CN115058606A - Method for reducing aluminum consumption of per ton vanadium iron smelting product - Google Patents
Method for reducing aluminum consumption of per ton vanadium iron smelting product Download PDFInfo
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- CN115058606A CN115058606A CN202210871116.7A CN202210871116A CN115058606A CN 115058606 A CN115058606 A CN 115058606A CN 202210871116 A CN202210871116 A CN 202210871116A CN 115058606 A CN115058606 A CN 115058606A
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- 238000003723 Smelting Methods 0.000 title claims abstract description 74
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 57
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 101
- 230000009467 reduction Effects 0.000 claims abstract description 92
- 239000002893 slag Substances 0.000 claims abstract description 60
- 229910000628 Ferrovanadium Inorganic materials 0.000 claims abstract description 49
- 238000007670 refining Methods 0.000 claims abstract description 49
- 229910052742 iron Inorganic materials 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 42
- 239000007921 spray Substances 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000012360 testing method Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 49
- 238000005507 spraying Methods 0.000 claims description 32
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 14
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 14
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000571 coke Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 7
- 238000001465 metallisation Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 230000002222 downregulating effect Effects 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 abstract description 28
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 description 76
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/02—Light metals
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
- C22B9/103—Methods of introduction of solid or liquid refining or fluxing agents
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- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of ferrovanadium smelting, and discloses a method for reducing aluminum consumption of a ton of ferrovanadium smelting product, which comprises the following steps: adding a solid additive into the refined tailing clinker, and sequentially mixing and carrying out gas-based pre-reduction to obtain reducing slag containing metallic iron, wherein the gas-based pre-reduction comprises two-stage reduction; preparing materials, and mixing to obtain a mixture for later use; carrying out conventional electro-aluminothermic reduction smelting on the mixture; testing the components of the slag, and adjusting the spray gun until the powder refining agent is completely sprayed; cooling and disassembling the furnace to obtain the ferrovanadium alloy. The invention is based on TiCl 4 Two-step reduction method for smelting ferrovanadium from refined tailingsReduce TiCl 4 The method for smelting vanadium, iron and aluminum by using the refined tailings has the advantages that the vanadium smelting yield is improved by 0.19-0.39 percentage points, and the aluminum consumption per ton of product is reduced by 11-25kg per ton of vanadium and iron.
Description
Technical Field
The invention specifically relates to the technical field of ferrovanadium smelting, and specifically relates to a method for reducing aluminum consumption of a ton product in ferrovanadium smelting.
Background
TiCl 4 The refined tailings containing vanadium are vanadium-containing tailings, are vanadium-removing products from a titanium extraction production line of blast furnace slag, have the advantages of high vanadium content, low impurity content and the like, and are generally used as ferrovanadium smelting raw materials to be mixed with vanadium flakes for ferrovanadium smelting after high-temperature roasting decarburization and dechlorination treatment. TiCl (titanium dioxide) 4 In the process of preparing clinker by roasting the refined tailings at the high temperature of 500-600 ℃, vanadium in the refined tailings is basically changed into V 2 O 5 Wherein the iron is substantially Fe 2 O 3 The form exists. With TiCl 4 When the refined tailing clinker is used for smelting ferrovanadium by an electro-aluminothermic process, a large amount of V exists in the raw materials 2 O 5 And Fe 2 O 3 And when metallic aluminum is used as a reducing agent, a drastic thermite reduction reaction inevitably occurs: 3V 2 O 5 +4Al＝3V 2 O 3 +2Al 2 O 3 、Fe 2 O 3 +3Al＝2Fe+Al 2 O 3 Thereby consuming a large amount of metallic aluminum reducing agent and causing the consumption of aluminum for smelting per ton of ferrovanadium to be increased.
The patent: a method for preparing a ferrovanadium alloy from titanium tetrachloride refining tailings (application number CN202110184317.5), and discloses a method for preparing a ferrovanadium alloy from titanium tetrachloride refining tailings. The method comprises the following steps: (1) crushing and grinding titanium tetrachloride refining tailings, and oxidizing and roasting in a rotary kiln to obtain vanadium-containing roasting clinker; (2) uniformly mixing vanadium-containing roasting clinker, vanadium oxide, iron particles, a reducing agent, a slagging agent and a heating agent to obtain a ferrovanadium smelting mixture, and uniformly distributing the ferrovanadium smelting mixture in a smelting furnace for smelting; (3) after smelting is finished, after the furnace body, slag and gold are naturally cooled, the furnace is disassembled, and the slag and the gold are separated, so that the ferrovanadium cake and the smelting slag are obtained. According to the method, titanium tetrachloride refined tailings are roasted to obtain vanadium-containing roasted clinker, and vanadium oxide is used as a mixed vanadium-containing raw material to be smelted according to an electrothermal reduction process and a self-propagating smelting process.
