CN115821070A - Method for extracting vanadium by oxidizing molten iron - Google Patents
Method for extracting vanadium by oxidizing molten iron Download PDFInfo
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- CN115821070A CN115821070A CN202211556097.5A CN202211556097A CN115821070A CN 115821070 A CN115821070 A CN 115821070A CN 202211556097 A CN202211556097 A CN 202211556097A CN 115821070 A CN115821070 A CN 115821070A
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- carbon dioxide
- mixed gas
- molten iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 121
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000001590 oxidative effect Effects 0.000 title claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 168
- 239000007789 gas Substances 0.000 claims abstract description 97
- 238000007664 blowing Methods 0.000 claims abstract description 90
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 84
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 84
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 20
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 239000002912 waste gas Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 20
- 230000003647 oxidation Effects 0.000 abstract description 19
- 239000002826 coolant Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- -1 sodium vanadates Chemical class 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
The invention provides a method for extracting vanadium from molten iron through oxidation, which comprises the following steps: carrying out top-bottom combined blowing on the vanadium-containing molten iron, and adding sodium salt in the top-bottom combined blowing process to form sodium vanadium slag; in the top-bottom combined blowing process, the gas used for top blowing is a first mixed gas, and the gas used for bottom blowing is a second mixed gas; the first mixed gas comprises carbon dioxide and oxygen; the second mixed gas comprises carbon dioxide and oxygen. In the process of extracting vanadium from molten iron, the mixed gas of carbon dioxide and oxygen is blown at the top, the mixed gas of carbon dioxide and oxygen is blown at the bottom, and the weak oxidizability of carbon dioxide is utilized to replace part of oxygen to participate in the reaction, so that the effect of extracting vanadium and protecting carbon is achieved without adding a coolant.
Description
Technical Field
The invention relates to the technical field of ferrous metallurgy, relates to a method for extracting vanadium, and particularly relates to a method for extracting vanadium by oxidizing molten iron.
Background
Vanadium is used as an important metal resource, has good stability and fatigue resistance, is widely applied to the fields of steel industry, electronic industry, chemical industry, medicine, aerospace and the like, is distributed and dispersed in nature, has no independently recoverable vanadium substance, is obtained from vanadium-titanium magnetite in 88 percent in the world, is usually obtained from vanadium-containing molten iron through a blast furnace or other iron making processes, and is blown into a converter to oxidize and enrich vanadium in metal into a slag phase.
In the process of vanadium extraction in a converter, a large amount of heat is generated by oxidation of elements such as silicon, manganese, vanadium and carbon in molten iron, so that the temperature in the converter is increased rapidly, and the conversion temperature of carbon and vanadium is easily exceeded in a short time, thereby restricting the oxidation of vanadium elements, accelerating the reaction consumption of carbon elements, resulting in too short vanadium extraction period and reduced vanadium yield. In the prior art, a proper amount of coolant is usually added in the reaction process, and the rising trend of the temperature of a molten pool is adjusted so as to enable vanadium to be in a low-temperature oxidation zone, thereby achieving the purposes of extracting vanadium and protecting carbon.
CN104060015A discloses a vanadium extraction process of a high-silicon vanadium-containing molten iron converter, which comprises the steps of blowing the high-silicon vanadium-containing molten iron in the converter, and adding a coolant in the blowing process, wherein the dosage of the coolant is 30-37kg/t of the high-silicon vanadium-containing molten iron, and the coolant contains 40-50% of Fe 2 O 3 40-50% FeO and 10-20% SiO 2 . The vanadium slag obtained by the technical scheme is high in grade, the carbon content of the obtained semisteel is high, and the temperature of the semisteel can meet the follow-up steelmaking requirement. However, the method has the disadvantages of high coolant consumption, unnecessary waste and increased extraction cost.
CN104073587A discloses a method for vanadium extraction in a converter, wherein a first coolant is added to the converter bath at the beginning of or before the top lance oxygen blowing phase and a second coolant is added to the converter bath at the time of 100-140s of vanadium extraction; the cooling agent comprises at least one of a cold pressing block, a pig iron block, an iron scale and a pellet, wherein the cold pressing block is a pellet formed by pressing converter dust and/or the iron scale through a binder. The coolant is added step by step, so that the use amount of the coolant in the blowing process can be reduced, but the requirements on process control and flow safety are high.
