Method for effectively utilizing vanadium slag of converter

Abstract

The method for effectively utilizing the converter vanadium slag disclosed by the embodiment of the invention comprises the following steps: adding a dephosphorizing agent and a cooling agent into vanadium-containing molten iron in a converter for oxygen blowing smelting to obtain molten vanadium slag and semi-steel; wherein the content of P in the semi-steel is lower than 0.005 wt%; the content of CaO in the molten vanadium slag is greater than 5wt%, and the content of P is greater than 0.05 wt%; adding a high-valence oxide-containing material into the obtained molten vanadium slag, introducing CO2-O2 gas, and stirring; during the reaction, ultrasonic, microwave and magnetic field are utilized to synergistically strengthen the reaction process, and the magnetic vanadium spinel and the fused silicate mixture are obtained; the content of the magnetic solid vanadium spinel is 20-100 wt%; separating the mixture of the magnetic vanadium spinel and the fused silicate under a magnetic field condition to obtain the magnetic vanadium spinel and the fused silicate; molten silicate is used as a cooling agent; reducing the magnetic solid vanadium spinel to obtain a vanadium-iron alloy; or carrying out roasting-chlorination treatment to obtain VOCl3 gas; or carrying out roasting-chlorination treatment to obtain VOCl3 gas.

Description

Technical Field

[0001] The present invention belongs to the technical field of iron and steel smelting, and particularly relates to a method for effectively utilizing converter vanadium slag. Background Art

[0002] Vanadium, as a strategic metal, has important applications in industries such as iron and steel, batteries, and catalysts. China produces a large amount of vanadium every year, and about 85% of it is used in the smelting of alloy steel. Chromium can improve the oxidation resistance and corrosion resistance of steel and is an important alloying element for heat-resistant steel.

[0003] Vanadium-titanium magnetite is a complex symbiotic mineral rich in various valuable components such as iron, vanadium, chromium, and titanium, and is an important strategic resource with Chinese characteristics. Every year, hundreds of thousands of tons of vanadium slag are produced in the smelting process of vanadium-titanium magnetite in China. The vanadium slag contains valuable metals vanadium and chromium. The V 2 O 3 content in the vanadium slag is 13-19 wt.%. The main phases of the vanadium slag are spinel phase (ferrovanadium spinel, manganese-vanadium spinel, and titanoferrite spinel), silicate phase (manganese-ferrous olivine), and metallic iron phase; vanadium mainly exists in the form of trivalent in ferrovanadium spinel (FeV 2 O 4 ).

[0004] Patent CN201310416429.4 discloses a method for separating vanadium resources from vanadium slag by high gravity, which discloses that molten vanadium slag undergoes centrifugal high gravity separation of spinel phase and silicate phase at 1240-1260 °C; Patent CN201610807157.4 discloses a method for dephosphorizing vanadium-containing hot metal in a vanadium extraction converter, which discloses dephosphorization by controlling the oxygen lance and adding scale; Patent CN201210239175.9 discloses a method for simultaneous dephosphorization and vanadium extraction in a converter, which discloses adding dephosphorizing agent lime to vanadium-containing hot metal in the converter during the vanadium extraction process for simultaneous dephosphorization and vanadium extraction; Patent CN201210238253.3 discloses a coolant for converter dephosphorization and vanadium extraction and its production method, and a converter dephosphorization and vanadium extraction method, which discloses that sodium salt, scale, bauxite fine powder, and water are mixed to form a mixture, and the moisture is removed by baking to obtain a cold bonded pellet product.

[0005] However, the existing vanadium oxide production process requires that the CaO content in vanadium slag is less than 2.5%, which makes it impossible to add calcium oxide for dephosphorization during the vanadium extraction process from vanadium-bearing hot metal in a converter. As a result, phosphorus in the hot metal enters the semi-steel, which is not conducive to the production of high-value clean steel. Because during the process of adding calcium for dephosphorization, high-calcium and high-phosphorus vanadium slag will be obtained. During the leaching process, vanadium and phosphorus are likely to combine into phosphovanadomolybdic acid and other phosphate precipitates, which hinder the precipitation of vanadium, greatly reducing the vanadium precipitation rate and affecting the quality of vanadium at the same time. During the sodium roasting and water leaching process, the phosphorus concentration is controlled below 0.015 g / L. During the calcification roasting and acid leaching process, the phosphorus concentration is controlled below 0.06 g / L. At present, due to the high requirements for the phosphorus content in vanadium slag in the roasting and leaching process. Therefore, it is difficult to extract vanadium and dephosphorize simultaneously during the converter vanadium extraction process. Summary of the Invention

[0006] In view of this, the embodiments of the present invention disclose a method for effectively utilizing converter vanadium slag, proposing to extract vanadium and dephosphorize simultaneously in the converter. After that, the molten vanadium slag is prepared into magnetic vanadium spinel through selective oxidation, further realizing the separation of vanadium spinel from phosphorus and silicate phases. The separated vanadium spinel has a low phosphorus content and a high vanadium content, which can avoid the problem of difficult dephosphorization in the later stage and improve the vanadium utilization rate.