The invention also belongs to the technical field of ferrovanadium smelting, but different from the invention, the invention aims to solve the problem that the consumption of per ton ferrovanadium and aluminum is increased because the existing refined tailing clinker is directly used for ferrovanadium smelting and the slag-bound metallic aluminum is sprayed in a large amount in the powder injection refining process, and the provided solution is as follows: firstly, the refined tailing clinker is pre-reduced before smelting, and vanadium in the refined tailing is firstly reduced and deoxidized to be V by using cheap (compared with the price of metallic aluminum) reducing gas from the chemical reaction mechanism 2 O 3 Reducing iron oxide in the refined tailings to metallic Fe; secondly, the process of adding potassium chlorate serving as a heating agent is cancelled in the burdening process, so that 3 reaction formulas (3V) are fundamentally eliminated 2 O 5 +4Al＝3V 2 O 3 +2Al 2 O 3 、Fe 2 O 3 +3Al＝2Fe+Al 2 O 3 And KClO 3 +2Al＝KCl+Al 2 O 3 ) The problem of high aluminum consumption in smelting per ton of ferrovanadium is caused, but the vanadium yield is not influenced: thirdly, aiming at the problem that the molten slag wrapped with the metallic aluminum is sprayed outside the furnace in the powder spraying refining link, under the condition that the total powder amount and the spraying pressure are not changed, the thickness change of a slag layer is calculated according to the change of theoretical slag amount, the lowering height of a spray gun is adjusted in time, and the deepening intermittent powder spraying refining is carried out according to the spraying state in the powder spraying process until the refining link is completed.
Disclosure of Invention
The invention aims to provide a method for reducing the aluminum consumption of a ton of ferrovanadium smelting products so as to solve the problems of the prior TiCl smelting method in the background technology 4 The problem of consumption of a large amount of metallic aluminum reducing agent caused by smelting ferrovanadium by refining tailings is solved.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for reducing aluminum consumption of per ton of vanadium iron smelting products comprises the following steps:
s10, adding the solid additive into the refined tailing clinker, mixing and carrying out gas-based pre-reduction successively to obtain the reducing slag containing metallic iron, wherein the gas-based pre-reduction comprises two stages of reduction, wherein:
the first-stage reduction temperature is 800-;
the temperature of the second-stage reduction is 1100-1300 ℃, and the time is 1-2h, and the second-stage reduction is used for reducing the iron oxide in the refined tailing clinker;
s20, according to the content of the reducing slag containing the metallic iron: calcium vanadate: mixing vanadium trioxide at a mass ratio of 120-;
s30, carrying out conventional electro-aluminothermic reduction smelting on the mixture;
s40, performing electric aluminothermic smelting until the TV content in the slag is 1.4% -1.8%, testing the components of the slag, and adjusting the spray gun according to the amount and thickness of the slag under the conditions that the total amount and the blowing pressure of the refining agent are unchanged until the powder refining agent is blown completely;
and S50, cooling and disassembling the furnace to obtain the ferrovanadium alloy.
As a further scheme of the invention: the mass ratio of the solid additive to the refined tailing clinker is 1-30%, wherein the solid additive is vanadium trioxide powder or at least one of ammonium polyvanadate and ammonium metavanadate, and the refined tailing clinker is TiCl 4 And refining the tailings.
As a still further scheme of the invention: in step S10, the reducing gas used in the gas-based pre-reduction is at least one of hydrogen, natural gas, coke oven gas, blast furnace gas, and converter gas.
As a still further scheme of the invention: the reducing gas is coke oven gas.
As a still further scheme of the invention: in step S10, the reduction device used in the gas-based pre-reduction is a reduction kiln or a fluidized bed, and finally the metallic iron-containing reduction slag with the iron metallization rate of 91-99% and the V (III) content of 20-40% is obtained.