CN104831091A discloses a method for extracting vanadium in a combined blown converter, which is to add a coolant before blowing, blow a mixed gas of oxygen and carbon dioxide into molten iron through an oxygen lance, blow carbon monoxide or a mixed gas of carbon monoxide and nitrogen into the molten iron through a furnace bottom, and utilize the oxidation-reduction balance relationship among carbon, carbon monoxide and carbon dioxide, thereby optimizing the resource utilization rate and reducing the production cost.
Therefore, it is necessary to provide a method for extracting vanadium from molten iron, which does not add a coolant during the process of extracting vanadium from molten iron, and can achieve the purpose of extracting vanadium and protecting carbon.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for extracting vanadium from molten iron by oxidation, which can achieve the aims of extracting vanadium and preserving carbon without adding a coolant in the process of extracting vanadium from molten iron.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for extracting vanadium from molten iron through oxidation, which comprises the following steps:
carrying out top-bottom combined blowing on the vanadium-containing molten iron, and adding sodium salt in the top-bottom combined blowing process to form sodium vanadium slag;
in the top-bottom combined blowing process, the gas used for top blowing is a first mixed gas, and the gas used for bottom blowing is a second mixed gas;
the first mixed gas comprises carbon dioxide and oxygen;
the second mixed gas comprises carbon dioxide and oxygen.
In the process of extracting vanadium from molten iron, the mixed gas of carbon dioxide and oxygen is blown at the top, the mixed gas of carbon dioxide and oxygen is blown at the bottom, and the weak oxidizability of the carbon dioxide is used for replacing part of the oxygen to participate in the reaction, so that vanadium in the molten iron containing vanadium is oxidized to enter a slag phase; the reaction of the carbon dioxide and the vanadium-containing molten iron is an endothermic reaction as a whole, so that the temperature of a fire point area can be effectively reduced, the temperature rise is delayed, and the effects of vanadium extraction and carbon protection are achieved under the condition of not adding a coolant; and the bottom blowing mixed gas enhances the stirring effect, so that the reaction is more complete, and the high-grade sodium vanadium slag is obtained.
Preferably, the mass fraction of vanadium in the vanadium-containing molten iron is 0.3 to 1.2wt%, and may be, for example, 0.3wt%, 0.5wt%, 0.7wt%, 0.9wt%, 1.1wt%, or 1.2wt%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the mass fraction of carbon element in the vanadium-containing molten iron is 3.5-4.8wt%, for example, 3.5wt%, 3.8wt%, 4.1wt%, 4.3wt%, 4.5wt%, or 4.8wt%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the sodium salt comprises any one of sodium carbonate, sodium oxide or sodium sulfate or a combination of at least two of them, typical but non-limiting combinations include sodium carbonate with sodium oxide, sodium oxide with sodium sulfate, sodium carbonate with sodium sulfate, or sodium carbonate, sodium oxide with sodium sulfate.
Preferably, the molar ratio of the sodium element in the sodium salt to the vanadium element in the vanadium-containing molten iron is (1.5-2.5): 1, and may be, for example, 1.5.
Preferably, the sodium salt is added at a time when the top-blowing is completed by 1/3 to 3/5, and may be, for example, 1/3, 2/5, 7/15, 1/2, 8/15 or 3/5, but is not limited to the exemplified values, and other values not exemplified in the numerical range are also applicable.
The sodium salt is added at one time when the top blowing is finished by 1/3-3/5, if the sodium salt is added too early, vanadium in the vanadium-containing molten iron is not completely oxidized and enters a slag phase, so that the consumption of the sodium salt is increased; if the addition is too late, the vanadium conversion rate before the blowing end point is low.
Preferably, the volume content of carbon dioxide in the first mixed gas is 10-30vol%, for example, 10vol%, 15vol%, 20vol%, 25vol% or 30vol%, but not limited to the exemplified values, and other non-exemplified values in the numerical range are also applicable.
Preferably, the volume content of carbon dioxide in the second mixed gas is 10-50vol%, for example, 10vol%, 15vol%, 20vol%, 25vol%, 30vol%, 35vol%, 40vol%, 45vol% or 50vol%, but not limited to the exemplified values, and other non-exemplified values in the numerical range are also applicable.