[0007] Some embodiments disclose a method for effectively utilizing converter vanadium slag, including the steps:

[0008] S1. Vanadium-bearing hot metal is blown with oxygen and smelted in a converter. During the smelting process, a dephosphorizing agent and a coolant are added to obtain molten vanadium slag and semi-steel. Among them, the mass contents of each component in the vanadium-bearing hot metal are: C is 3.5 - 4.8 wt%, Si is 0.01 - 0.36 wt%, Ti is 0.01 - 0.32 wt%, P is 0.01 - 0.1 wt%, V is 0.05 - 0.5 wt%, Cr is 0 - 0.5 wt%; the P content in the semi-steel is lower than 0.003 wt%; the CaO content in the molten vanadium slag is greater than 5 wt%, and the P content is greater than 0.05 wt%.

[0009] S2. A material containing a high-valence oxide is added to the obtained molten vanadium slag, and CO 2 -O 2 gas is introduced for stirring, and the reaction is carried out at a set temperature. During the reaction, the reaction process is synergistically enhanced by ultrasound, microwave, and magnetic field to obtain a mixture of magnetic solid vanadium spinel and molten silicate; the content of the magnetic solid vanadium spinel is 20 - 100 wt%.

[0010] S3. The mixture of magnetic solid vanadium spinel and molten silicate is separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten silicate respectively.

[0011] S4. The obtained molten silicate is cooled and added to the converter as a coolant to realize the recycling of iron.

[0012] S5. The obtained magnetic solid vanadium spinel is reduced to ferrovanadium alloy; or,

[0013] S6. The obtained magnetic solid vanadium spinel is calcined - leached with water - precipitated - hydrothermally treated to obtain a Na - containing VO 2 material.

[0014] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S2, ultrasonic strengthening heating is adopted in the initial slag mixing stage, and the ultrasonic intensity is set to 20 - 40 kHz; microwave strengthening heating is adopted in the middle reaction stage, and the microwave frequency is set to 2.45 GHz; magnetic field strengthening reaction process is adopted in the later reaction stage, and the magnetic field intensity is set at 0.1 - 0.5 T.

[0015] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, the dephosphorizer includes one or a combination of more of CaO, CaCO 3 , Na 2 CO 3 , MgO, Al 2 O 3 , CaF 2 , and the coolant includes silicate.

[0016] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S2, the set temperature is 1000 - 1600 °C, the flow rate of CO 2 -O 2 gas is 0 - 12 m 3 per ton of vanadium slag, and the high - valence oxide - containing material includes MnO 2 , Mn 2 O 3 , Fe 3 O 4 , Fe 2 VO 4 , CeO 2 , nanoscale core - shell structure Fe 2 O 3 @CeO 2 .

[0017] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, the high - valence oxide - containing material is a combination of MnO 2 or Mn 2 O 3 , Fe 3 O 4 or Fe 2 VO 4 ; or, MnO 2 or Mn 2 O 3 , Fe 3 O 4 or Fe2 VO 4 and the combination of CeO 2 ; or the nano-scale core-shell structure Fe 2 O 3 @CeO 2 .

[0018] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S3, the magnetic solid vanadium spinel and the molten silicate mixture are separated at a temperature of 1000-1600 °C.

[0019] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S5, the reduction temperature of the magnetic solid vanadium spinel is 800-1400 °C, and the reducing agent is carbon, methane or CO.

[0020] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S6, in the roasting-chlorination treatment process of the magnetic solid vanadium spinel, the additive for roasting is Na 2 CO 3 , NaOH or CaCO 3 ; the chlorinating agent is CrCl 3 , FeCl 3 or AlCl 3 .

[0021] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S1, the addition amount of the dephosphorizer is 10-40 kg / ton of vanadium-bearing hot metal, and the addition amount of the coolant is 10-70 kg / ton of vanadium-bearing hot metal.

[0022] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S3, the magnetic field intensity is set at 0.1-0.5 T.

[0023] The method for effectively utilizing converter vanadium slag disclosed in the embodiments of the present invention has the following beneficial technical effects:

[0024] (1) Simultaneously realize vanadium extraction and dephosphorization to obtain vanadium slag, the phosphorus content in the semi-steel is lower than 0.003 wt%, initially separate the vanadium spinel from the molten slag phase through the dephosphorizer, then convert the spinel into magnetic vanadium spinel through selective oxidation, further separate through magnetism, and through two-step slag adjustment, 95% of the phosphorus in apatite and spinel enters the silicate phase, and the phosphorus content in the obtained vanadium spinel is lower than 0.003 wt%;

[0025] (2) Directly obtain magnetic vanadium spinel with high vanadium content and low phosphorus content; the enriched magnetic vanadium spinel is reduced to obtain ferrovanadium alloy, which has a shorter process flow than the traditional process for preparing ferrovanadium alloy; or the enriched magnetic vanadium spinel is subjected to roasting-chlorination treatment to obtain VOCl 3 gas;

[0026] (3) Vanadium slag prepared by traditional processes has a large amount of iron entering the tailings because spinel and olivine cannot be separated; however, in the embodiments of the present invention, the silicate obtained from the reaction is added as a coolant to the converter to achieve the recycling of iron, greatly reducing the content of tailings; at the same time, reducing the content of the olivine phase in the slag; in the process of roasting and extracting vanadium, the amount of additives such as Na 2 CO 3 , CaCO 3 etc. reacting with silicon to form silicate is reduced, and the addition amount of the additives is reduced by 50% compared with the traditional process;