As a still further scheme of the invention: in step S20, the mass of the aluminum and iron is obtained by carrying out stoichiometric calculation on the alloy composition requirements according to the national standard GB/T4139-2012.
As a still further scheme of the invention: in step S40, the method of adjusting the spray gun includes: the height of the spray gun, the single powder spraying time and the spraying times are adjusted downwards.
As a still further scheme of the invention: the height of the spray gun is adjusted down to be 0.5-1.0 of the thickness change value of the slag, the time length of single powder spraying is 10-60s, and the spraying frequency is 2-6 times.
Compared with the prior art, the invention has the beneficial effects that:
(1) based on TiCl 4 The process for smelting ferrovanadium by refining tailings through two-step reduction method obtains a method for reducing TiCl 4 The method for smelting vanadium, iron and aluminum consumption by the refined tailings improves the vanadium smelting yield by 0.19 to 0.39 percentage point, and reduces the aluminum consumption per ton of product by 11 to 25kg per ton of vanadium and iron;
(2) the calcium vanadate is used for replacing expensive potassium chlorate serving as a heating agent, so that the raw material cost is reduced.
(3) Considering the change of the slag quantity brought by the pre-reduction of the raw materials, the deepening intermittent powder injection refining is adopted under the condition that the total amount of powder used for powder injection refining and the injection pressure are not changed, and the aluminum consumption caused by splashing is effectively reduced.
Drawings
FIG. 1 is a flow chart of a method for reducing aluminum consumption of per ton of ferrovanadium smelting products.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, in an embodiment of the present invention, a method for reducing aluminum consumption of per ton of vanadium iron smelting products includes the following steps:
s10, adding the solid additive into the refined tailing clinker, mixing and carrying out gas-based pre-reduction successively to obtain reducing slag containing metallic iron, wherein the gas-based pre-reduction comprises two-stage reduction, wherein:
the first-stage reduction temperature is 800 ℃ and the time is 1h, and the first-stage reduction temperature is used for reducing vanadium oxide in the refined tailing clinker;
the temperature of the second-stage reduction is 1100 ℃, the time is 1h, and the second-stage reduction is used for reducing iron oxide in the refined tailing clinker;
step S10 is based on thermophysical coupling idea, utilizes the characteristic that solid additive has high melting point or generates decomposed gas to dilute low melting point substance and prevent a great amount of low melting point substance V in refined tailing clinker in heating process 2 O 5 The melting causes the material to be bonded and agglomerated, and the subsequent reduction process is influenced kinetically
S20, according to the content of the reducing slag containing the metallic iron: calcium vanadate: preparing vanadium trioxide at a mass ratio of 180:80:40, then performing stoichiometric calculation on alloy components according to the requirements of the national standard GB/T4139-2012 to prepare aluminum and iron, and mixing to obtain a mixture for later use;
s30, carrying out conventional electro-aluminothermic reduction smelting on the mixture;
s40, testing the components of the slag when the TV content in the slag is 1.8% through electro-aluminothermic smelting, calculating the amount and thickness of the slag according to a theoretical model under the condition that the total amount of a refining agent and the blowing pressure are not changed, and adjusting a spray gun based on the amount and thickness of the slag until the powder refining agent is blown completely;
and S50, cooling and disassembling the furnace to obtain the ferrovanadium alloy.
In step S10 of the embodiment of the present invention, the mass ratio of the solid additive to the refined tailings clinker is 1%, the solid additive is vanadium trioxide powder, and the refined tailings clinker is TiCl 4 Refining the tailings by TiCl 4 The two-step reduction method for refining the tailings is used for smelting the ferrovanadium, so that the aluminum consumption of smelting per ton of ferrovanadium is reduced.
In step S10 of the embodiment of the present invention, the reducing gas used in the gas-based pre-reduction is coke oven gas.
In step S10 of the embodiment of the present invention, the reduction apparatus used in the gas-based pre-reduction is a reduction kiln or a fluidized bed, and finally the metallic iron-containing reduction slag having an iron metallization rate of 91% and a V (iii) content of 20% is obtained.
In step S40, the method of adjusting the spray gun includes: adjusting the height of the spray gun, the single powder spraying time and the spraying times downwards, wherein: the height of the spray gun is adjusted down to be 0.5 of the thickness change value of the slag, the time of single powder spraying is 10s, the spraying frequency is 6 times until the powder refining agent is sprayed completely and no obvious splashing exists in the whole process.