When the volume content of carbon dioxide in the first mixed gas is 10-30vol%, the temperature of a fire point area is favorably reduced, the temperature rise in the furnace is delayed, the vanadium element is preferentially oxidized, the carbon element is reserved, the purpose of vanadium extraction and carbon preservation is achieved, and meanwhile, the bottom blowing mixed gas enhances the stirring effect, so that the oxidation reaction is more sufficient.
When the volume content of carbon dioxide in the first mixed gas is lower than 10vol%, the temperature in the furnace rises sharply, so that the oxidation of vanadium is restricted, the reaction consumption of carbon is accelerated, the yield of vanadium extraction is reduced, and the carbon oxidation loss is serious; when the volume content of carbon dioxide in the first mixed gas is higher than 30vol%, vanadium in the vanadium-containing molten iron is insufficiently oxidized and cannot completely enter a slag phase, so that the yield of the obtained sodium vanadium slag is low.
Preferably, the air supply intensity of the first mixed air is 2.0-3.5m during the top blowing 3 /(min·t Fe ) For example, it may be 2.0m 3 /(min·t Fe )、2.2m 3 /(min·t Fe )、2.5m 3 /(min·t Fe )、2.8m 3 /(min·t Fe )、3.0m 3 /(min·t Fe )、3.3m 3 /(min·t Fe ) Or 3.5m 3 /(min·t Fe ) But not limited to the exemplified values, other values within the numerical range not exemplified are equally applicable.
Preferably, the first mixture has a mach number of 1.8 to 2.5, for example 1.8, 2.0, 2.2, 2.4 or 2.5, but not limited to the exemplified values, and other values within the range are equally applicable.
When the top blowing is carried out, the first mixed gas is sprayed in from a top-blowing oxygen lance nozzle.
Illustratively, the intake pressure of the first mixed gas is 0.2-1.2MPa in the top blowing; and when bottom blowing is carried out, the air inlet pressure of the second mixed gas is 0.3-1.5MPa.
Preferably, the top-blown converting time is 5-15min, such as 5min, 7min, 9min, 11min, 13min or 15min, but not limited to the exemplified values, and other non-exemplified values within the range of values are equally applicable.
Preferably, the air supply intensity of the second mixed air is 0.1-1m during bottom blowing 3 /(min·t Fe ) For example, it may be 0.1m 3 /(min·t Fe )、0.3m 3 /(min·t Fe )、0.5m 3 /(min·t Fe )、0.8m 3 /(min·t Fe ) Or 1m 3 /(min·t Fe ) But not limited to the exemplified values, other values within the numerical range not exemplified are equally applicable.
Preferably, the blow time of the bottom blowing is 5-10min, such as 5min, 6min, 7min, 8min, 9min or 10min, but not limited to the exemplified values, and other non-exemplified values within the numerical range are equally applicable.
Preferably, the top-bottom blowing temperature is 1300-1400 ℃, for example 1300 ℃, 1330 ℃, 1350 ℃, 1380 ℃ or 1400 ℃, but not limited to the exemplified values, and other non-exemplified values within the range of values are equally applicable.
The reaction vessel for vanadium extraction by iron oxidation in the present invention is not particularly limited, and may be, for example, a converter, a ladle or other devices, and the capacity of the reaction vessel is not particularly limited, and is specifically selected and adjusted according to actual needs.
Preferably, the source of the carbon dioxide in the first mixed gas comprises any one or a combination of at least two of the carbon dioxide separated from steel mill gas recovery, the carbon dioxide treated by other industrial furnace waste gas recovery, or the carbon dioxide in nature, and typical but non-limiting combinations comprise the carbon dioxide separated from steel mill gas recovery and the carbon dioxide treated by other industrial furnace waste gas recovery, the carbon dioxide separated from steel mill gas recovery and the carbon dioxide in nature, and the carbon dioxide treated by other industrial furnace waste gas recovery and the carbon dioxide in nature.
Preferably, the source of carbon dioxide in the second mixed gas comprises any one or a combination of at least two of carbon dioxide separated from steel mill gas recovery, carbon dioxide obtained from other industrial furnace waste gas recovery processes, or carbon dioxide obtained from nature, and typical but non-limiting combinations include carbon dioxide separated from steel mill gas recovery and carbon dioxide obtained from other industrial furnace waste gas recovery processes, carbon dioxide separated from steel mill gas recovery and carbon dioxide obtained from nature, and carbon dioxide obtained from other industrial furnace waste gas recovery processes and carbon dioxide obtained from nature.