[0027] (4) By converting FeV 2 O 4 into Fe 2 VO 4 , the magnetic separation of magnetic vanadium spinel and molten silicate is achieved;

[0028] (5) Compared with magnetic enrichment of vanadium in stone coal, the formation of magnetic substances in stone coal is obtained through solid-solid reactions. Fe 2 O 3 and V 2 O 3 are relatively easy to obtain Fe 2 VO 4 . The process of enriching vanadium in stone coal emphasizes avoiding sintering caused by excessive temperature. Magnetic enrichment of stone coal separates magnetic substances and non-magnetic substances by ball milling at low temperatures. The formation of magnetic substances in the new method is in liquid silicate, and magnetic substances are obtained by precipitation. The reaction mechanism and formation process are completely different; the separation process is simple and does not require additional processes such as ball milling; through vanadium extraction and dephosphorization, and magnetic separation, phosphorus remains in the silicate phase, and the enriched vanadium iron spinel is phosphorus-free and can be directly used for vanadium extraction.

[0029] (6) By regulating the composition and magnetism, the preferential precipitation of V 2 O 3 is achieved, and then Fe 2 VO 4 wraps V 2 O 3 , or magnetic substances such as Fe 2 VO 4 and Fe 3 O 4 etc. are added to wrap the precipitated V 2 O 3 , and a solid phase with a high V 2 O 3 content is obtained by magnetic separation; CeO 2 can be used as an oxidant or as a substance to strengthen the solid phase magnetism to achieve separation.

[0030] (7) The appearance of the apatite phase leads to an increase in the phosphorus content in the spinel phase. By regulating the slag system with sodium carbonate, the apatite precipitated from the molten slag turns into a molten liquid phase, and the phosphorus entering the molten slag is regulated to reduce the phosphorus content in the spinel phase.

[0031] (8) Through the technical combination of multi-physical field enhanced reaction, high-temperature in-situ separation, and phosphorus directional circulation, the problems of low vanadium recovery rate, serious phosphorus pollution, and high energy consumption are solved.

[0032] (9) The multi-physical fields of ultrasound, microwave, and magnetic field are synergistically regulated. The ultrasound with a frequency of 20 - 40 kHz acts preferentially on the initial mixing stage of the molten slag to break the high-valence oxide particles; the microwave selectively heats FeV 2 O 4 to promote the conversion to Fe 2 VO 4 ; the magnetic field guides the directional growth of vanadium spinel in the later stage of the reaction to promote the separation of vanadium and silicon; the obtained particle size is concentrated around 50 μm.

[0033] (10) The proportion of CO 2 -O 2 gas is dynamically adjusted, and the CO 2 / O 2 proportion is adjusted in real time according to the molten slag temperature to avoid the overoxidation of vanadium to V 2 O 5 , and at the same time inhibit the excessive generation of Fe 3+ .

[0034] (11) Add a nano-scale Fe 2 O 3 @CeO 2 core-shell structure catalyst with a particle size of 20 - 50 nm. Utilize the oxygen vacancies of CeO 2 to promote the activation of CO 2 , reduce the activation energy for the conversion of V 4+ to V 3+ , shorten the reaction time by 30%, and increase the vanadium recovery rate to over 95%. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Flowchart of the method for effectively utilizing converter vanadium slag disclosed in some embodiments. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] The specific term "embodiment" used here does not necessarily mean better or superior to other embodiments as described by "exemplary". For the performance index tests in the embodiments of the present invention, unless otherwise specified, the conventional test methods in the art are adopted. It should be understood that the terms described in the embodiments of the present invention are only used to describe specific embodiments and are not intended to limit the content disclosed in the embodiments of the present invention.

[0037] Unless otherwise specified, the technical and scientific terms used herein have the same meanings as commonly understood by those of ordinary skill in the technical field to which the embodiments of the present invention belong; other test methods and technical means not specifically noted in the embodiments of the present invention refer to the test methods and technical means commonly adopted by those of ordinary skill in the art.

[0038] The terms "substantially" and "about" as used herein are used to describe minor fluctuations. For example, they can refer to less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%. Numerical data presented or represented in a range format herein is used only for convenience and brevity and should therefore be flexibly interpreted as including not only the values explicitly listed as the bounds of the range but also all individual values or sub-ranges included within that range. For example, the numerical range of "1 to 5%" should be interpreted as including not only the explicitly listed values of 1% to 5% but also the individual values and sub-ranges within the indicated range. Thus, within this numerical range, individual values such as 2%, 3.5%, and 4% are included, and sub-ranges such as 1% to 3%, 2% to 4%, and 3% to 5% etc. This principle also applies to ranges that list only one numerical value. In addition, such an interpretation applies regardless of the width of the range or the characteristics described.

[0039] In this document, including in the claims, conjunctions such as "comprising", "including", "carrying", "having", "containing", "involving", "accommodating", etc. are understood to be open-ended, that is, meaning "including but not limited to". Only the conjunctions "consisting of" and "composed of" are closed conjunctions.

[0040] To better illustrate the content of the present invention, numerous specific details are given in the following specific embodiments. Those skilled in the art should understand that the present invention can also be implemented without some of these specific details. In the embodiments, some methods, means, instruments, devices, etc. well-known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.

[0041] On the premise of no conflict, the technical features disclosed in the embodiments of the present invention can be combined arbitrarily, and the obtained technical solutions belong to the content disclosed in the embodiments of the present invention.