Example 2
Referring to fig. 1, in an embodiment of the present invention, a method for reducing aluminum consumption of per ton of vanadium iron smelting products includes the following steps:
s10, adding the solid additive into the refined tailing clinker, mixing and carrying out gas-based pre-reduction successively to obtain reducing slag containing metallic iron, wherein the gas-based pre-reduction comprises two-stage reduction, wherein:
the first-stage reduction temperature is 1100 ℃ and the time is 1h, and the first-stage reduction temperature is used for reducing vanadium oxide in the refined tailing clinker;
the temperature of the second-stage reduction is 1300 ℃, the time is 2 hours, and the second-stage reduction is used for reducing iron oxide in the refined tailing clinker;
step S10 is based on thermophysical coupling idea, utilizes the characteristic that solid additive has high melting point or generates decomposed gas to dilute low melting point substance and prevent a great amount of low melting point substance V in refined tailing clinker in heating process 2 O 5 The melting leads the materials to be bonded into a mass, and the subsequent reduction process is influenced kinetically
S20, according to the content of the reducing slag containing the metallic iron: calcium vanadate: proportioning vanadium trioxide at a mass ratio of 120:120:80, then carrying out stoichiometric calculation according to the requirements of the national standard GB/T4139-2012 on alloy components to prepare aluminum and iron, and mixing to obtain a mixture for later use;
s30, carrying out conventional electro-aluminothermic reduction smelting on the mixture;
s40, testing slag components when the TV content in the slag is 1.4%, calculating the slag amount and the slag thickness according to a theoretical model under the condition that the total amount of a refining agent and the blowing pressure are not changed, and adjusting a spray gun based on the slag amount and the slag thickness until the powder refining agent is blown completely;
and S50, cooling and disassembling the furnace to obtain the ferrovanadium alloy.
In step S10 of the embodiment of the present invention, the mass ratio of the solid additive to the refined tailings clinker is 1%, the solid additive is vanadium trioxide powder, and the refined tailings clinker is TiCl 4 Refining the tailings by TiCl 4 The two-step reduction method for refining the tailings is used for smelting the ferrovanadium, so that the aluminum consumption of smelting per ton of ferrovanadium is reduced.
In step S10 of the embodiment of the present invention, the reducing gas used in the gas-based pre-reduction is coke oven gas.
In step S10 of the embodiment of the present invention, the reduction apparatus used in the gas-based pre-reduction is a reduction kiln or a fluidized bed, and finally the metallic iron-containing reduction slag having an iron metallization rate of 99% and a V (iii) content of 20% is obtained.
In step S40, the method of adjusting the spray gun includes: adjusting the height of the spray gun, the single powder spraying time and the spraying times downwards, wherein: the height of the spray gun is adjusted downwards to be 1.0 of the thickness change value of the slag, the single powder spraying time is 60s, and the spraying frequency is 2 times until the powder refining agent is completely sprayed.
Example 3
Referring to fig. 1, in an embodiment of the present invention, a method for reducing aluminum consumption of per ton of vanadium iron smelting products includes the following steps:
s10, adding the solid additive into the refined tailing clinker, mixing and carrying out gas-based pre-reduction successively to obtain the reducing slag containing metallic iron, wherein the gas-based pre-reduction comprises two stages of reduction, wherein:
the first-stage reduction temperature is 800 ℃, the time is 0.5h, and the first-stage reduction is used for reducing vanadium oxide in the refined tailing clinker;
the temperature of the second-stage reduction is 1100 ℃, the time is 1h, and the second-stage reduction is used for reducing iron oxide in the refined tailing clinker;
step S10 is based on thermophysical coupling idea, utilizes the characteristic that solid additive has high melting point or generates decomposed gas to dilute low melting point substance and prevent a great amount of low melting point substance V in refined tailing clinker in heating process 2 O 5 The melting causes the material to be bonded and agglomerated, and the subsequent reduction process is influenced kinetically
S20, according to the content of the reducing slag containing the metallic iron: calcium vanadate: proportioning vanadium trioxide at a mass ratio of 150:100:60, then carrying out stoichiometric calculation according to the requirements of the national standard GB/T4139-2012 on alloy components to prepare aluminum and iron, and mixing to obtain a mixture for later use;
s30, carrying out conventional electro-aluminothermic reduction smelting on the mixture;
s40, testing the components of the slag when the TV content in the slag is 1.6% through electro-aluminothermic smelting, calculating the amount and thickness of the slag according to a theoretical model under the condition that the total amount of a refining agent and the blowing pressure are not changed, and adjusting a spray gun based on the amount and thickness of the slag until the powder refining agent is blown completely;
and S50, cooling and disassembling the furnace to obtain the ferrovanadium alloy.