As a preferred technical scheme of the method, the method comprises the following steps:
(1) Carrying out top-bottom combined blowing on the vanadium-containing molten iron at 1300-1400 ℃, wherein the mass fraction of vanadium in the vanadium-containing molten iron is 0.3-1.2wt%, and the mass fraction of carbon is 3.5-4.8wt%;
the top blowing gas is a mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 10-30vol%, and the gas supply intensity is 2.0-3.5m 3 /(min·t Fe ) And top-blowing at a flow rate of Mach number 1.8-2.5 for 5-15min; the gas used for bottom blowing is a mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 10-50vol%, and the gas supply intensity is 0.1-1m 3 /(min·t Fe ) Bottom blowing for 5-10min;
(2) The sodium salt is added at one time when the top blowing is finished by 1/3-3/5, and sodium vanadium slag is formed until the top-bottom combined blowing is finished; the sodium salt comprises any one or combination of at least two of sodium carbonate, sodium oxide or sodium sulfate; the molar ratio (1.5-2.5) of the sodium element in the sodium salt to the vanadium element in the vanadium-containing molten iron is 1.
The numerical ranges set forth herein include not only the recited values but also any values between the recited numerical ranges not enumerated herein, and are not intended to be exhaustive or otherwise clear from the intended disclosure of the invention in view of brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
in the process of extracting vanadium from molten iron, the mixed gas of carbon dioxide and oxygen is blown at the top, the mixed gas of carbon dioxide and oxygen is blown at the bottom, and the weak oxidizability of the carbon dioxide is used for replacing part of the oxygen to participate in the reaction, so that the effect of extracting vanadium and protecting carbon is achieved without adding a coolant.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In order to illustrate the technical solution of the present invention, the converter capacity used in the following embodiments is 120t, and the technical solution is not considered to be further limited for convenience of explanation.
Example 1
The embodiment provides a method for extracting vanadium by oxidizing molten iron, which comprises the following steps:
(1) Under the condition of 1350 ℃, carrying out top-bottom combined blowing on the vanadium-containing molten iron, wherein the gas used in the top blowing is the mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 15vol%, and the gas supply intensity is 3.0m 3 /(min·t Fe ) And flow top-blowing for 12min with Mach number of 2.0; the gas used for bottom blowing is a mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 20vol%, and the volume content is 0.7m 3 /(min·t Fe ) Bottom blowing for 8min at the air supply intensity; the top blowing and the bottom blowing are simultaneously started;
(2) And adding sodium carbonate once when 1/2 of the top blowing is finished to form sodium vanadium slag until the top-bottom combined blowing is finished, wherein the molar ratio of sodium in the sodium carbonate to vanadium in the vanadium-containing molten iron is 2.
Example 2
The embodiment provides a method for extracting vanadium by oxidizing molten iron, which comprises the following steps:
(1) Under the condition of 1300 ℃, the vanadium-containing molten iron is blown from top to bottom and blown from top to bottomThe blowing gas is a mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 10vol%, and the gas supply intensity is 3.5m 3 /(min·t Fe ) And top-blown at a flow rate of Mach 2.1 for 15min; the gas used for bottom blowing is a mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 10vol%, and the volume content is 1m 3 /(min·t Fe ) Bottom blowing for 10min; the top blowing and the bottom blowing are simultaneously started;
(2) And sodium oxide is added at one time when 1/3 of the top blowing is finished to form sodium vanadium slag until the top-bottom combined blowing is finished, wherein the molar ratio of sodium in the sodium oxide to vanadium in vanadium-containing molten iron is 2.5.
Example 3
The embodiment provides a method for extracting vanadium by oxidizing molten iron, which comprises the following steps:
(1) Under the condition of 1400 ℃, carrying out top-bottom combined blowing on the vanadium-containing molten iron, wherein the gas used in the top blowing is the mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 30vol%, and the gas supply intensity is 2.5m 3 /(min·t Fe ) And flow top-blown for 5min with Mach number of 1.8; the gas used for bottom blowing is a mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 50vol%, and the volume content is 0.5m 3 /(min·t Fe ) Bottom blowing for 5min with the air supply intensity; the top blowing and the bottom blowing are simultaneously started;
(2) And adding sodium sulfate at one time when the top blowing is finished by 3/5 to form sodium vanadium slag until the top-bottom combined blowing is finished, wherein the molar ratio of sodium in the sodium sulfate to vanadium in the vanadium-containing molten iron is 1.5.