[0042] In some embodiments, as Figure 1 shown, the method for the effective utilization of converter vanadium slag includes the steps:

[0043] S1. The vanadium-containing hot metal is smelted by blowing oxygen in a converter. During the smelting process, a dephosphorizer and a coolant are added to obtain molten vanadium slag and semi-steel. Among them, the mass contents of each component in the vanadium-containing hot metal are: C is 3.5 - 4.8%, Si is 0.01 - 0.36%, Ti is 0.01 - 0.32%, P is 0.01 - 0.1%, V is 0.05 - 0.5%, and Cr is 0 - 0.5%; the P content in the semi-steel is lower than 0.003 wt%; the CaO content in the molten vanadium slag is greater than 5 wt%, and the P content is greater than 0.05 wt%.

[0044] Generally, the dephosphorizer is used to remove phosphorus in the vanadium-containing hot metal, convert phosphorus into apatite and spinel, and then regulate the converted apatite and spinel in the silicate phase; generally, the addition amount of the dephosphorizer is 10 - 40 kg per ton of vanadium-containing hot metal; the coolant does not participate in the reaction and is used to reduce the temperature of the reaction melt to improve the oxidation rate of vanadium. Generally, the addition amount of the coolant is 10 - 70 kg per ton of vanadium-containing hot metal.

[0045] S2. A material containing a high-valence oxide is added to the obtained molten vanadium slag, and CO 2 -O 2 gas is introduced for stirring, and the reaction is carried out at a set temperature to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate, where the proportion of the magnetic solid vanadium spinel is 20 - 100%.

[0046] Generally, the obtained magnetic solid vanadium spinel contains the following components: 20 - 45 wt% V 2 O 3 、0 - 11 wt% Cr 2 O 3 、0.5 - 5 wt% SiO 2 、0 - 0.08 wt% P, 20 - 45 wt% FeO, 6 - 12 wt% MnO, 8 - 12 wt% TiO 2 ;

[0047] The molten silicate contains the following components: SiO 2 27 - 35 wt%, TiO 2 8 - 15 wt%, CaO 4 - 10 wt%;

[0048] S3. The mixture of magnetic solid vanadium spinel and molten silicate is separated under a magnetic field condition to obtain magnetic solid vanadium spinel and molten silicate respectively; generally, the magnetic field intensity is set at 0.1 - 0.5 T.

[0049] S4. The obtained molten silicate is cooled and added to the converter as a coolant to realize the recycling of iron. Usually, the TFe content in the tail slag obtained by the method disclosed in the embodiments of the present invention can be reduced by more than 30 wt% compared with the TFe content in the traditional process.

[0050] S5. The obtained magnetic solid vanadium spinel is reduced to ferrovanadium alloy; or,

[0051] S6. The obtained magnetic solid vanadium spinel is subjected to roasting - water leaching - precipitation - hydrothermal treatment to obtain a Na-ion-containing VO 2 material; or the magnetic solid vanadium spinel is subjected to roasting - chlorination treatment to obtain VOCl 3 gas. Generally, the Na-ion-containing VO 2 material can be used as the cathode material for zinc-ion batteries.

[0052] For the method for effectively utilizing converter vanadium slag disclosed in some embodiments, the dephosphorizer includes one or a combination of more of CaO, CaCO 3 , Na 2 CO 3 , MgO, Al 2 O 3 , CaF 2 , and the coolant includes silicate.

[0053] For the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S2, the set temperature is 1000 - 1600 °C, and the flow rate of CO 2 -O 2 gas is 0 - 12 m 3 per ton of vanadium slag, and the high-valence oxide-containing material includes MnO 2 , Mn 2 O 3 , Fe 3 O 4 , Fe 2 VO 4 or CeO 2 . Among them, MnO 2 , Mn 2 O 3 has an oxidizing effect, Fe 3 O 4 , Fe 2 VO 4 , CeO 2 has the effect of enhancing magnetism; the nanoscale core-shell structure Fe 2 O 3 @CeO 2 has both oxidizing and magnetism-enhancing effects.

[0054] In some embodiments, the high-valence oxide-containing material is more preferably MnO 2 or Mn 2 O 3 , Fe 3 O 4 or Fe 2 VO 4Combinations. For example, MnO 2 , Fe 3 O 4 combination, or Mn 2 O 3 , Fe 2 VO 4 combination. Generally, in the combination of MnO 2 or Mn 2 O 3 , Fe 3 O 4 or Fe 2 VO 4 , the mass ratio of the two is 4 - 6:4 - 6.

[0055] In some embodiments, the high - valence oxide - containing material is further preferably a combination of MnO 2 or Mn 2 O 3 , Fe 3 O 4 or Fe 2 VO 4 and CeO 2 . For example, the combination of MnO 2 , Fe 3 O 4 , CeO 2 , or the combination of MnO 2、 Fe 2 VO 4 , CeO 2 . Generally, in the combination of MnO 2 or Mn 2 O 3 , Fe 3 O 4 or Fe 2 VO 4 and CeO 2 , the mass ratio of the three is 3 - 5:3 - 4:1 - 2 in sequence.

[0056] In some embodiments, the high - valence oxide - containing material is further more preferably nanoscale core - shell structured Fe 2 O 3 @CeO 2 .

[0057] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, in step S3, the magnetic solid - state vanadium spinel and the molten silicate mixture are separated at a temperature of 1000 - 1600 °C.