In step S10 of the embodiment of the present invention, the mass ratio of the solid additive to the refined tailing clinker is 30%, the solid additive is ammonium polyvanadate, and the refined tailing clinker is TiCl 4 Refining the tailings by TiCl 4 The two-step reduction method for refining the tailings is used for smelting the ferrovanadium, so that the aluminum consumption of smelting per ton of ferrovanadium is reduced.
In step S10 of the embodiment of the present invention, the reducing gas used in the gas-based pre-reduction is coke oven gas.
In step S10 of the embodiment of the present invention, the reduction apparatus used in the gas-based pre-reduction is a reduction kiln or a fluidized bed, and finally the metallic iron-containing reduction slag having an iron metallization rate of 95% and a V (iii) content of 30% is obtained.
In step S40, the method of adjusting the spray gun includes: adjusting the height of the spray gun, the single powder spraying time and the spraying times downwards, wherein: the height of the spray gun is adjusted downwards to be 1.0 of the thickness change value of the slag, the single powder spraying time is 35s, and the spraying frequency is 4 times until the powder refining agent is completely sprayed.
Example 4
Referring to fig. 1, in an embodiment of the present invention, a method for reducing aluminum consumption of per ton of vanadium iron smelting products includes the following steps:
s10, adding the solid additive into the refined tailing clinker, mixing and carrying out gas-based pre-reduction successively to obtain the reducing slag containing metallic iron, wherein the gas-based pre-reduction comprises two stages of reduction, wherein:
the first-stage reduction temperature is 1100 ℃ and the time is 1h, and the first-stage reduction temperature is used for reducing vanadium oxide in the refined tailing clinker;
the temperature of the second-stage reduction is 1300 ℃, the time is 2 hours, and the second-stage reduction is used for reducing iron oxide in the refined tailing clinker;
step S10 is based on the concept of thermophysical coupling, and utilizes the characteristic that solid additive has high melting point or generates decomposed gas to dilute low-melting-point substances and prevent a great amount of low-melting-point substances V in the refined tailing clinker in the heating process 2 O 5 The melting leads the materials to be bonded into a mass, and the subsequent reduction process is influenced kinetically
S20, according to the weight percentage of the reducing slag containing the metallic iron: calcium vanadate: preparing materials according to the mass ratio of 180:120:60 of vanadium trioxide, then performing stoichiometric calculation on the alloy component according to the national standard GB/T4139-2012 to prepare aluminum and iron, and mixing to obtain a mixture for later use;
s30, carrying out conventional electro-aluminothermic reduction smelting on the mixture;
s40, testing the components of the slag when the TV content in the slag is 1.4% through electro-aluminothermic smelting, calculating the amount and thickness of the slag according to a theoretical model under the condition that the total amount of a refining agent and the blowing pressure are not changed, and adjusting a spray gun based on the amount and thickness of the slag until the powder refining agent is blown completely;
and S50, cooling, and removing the furnace to obtain the ferrovanadium alloy.
In step S10 of the embodiment of the present invention, the mass ratio of the solid additive to the refined tailings clinker is 30%, the solid additive is ammonium metavanadate, and the refined tailings clinker is TiCl 4 Refining the tailings by TiCl 4 The two-step reduction method for refining the tailings is used for smelting the ferrovanadium, so that the aluminum consumption of smelting per ton of ferrovanadium is reduced.
In step S10 of the embodiment of the present invention, the reducing gas used in the gas-based pre-reduction is coke oven gas.
In step S10 of the embodiment of the present invention, the reduction apparatus used in the gas-based pre-reduction is a reduction kiln or a fluidized bed, and finally the reduced slag containing metallic iron with 99% iron metallization and 40% V (iii) content is obtained.
In step S40 of the embodiment of the present invention, the method of adjusting the spray gun includes: adjusting the height of the spray gun, the single powder spraying time and the spraying times downwards, wherein: the height of the spray gun is adjusted down to be 0.5 of the thickness change value of the slag, the time of single powder spraying is 10-35s, and the spraying frequency is 2 times until the powder refining agent is completely sprayed.