Example 4
This example provides a method for extracting vanadium from molten iron by oxidation, which is the same as example 1 except that the carbon dioxide content in the top-blown mixed gas in step (1) is 5 vol%.
Example 5
This example provides a method for extracting vanadium by oxidizing molten iron, which is the same as example 1 except that the content of carbon dioxide in the top-blown mixed gas in step (1) is 35 vol%.
Example 6
This example provides a method for extracting vanadium by oxidizing molten iron, which is the same as example 1 except that sodium carbonate is added once in step (2) after 1/5 of the top-blown converter is completed.
Example 7
This example provides a method for extracting vanadium by oxidizing molten iron, which is the same as example 1 except that sodium carbonate is added once in step (2) when 4/5 of top-blown converting is completed.
Comparative example 1
The comparative example provides a method for extracting vanadium by oxidizing molten iron, which is the same as the method in the example 1 except that the bottom blowing gas in the step (1) is carbon dioxide.
Comparative example 2
The comparative example provides a method for extracting vanadium by oxidizing molten iron, which is the same as the method in the example 1 except that the bottom blowing gas in the step (1) is oxygen.
Comparative example 3
The comparative example provides a method for extracting vanadium by oxidizing molten iron, and the method is the same as the method in the example 1 except that carbon dioxide in the bottom blowing mixed gas in the step (1) is replaced by nitrogen with the same volume content.
Comparative example 4
The comparative example provides a method for extracting vanadium by oxidizing molten iron, and the method is the same as the method in the example 1 except that the oxygen in the bottom blowing mixed gas in the step (1) is replaced by nitrogen with the same volume content.
Performance testing
For the methods provided in examples 1 to 7 and comparative examples 1 to 4, the carbon content and vanadium content in the vanadium-containing molten iron and semisteel were compared, and the carbon burn-out rate, vanadium oxidation rate, vanadium slag sodium modification rate, and vanadium yield were tested, wherein:
the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, in the method provided by the invention, the carbon burning loss rate is below 20%, the vanadium oxidation rate is above 91%, and the vanadium slag sodium modification rate can reach about 95%, so that high-grade sodium-modified vanadium slag can be obtained, and the vanadium yield is high.
As can be seen from the comparison between examples 4 and 5 and example 1, when the volume content of carbon dioxide in the top-blown mixed gas is less than 10vol%, the temperature in the furnace rises sharply, which restricts the oxidation of vanadium, accelerates the reaction consumption of carbon, reduces the vanadium extraction yield, and causes severe iron oxidation loss; when the volume content of carbon dioxide in the top-blown mixed gas is higher than 30vol%, vanadium in the molten iron is not fully oxidized and cannot completely enter a slag phase, and the yield of the obtained sodium vanadium is low.
As can be seen from the comparison between examples 6 and 7 and example 1, the sodium salt is added once when the top-blowing converting is completed by 1/3 to 3/5, which is beneficial to converting the oxidized vanadium into sodium vanadates, and if the sodium salt is added too early, the vanadium element in the vanadium-containing molten iron is not completely oxidized and enters the slag phase, so that the sodium salt consumption is increased; if the addition is too late, the vanadium yield before the end of the blowing will decrease.
Comparison of comparative examples 1 and 2 with example 1 shows that when the bottom-blowing gas is only carbon dioxide, the vanadium in the molten iron is not completely oxidized, so that the vanadium oxidation rate is reduced and the vanadium loss is serious; when the bottom blowing gas is only oxygen, the temperature rise rate in the furnace is accelerated, the carbon burning loss rate is increased, and the vanadium yield is also reduced.
As can be seen from comparison of comparative examples 3 and 4 with example 1, when the bottom-blown gas is a mixed gas of nitrogen and oxygen, the temperature rise in the furnace is increased, vanadium oxidation is restricted, carbon oxidation is severe, and the carbon content in the semisteel is reduced; when the bottom blowing gas is the mixed gas of carbon dioxide and nitrogen, the vanadium in the molten iron is not completely oxidized, so that the vanadium oxidation rate is reduced, and the vanadium loss is serious.