[0058] In the method for effectively utilizing converter vanadium slag disclosed in some embodiments, the reduction temperature of the magnetic solid - state vanadium spinel is 800 - 1400 °C, and the reducing agent is carbon, methane or CO.

[0059] In some embodiments, a method for effectively utilizing converter vanadium slag is disclosed. In the roasting and chlorination treatment process of magnetic solid vanadium spinel, the additive for roasting is Na 2 CO 3 , NaOH or CaCO 3 ; the chlorinating agent is CrCl 3 , FeCl 3 or AlCl 3 .

[0060] The following examples are used to further exemplify the technical details.

[0061] Example 1

[0062] In Example 1, the method for effectively utilizing converter vanadium slag includes:

[0063] S1. Vanadium-bearing hot metal (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, V is 0.35%, Cr is 0.2%) is blown with oxygen in a converter. During the smelting process, a dephosphorizing agent and a coolant are added to obtain molten vanadium slag and semi-steel. Among them, the vanadium-bearing hot metal is 200t, the oxygen-blowing smelting temperature is 1290°C, the oxygen-blowing smelting time is 5 minutes, the dephosphorizing agent CaO is 5t, and the coolant silicate is 10t;

[0064] S2. 0.01t of MnO 2 is added to the obtained molten vanadium slag, and CO 2 -O 2 gas is introduced for stirring, and it is heated to a set temperature for reaction to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; in the CO 2 -O 2 gas, the ratio of CO 2 to O 2 is 10:1, the total flow rate is 50m 3 , the reaction time is 10min, and the set temperature is 1350°C;

[0065] S3. The mixture of magnetic solid vanadium spinel and molten liquid silicate is separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively. The molten liquid silicate is poured out to obtain a solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2T.

[0066] Example 2

[0067] In Example 2, the method for effectively utilizing converter vanadium slag includes:

[0068] S1. Smelting vanadium-containing molten iron (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, V is 0.35%, and Cr is 0.2%) in a converter by oxygen blowing, adding a dephosphorizing agent and a coolant during the smelting process to obtain molten vanadium slag and semi-steel; wherein, the vanadium-containing molten iron is 200 tons, the oxygen blowing smelting temperature is 1290° C., the oxygen blowing smelting time is 5 minutes, the dephosphorizing agent CaO is 5 tons, and the coolant silicate is 10 tons;

[0069] S2, add 0.01t of Mn to the obtained molten vanadium slag 2 O 3 , CO 2 -O 2 The gas is stirred and heated to a set temperature to react to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; CO 2 -O 2 CO in gas 2 With O 2 The ratio is 10:1, and the total flow is 50m 3 , reaction time 10min, set temperature 1350℃;

[0070] S3, the magnetic solid vanadium spinel and the molten liquid silicate mixture are separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively, and the molten liquid silicate is poured out to obtain solid Fe 2 VO 4 Phase. Among them, the magnetic field strength is 0.5T.

[0071] Example 3

[0072] In Example 3, the method for effectively utilizing converter vanadium slag includes:

[0073] S1. Vanadium-containing molten iron (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, V is 0.35%, and Cr is 0.2%) is smelted by oxygen blowing in a converter, and dephosphorization agent and coolant are added during the smelting process to obtain molten vanadium slag and semi-steel; wherein, the vanadium-containing molten iron is 200t, the oxygen blowing smelting temperature is 1290℃, the oxygen blowing smelting time is 5 minutes, and the dephosphorization agent Na 2 CO 3 The cooling agent is 5t, and the coolant silicate is 10t;

[0074] S2, add 0.01t of Fe 3 O 4 , CO 2 -O 2 The gas is stirred and heated to a set temperature to react to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; CO 2 -O2 CO in the gas 2 and O 2 The ratio is 10:1, the total flow rate is 50 m 3 , the reaction time is 10 min, and the set temperature is 1350 °C;

[0075] S3. The mixture of magnetic solid vanadium spinel and molten liquid silicate is separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively. The molten liquid silicate is poured out to obtain solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2 T.

[0076] Example 4

[0077] In Example 4, the method for the effective utilization of converter vanadium slag includes:

[0078] S1. Vanadium-bearing hot metal (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, V is 0.35%) is blown with oxygen in a converter. During the smelting process, a dephosphorizing agent and a coolant are added to obtain molten vanadium slag and semi-steel; among them, the vanadium-bearing hot metal is 200 t, the oxygen-blowing smelting temperature is 1290 °C, the oxygen-blowing smelting time is 5 minutes, the dephosphorizing agent Na 2 CO 3 is 5 t, and the coolant silicate is 10 t;

[0079] S2. 0.06 t of Fe 2 VO 4 and 0.04 t of Mn 2 O 3， are introduced and stirred with CO 2 -O 2 gas. It is heated to the set temperature for reaction, and ultrasound is introduced during the initial stage of stirring. The ultrasound intensity is set to 200 kHz to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; CO 2 -O 2 In the gas, the ratio of CO 2 to O 2 is 10:1, the total flow rate is 50 m 3 , the reaction time is 6 min, and the set temperature is 1350 °C;

[0080] S3. The mixture of magnetic solid vanadium spinel and molten liquid silicate is separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively. The molten liquid silicate is poured out to obtain solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2 T.