Comparative example 1
Refining tailings clinker: calcium vanadate: vanadium trioxide: metal aluminum: metallic iron 120:120:80, then carrying out aluminum preparation and iron preparation according to the requirements of the national standard GB/T4139-2012 on the alloy components, and obtaining a mixture for later use after mixing; the mixture is used for conventional electro-aluminothermic reduction smelting and powder injection refining, and the splashing is serious.
Comparative example 2
Refining the tailing clinker: calcium vanadate: vanadium trioxide: metal aluminum: metallic iron 120:120:80, then carrying out aluminum preparation and iron preparation according to the requirements of the national standard GB/T4139-2012 on the alloy components, and obtaining a mixture for later use after mixing; the mixture is used for conventional electro-aluminothermic reduction smelting and powder injection refining, and the splashing is serious.
Comparative example 3
Refining tailings clinker: calcium vanadate: vanadium trioxide: metal aluminum: 150 parts of metallic iron: 100:60, then aluminum and iron are mixed according to the requirements of national standard GB/T4139-2012 for the alloy components, and a mixture is obtained for later use after mixing; the mixture is used for conventional electro-aluminothermic reduction smelting and constant-spraying powder refining, and splashing is serious.
Comparative example 4
Refining tailings clinker: calcium vanadate: vanadium trioxide: metal aluminum: 180 parts of metallic iron: 120:60, then carrying out aluminum preparation and iron preparation according to the requirements of the national standard GB/T4139-; the mixture is used for conventional electro-aluminothermic reduction smelting and powder injection refining, and the splashing is serious.
Test example 1
The vanadium smelting yield and the aluminum consumption per ton of the product after the completion of the conventional smelting in examples 1 to 4 and comparative examples 1 to 4 were measured.
The method for measuring the vanadium smelting yield comprises the following steps: the percentage of the ratio of the total vanadium element in the finished ferrovanadium alloy to the total vanadium element brought by the vanadium-containing oxide;
the method for measuring the aluminum consumption of the ton product comprises the following steps: the ratio of the consumption of the aluminum reducing agent in a single furnace to the mass of the ferrovanadium alloy cake;
statistics is carried out on smelting conditions of different heats in examples 1-4 and comparative examples 1-4, and it is found that indexes of the examples of the invention are relatively good, and relevant comparative data are shown in table 1:
TABLE 1
| Item | Vanadium smelting yield/% | Per kg of consumption of vanadium, iron and aluminum |
| Example 1 | 97.04 | 564 |
| Example 2 | 97.02 | 553 |
| Example 3 | 97.01 | 559 |
| Example 4 | 97.03 | 562 |
| Comparative example 1 | 96.85 | 572 |
| Comparative example 2 | 96.74 | 578 |
| Comparative example 3 | 96.79 | 577 |
| Comparative example 4 | 96.64 | 573 |
The results in Table 1 show that the vanadium smelting yield is improved by 0.19-0.39 percentage points and the aluminum consumption per ton of product is reduced by 11-25kg per ton of ferrovanadium by adopting the method of the invention.
In conclusion, the invention is based on TiCl 4 The process for smelting ferrovanadium by refining tailings through two-step reduction method obtains a method for reducing TiCl 4 The method for smelting vanadium, iron and aluminum consumption by refined tailings has the advantages that the vanadium smelting yield is improved by 0.19-0.39 percentage point, the aluminum consumption per ton of product is reduced by 11-25kg per ton of ferrovanadium, the calcium vanadate is used for replacing expensive heating agent potassium chlorate, the raw material cost is reduced, the change of slag amount caused by the pre-reduction of the raw material is considered, and the deepening intermittent powder spraying refining is adopted under the conditions that the total amount of powder used for powder spraying refining and the spraying pressure are not changed, so that the aluminum consumption caused by spraying is effectively reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A method for reducing aluminum consumption of a ton of ferrovanadium smelting products is characterized by comprising the following steps:
s10, adding the solid additive into the refined tailing clinker, mixing and carrying out gas-based pre-reduction successively to obtain the reducing slag containing metallic iron, wherein the gas-based pre-reduction comprises two stages of reduction, wherein:
the first-stage reduction temperature is 800-;
the temperature of the second-stage reduction is 1100-1300 ℃, and the time is 1-2h, and the second-stage reduction is used for reducing the iron oxide in the refined tailing clinker;
s20, according to the content of the reducing slag containing the metallic iron: calcium vanadate: mixing vanadium trioxide at a mass ratio of 120-180:80-120:40-80, adding aluminum and iron during mixing, and mixing to obtain a mixture for later use;
s30, carrying out conventional electro-aluminothermic reduction smelting on the mixture;
s40, performing electric aluminothermic smelting until the TV content in the slag is 1.4% -1.8%, testing the components of the slag, and adjusting the spray gun according to the amount and thickness of the slag under the conditions that the total amount and the blowing pressure of the refining agent are unchanged until the powder refining agent is blown completely;
and S50, cooling and disassembling the furnace to obtain the ferrovanadium alloy.
