carbon and high-efficiency utilization of vanadium titano-magnetite according to any one of claims 1 to 10, wherein the utilization rate of iron in the vanadium titano-magnetite is 90% or more, the utilization rate of vanadium is 75% or more, and the utilization rate of titanium is 70% or more.
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