[0081] Example 5

[0082] In Example 5, the method for effectively utilizing converter vanadium slag includes:

[0083] S1. Vanadium-containing molten iron (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, and V is 0.35%) is smelted by oxygen blowing in a converter, and dephosphorization agent and coolant are added during the smelting process to obtain molten vanadium slag and semi-steel; wherein, the vanadium-containing molten iron is 200t, the oxygen blowing smelting temperature is 1290℃, the oxygen blowing smelting time is 5 minutes, and the dephosphorization agent Na 2 CO 3 The cooling agent is 5t, and the coolant silicate is 10t;

[0084] S2, add 0.05t of Fe 2 VO 4 and 0.05t of MnO 2 , CO 2 -O 2 The gas is stirred and heated to a set temperature for reaction. A magnetic field is added in the later stage of the reaction, and the magnetic field strength is set at 0.1T to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; CO 2 -O 2 CO in gas 2 With O 2 The ratio is 10:1, and the total flow is 50m 3 , reaction time is 5min, set temperature is 1350℃;

[0085] S3, the magnetic solid vanadium spinel and the molten liquid silicate mixture are separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively, and the molten liquid silicate is poured out to obtain solid Fe 2 VO 4 Phase. Among them, the magnetic field strength is 0.2T.

[0086] Example 6

[0087] In Example 6, the method for effectively utilizing converter vanadium slag includes:

[0088] S1. Vanadium-containing molten iron (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, and V is 0.35%) is smelted by oxygen blowing in a converter, and dephosphorization agent and coolant are added during the smelting process to obtain molten vanadium slag and semi-steel; wherein, the vanadium-containing molten iron is 200t, the oxygen blowing smelting temperature is 1290℃, the oxygen blowing smelting time is 5 minutes, and the dephosphorization agent Na 2 CO 3 The cooling agent is 5t, and the coolant silicate is 10t;

[0089] S2. Add 0.04 t of Fe to the obtained molten vanadium slag. 2 VO 4 , 0.04 t of MnO 2 and 0.01 t of CeO 2 Introduce CO 2 -O 2 gas for stirring, heat to the set temperature and react for 2 min, then react for 5 min under magnetic conditions to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; The CO 2 -O 2 gas has a ratio of CO 2 to O 2 of 10:1, a total flow rate of 50 m 3 , a reaction time of 5 min, and a set temperature of 1350 °C;

[0090] S3. Separate the mixture of magnetic solid vanadium spinel and molten liquid silicate under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively. Pour out the molten liquid silicate to obtain solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2 T.

[0091] Example 7

[0092] In Example 7, the method for effectively utilizing converter vanadium slag includes:

[0093] S1. The vanadium-bearing hot metal (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, V is 0.35%) is blown with oxygen in a converter. During the smelting process, a dephosphorizer and a coolant are added to obtain molten vanadium slag and semi-steel; Among them, the vanadium-bearing hot metal is 200 t, the oxygen-blowing smelting temperature is 1290 °C, the oxygen-blowing smelting time is 5 minutes, the dephosphorizer Na 2 CO 3 is 5 t, and the coolant silicate is 10 t;

[0094] S2. Add 0.01 t of Fe 2 O 3 @CeO 2 core-shell structure catalyst with a particle size of 20 nm, introduce CO 2 -O 2 gas for stirring, heat to the set temperature and react for 2 min, then react for 5 min under magnetic conditions to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; The CO 2 -O 2 gas has a ratio of CO 2 to O 2 of 10:1, a total flow rate of 50 m 3, the reaction time is 5 min, and the set temperature is 1350 °C;

[0095] S3. The mixture of magnetic solid vanadium spinel and molten liquid silicate is separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively. The molten liquid silicate is poured out to obtain solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2 T.

[0096] Example 8

[0097] In Example 8, the method for effectively utilizing converter vanadium slag includes:

[0098] S1. Vanadium-bearing hot metal (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, V is 0.35%, Cr is 0.2%) is blown and smelted in a converter. During the smelting process, a dephosphorizing agent and a coolant are added to obtain molten vanadium slag and semi-steel; among them, the vanadium-bearing hot metal is 200 t, the blowing and smelting temperature is 1290 °C, the blowing and smelting time is 5 minutes, and the dephosphorizing agent Na 2 CO 3 is 5 t, and the coolant silicate is 10 t;

[0099] S2. In the obtained molten vanadium slag, 0.04 t of Fe 2 VO 4 , 0.04 t of MnO 2 and 0.02 t of CeO 2 are added, and CO 2 -O 2 gas is introduced for stirring, heated to the set temperature and reacted for 2 min, and then reacted for 5 min under magnetic conditions to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; CO 2 -O 2 in the gas, the ratio of CO 2 to O 2 is 10:1, the total flow rate is 50 m 3 , the reaction time is 5 min, and the set temperature is 1350 °C;

[0100] S3. The mixture of magnetic solid vanadium spinel and molten liquid silicate is separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively. The molten liquid silicate is poured out to obtain solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2 T.