2. The method for reducing the aluminum consumption of per-ton vanadium iron smelting products according to claim 1, wherein the mass ratio of the solid additive to the refined tailing clinker is 1% -30%, and the mass ratio isIn the method, the solid additive is vanadium trioxide powder or at least one of ammonium polyvanadate and ammonium metavanadate, and the refined tailing clinker is TiCl 4 And refining the tailings.
3. The method for reducing the aluminum consumption of per-ton products from ferrovanadium smelting according to claim 1, wherein in step S10, the reducing gas used in the gas-based pre-reduction is at least one of hydrogen, natural gas, coke oven gas, blast furnace gas or converter gas.
4. The method for reducing the aluminum consumption of per-ton vanadium iron smelting products according to claim 3, wherein the reducing gas is coke oven gas.
5. The method for reducing the aluminum consumption of per ton of ferrovanadium products according to claim 1, wherein in step S10, the reduction device used in the gas-based pre-reduction is a reduction kiln or a fluidized bed, and finally the metallic iron-containing reduction slag with the iron metallization rate of 91-99% and the V (iii) content of 20-40% is obtained.
6. The method for reducing the aluminum consumption of a ton of vanadium iron smelting products according to claim 1, wherein in the step S20, the mass of the aluminum and iron is calculated according to the stoichiometric requirement of the national standard GB/T4139-2012 on the alloy components.
7. The method for reducing the aluminum consumption of the ferrovanadium ton products according to claim 1, wherein in the step S40, the manner of adjusting the spray gun comprises the following steps: the height of the spray gun, the single powder spraying time and the spraying times are adjusted downwards.
8. The method for reducing the aluminum consumption of a ferrovanadium ton product according to claim 7 wherein the height of the down-regulating lance is 0.5 to 1.0 of the value of the variation in slag thickness.
9. The method for reducing the aluminum consumption of a ferrovanadium ton product according to claim 8, wherein the time of single powder injection of the spray gun is 10-60 s.
10. The method for reducing the aluminum consumption of the ferrovanadium ton products according to claim 9, wherein the number of times of blowing of the lance is 2 to 6 times.
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| CN101100720A (en) * | 2007-08-22 | 2008-01-09 | 攀枝花新钢钒股份有限公司 | Production process for smelting ferrovanadium by calcium vanadate |
| CN102115821A (en) * | 2010-09-13 | 2011-07-06 | 攀钢集团钢铁钒钛股份有限公司 | Method for smelting ferrovanadium |
| CN103045928A (en) * | 2012-12-31 | 2013-04-17 | 攀钢集团西昌钢钒有限公司 | Method for producing ferrovanadium by aluminothermic process |
| CN112981141A (en) * | 2021-02-08 | 2021-06-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing ferrovanadium alloy from titanium tetrachloride refining tailings |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101100720A (en) * | 2007-08-22 | 2008-01-09 | 攀枝花新钢钒股份有限公司 | Production process for smelting ferrovanadium by calcium vanadate |
| CN102115821A (en) * | 2010-09-13 | 2011-07-06 | 攀钢集团钢铁钒钛股份有限公司 | Method for smelting ferrovanadium |
| CN103045928A (en) * | 2012-12-31 | 2013-04-17 | 攀钢集团西昌钢钒有限公司 | Method for producing ferrovanadium by aluminothermic process |
| CN112981141A (en) * | 2021-02-08 | 2021-06-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing ferrovanadium alloy from titanium tetrachloride refining tailings |
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