According to the invention, in the process of vanadium extraction from molten iron, the mixed gas of carbon dioxide and oxygen is blown at the top, and the mixed gas of carbon dioxide and oxygen is blown at the bottom, so that the weak oxidizability of carbon dioxide is utilized to replace part of oxygen to participate in the reaction, thereby being beneficial to delaying the temperature rise of the molten iron in the furnace, improving the vanadium oxidation rate, reducing the carbon burning loss rate, further obtaining high-grade vanadium sodium, and achieving the effect of vanadium extraction and carbon preservation without adding a coolant.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for extracting vanadium by oxidizing molten iron is characterized by comprising the following steps of:
carrying out top-bottom combined blowing on the vanadium-containing molten iron, and adding sodium salt in the top-bottom combined blowing process to form sodium vanadium slag;
in the top-bottom combined blowing process, the gas used for top blowing is a first mixed gas, and the gas used for bottom blowing is a second mixed gas;
the first mixed gas comprises carbon dioxide and oxygen;
the second mixed gas comprises carbon dioxide and oxygen.
2. The method according to claim 1, wherein the mass fraction of vanadium in the vanadium-containing molten iron is 0.3-1.2wt%;
preferably, the mass fraction of carbon element in the vanadium-containing molten iron is 3.5-4.8wt%.
3. The method of claim 1 or 2, wherein the sodium salt comprises any one of sodium carbonate, sodium oxide or sodium sulfate or a combination of at least two thereof;
preferably, the molar ratio of the sodium element in the sodium salt to the vanadium element in the vanadium-containing molten iron (1.5-2.5) is 1;
preferably, the sodium salt is added at a time when the top-blowing is completed by 1/3 to 3/5.
4. A method according to any one of claims 1 to 3, wherein the volume content of carbon dioxide in the first mixed gas is 10 to 30vol%;
preferably, the volume content of the carbon dioxide in the second mixed gas is 10-50vol%.
5. The method according to any one of claims 1 to 4, wherein the intensity of the gas supply of the first mixed gas is 2.0 to 3.5m at the time of the top-blowing 3 /(min·t Fe )；
Preferably, the Mach number of the first mixed gas is 1.8-2.5 in the top-blowing;
preferably, the blowing time of the top blowing is 5-15min.
6. The method according to any one of claims 1 to 5, wherein the second mixed gas is supplied at an intensity of 0.1 to 1m in the bottom-blowing 3 /(min·t Fe )；
Preferably, the converting time of the bottom blowing is 5-10min.
7. The method according to any one of claims 1 to 6, wherein the bottom blowing is started simultaneously with the top blowing;
preferably, the temperature of the top-bottom combined blowing is 1300-1400 ℃.
8. The method according to any one of claims 1 to 7, wherein the source of the carbon dioxide in the first mixed gas comprises any one or a combination of at least two of carbon dioxide separated from steel mill gas recovery, carbon dioxide obtained from other industrial furnace waste gas recovery processes, or carbon dioxide in nature.
9. The method according to any one of claims 1 to 8, wherein the source of the carbon dioxide in the second mixed gas comprises any one or a combination of at least two of carbon dioxide separated from steel mill gas recovery, carbon dioxide obtained from other industrial furnace waste gas recovery processes, or carbon dioxide in nature.
10. A method according to any of claims 1-9, characterized in that the method comprises the steps of:
(1) Carrying out top-bottom combined blowing on the vanadium-containing molten iron at 1300-1400 ℃, wherein the mass fraction of vanadium in the vanadium-containing molten iron is 0.3-1.2wt%, and the mass fraction of carbon is 3.5-4.8wt%;
the top blowing gas is a mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 10-30vol%, and the gas supply intensity is 2.0-3.5m 3 /(min·t Fe ) And top-blowing at a flow rate of Mach number 1.8-2.5 for 5-15min; the gas used for bottom blowing is a mixed gas of carbon dioxide and oxygen, the volume content of the carbon dioxide is 10-50vol%, and the gas supply intensity is 0.1-1m 3 /(min·t Fe ) Bottom blowing for 5-10min;
(2) Adding sodium salt once when the top blowing is finished by 1/3-3/5, and forming sodium vanadium slag until the top-bottom combined blowing is finished; the sodium salt comprises any one or combination of at least two of sodium carbonate, sodium oxide or sodium sulfate; the molar ratio (1.5-2.5) of the sodium element in the sodium salt to the vanadium element in the vanadium-containing molten iron is 1.
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