[0101] Example 9

[0102] In Example 9, the method for effectively utilizing converter vanadium slag includes:

[0103] S1. Vanadium-bearing hot metal (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, V is 0.35%, Cr is 0.2%) is smelted by blowing oxygen in a converter. During the smelting process, a dephosphorizer and a coolant are added to obtain molten vanadium slag and semi-steel; among them, the vanadium-bearing hot metal is 200 t, the oxygen-blowing smelting temperature is 1290 °C, the oxygen-blowing smelting time is 5 minutes, and the dephosphorizer Na 2 CO 3 is 5 t, and the coolant silicate is 10 t;

[0104] S2. In the obtained molten vanadium slag, 0.04 t of Fe 2 VO 4 , 0.04 t of MnO 2 and 0.02 t of CeO 2 are added, and CO 2 -O 2 gas is introduced for stirring, heated to a set temperature and reacted for 2 min, and then reacted for 5 min under magnetic conditions to obtain a magnetic solid vanadium spinel and a molten liquid silicate mixture; CO 2 -O 2 in the gas, the ratio of CO 2 to O 2 is 10:1, the total flow rate is 50 m 3 , the reaction time is 5 min, and the set temperature is 1350 °C;

[0105] S3. The magnetic solid vanadium spinel and the molten liquid silicate mixture are separated under magnetic field conditions to obtain a magnetic solid vanadium spinel and a molten liquid silicate respectively. The molten liquid silicate is poured out to obtain a solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2 T.

[0106] Example 10

[0107] In Example 10, the method for effectively utilizing converter vanadium slag includes:

[0108] S1. Vanadium-bearing hot metal (wherein, by mass, C is 4.4%, Si is 0.2%, Ti is 0.2%, P is 0.05%, V is 0.35%, Cr is 0.2%) is smelted by blowing oxygen in a converter. During the smelting process, a dephosphorizer and a coolant are added to obtain molten vanadium slag and semi-steel; among them, the vanadium-bearing hot metal is 200 t, the oxygen-blowing smelting temperature is 1290 °C, the oxygen-blowing smelting time is 5 minutes, and the dephosphorizer Na 2 CO 3 is 5 t, and the coolant is silicate 10 t;

[0109] S2. In the obtained molten vanadium slag, 0.01 t of Fe2 O 3 @CeO 2 Core-shell structured catalyst with a particle size of 30 nm; CO is introduced 2 -O 2 Gas stirring, heated to the set temperature, ultrasonic is introduced in the first 2 min, microwave is introduced after 2 min, and then magnetic field is added for 2 min to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; CO 2 -O 2 CO in the gas 2 and O 2 The ratio is 10:1, and the total flow rate is 50 m 3 , the reaction time is 5 min, and the set temperature is 1350 °C;

[0110] S3. The mixture of magnetic solid vanadium spinel and molten liquid silicate is separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively. The molten liquid silicate is poured out to obtain solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2 T.

[0111] Comparative Example 1

[0112] In Comparative Example 1, the treatment method of vanadium slag includes:

[0113] S1. Vanadium-bearing hot metal is blown with oxygen in a converter, and a dephosphorizer and a coolant are added during the smelting process to obtain molten vanadium slag and semi-steel; among them, the vanadium-bearing hot metal is 200 t, the oxygen-blowing smelting temperature is 1290 °C, the oxygen-blowing smelting time is 5 minutes, and the dephosphorizer Na 2 CO 3 is 5 t, and the coolant silicate is 10 t.

[0114] Comparative Example 2

[0115] In Comparative Example 2, the treatment method of vanadium slag includes:

[0116] S1. Vanadium-bearing hot metal is blown with oxygen in a converter, and a dephosphorizer and a coolant are added during the smelting process to obtain molten vanadium slag and semi-steel; among them, the vanadium-bearing hot metal is 200 t, the oxygen-blowing smelting temperature is 1290 °C, the oxygen-blowing smelting time is 5 minutes, the dephosphorizer CaO is 5 t, and the coolant silicate is 10 t;

[0117] S2. In the obtained molten vanadium slag, CO 2 -O 2 gas stirring, heated to the set temperature for reaction to obtain a mixture of magnetic solid vanadium spinel and molten liquid silicate; CO 2 -O 2 CO in the gas 2 and O 2The ratio is 10:1 and the total flow rate is 50 m 3 , the reaction time is 10 min, and the set temperature is 1350 °C;

[0118] S3. The mixture of magnetic solid vanadium spinel and molten liquid silicate is separated under magnetic field conditions to obtain magnetic solid vanadium spinel and molten liquid silicate respectively. The molten liquid silicate is poured out to obtain solid Fe 2 VO 4 phase. Among them, the magnetic field strength is 0.2 T.

[0119] The list of the main components of the vanadium slag obtained in Examples 1 to 10 and Comparative Examples 1 to 2 is shown in Table 1;

[0120] Table 1 List of the main components of vanadium slag

[0121] Component <![CDATA[V 2 O 3 > <![CDATA[Cr 2 O 3 > <![CDATA[SiO 2 > P Comparative Example 1 15 6 12 0.3 Comparative Example 2 20 9 5 0.008 Example 1 25 11 3 0.003 Example 2 26 11 1 0.001 Example 3 27 11 0.5 0.001 Example 4 33 0 0 0 Example 5 35 0 0 0 Example 6 40 0 0 0 Example 7 42 0 0 0 Example 8 42 0 0 0 Example 9 38 11 0 0 Example 10 50 12 0 0

[0122] From the data listed in Table 1, it can be seen that in the vanadium slag obtained in Examples 1 to 3, the contents of V 2 O 3 and Cr 2 O 3 can reach 27 wt% and 11 wt% respectively, which are much higher than those of the vanadium slag in Comparative Examples 1 to 2. At the same time, the content of SiO 2 decreases, and the content of P is lower than 0.003 wt.%; in Examples 4 to 8, the contents of V 2 O 3 and Cr 2 O 3 can reach 42 wt%, which is much higher than those in Comparative Examples 1 to 2, and the contents of Cr 2 O 3、 SiO 2 and P are zero; in Examples 9 to 10, the contents of V 2 O 3 and Cr 2 O 3 can reach 50 wt%, which is much higher than those in Comparative Examples 1 to 2, and the content of Cr 2 O 3 can reach 12 wt%, and the contents of SiO 2 and P are zero.

[0123] Example 11

[0124] Using the magnetic solid vanadium spinel obtained in Example 1 as the raw material, a reaction is carried out with a reducing agent to prepare ferrovanadium alloy. The specific method includes:

[0125] The magnetic solid-state vanadium spinel reacts with the reducing agent carbon at 1100 °C. The molar ratio of the reducing agent C / V is 5:1, and the reduction time is 2 h to obtain an Fe-V alloy.

[0126] Example 12

[0127] Using the magnetic solid-state vanadium spinel obtained in Example 1 as the raw material, through roasting or chlorination treatment, specifically including:

[0128] The magnetic solid-state vanadium spinel is roasted with the additive sodium carbonate at a temperature of 800 °C. The mass ratio of sodium carbonate to the magnetic solid-state spinel is 3:10, and the time is 2 h. The extraction rate of vanadium is 98%.

[0129] The magnetic solid-state vanadium spinel reacts with AlCl 3 for chlorination reaction. The chlorination temperature is 900 °C. The mass ratio of the magnetic solid-state vanadium spinel to AlCl 3 is 1:1.5, and the time is 2 h. The chlorination rate of vanadium is 90%.

[0130] Example 13

[0131] Using the magnetic solid-state vanadium spinel obtained in Example 1 as the raw material, through roasting - water leaching - precipitation - hydrothermal treatment, a VO 2 material containing Na ions is obtained;

[0132] Specifically, the magnetic solid-state vanadium spinel goes through a roasting stage in sequence: the mass ratio of CaCO 3 / vanadium slag is 1:10, the roasting temperature is 1100 °C, the roasting time is 2 h, and the Ar atmosphere; the leaching stage: pH = 2.8, and the filtrate is obtained by filtration; the precipitation stage: the precipitation pH of the filtrate is 1.8; the hydrothermal stage: put it into a hydrothermal autoclave, add an NaCl solution, the hydrothermal temperature is 180 °C, and the time is 24 h to obtain VO 2 .

[0133] The method for effectively utilizing converter vanadium slag disclosed in the embodiments of the present invention initially separates vanadium spinel from the molten slag phase through a dephosphorizer, and then converts the spinel into magnetic vanadium spinel through selective oxidation. Further separation is achieved through magnetism, and the phosphorus content in the obtained vanadium spinel is lower than 0.003 wt%. The obtained magnetic vanadium spinel has a high vanadium content and a low phosphorus content; further separation of the magnetic vanadium spinel from the molten silicate is achieved through a normal magnetic field; the enriched magnetic vanadium spinel is reduced to obtain ferrovanadium alloy, and the process flow for preparing ferrovanadium alloy is shorter than the traditional one; the silicate obtained by the reaction is added to the converter as a coolant to realize the recycling of iron, greatly reducing the content of tail slag; through vanadium extraction and dephosphorization and magnetic separation, phosphorus remains in the silicate phase, while the enriched vanadium iron spinel is phosphorus-free and can be directly used for vanadium extraction; the separated silicate phase is added to the vanadium extraction converter as a coolant to further recover iron and vanadium in the silicate, reducing the contents of iron and vanadium in the tail slag.

[0134] The technical solutions disclosed in the embodiments of the present invention and the technical details disclosed in the examples are only illustrative of the inventive concept of the present invention and do not constitute a limitation on the technical solutions of the embodiments of the present invention. Any conventional changes, substitutions, combinations, etc. made to the technical details disclosed in the embodiments of the present invention have the same inventive concept as the present invention and are within the protection scope of the claims of the present invention.

Claims

1. A method for effectively utilizing converter vanadium slag, characterized in that: Includes steps: S1. Smelting vanadium-containing molten iron with oxygen in a converter, adding a dephosphorizing agent and a coolant during the smelting process, and obtaining molten vanadium slag and semi-steel; wherein the mass content of each component in the vanadium-containing molten iron is: C is 3.5-4.8wt%, Si is 0.01-0.36wt%, Ti is 0.01-0.32wt%, P is 0.01-0.1wt%, V is 0.05-0.5wt%, Cr is 0-0.5wt%; the P content in the semi-steel is less than 0.003wt%; the CaO content in the molten vanadium slag is greater than 5wt%, and the P content is greater than 0.05wt%; S2, adding high-valent oxide materials to the obtained molten vanadium slag, introducing CO2-O2 gas for stirring, and reacting at a set temperature; during the reaction, using ultrasound, microwaves and magnetic fields to synergistically strengthen the reaction process to obtain a magnetic solid vanadium spinel and a molten silicate mixture; the content of the magnetic solid vanadium spinel is 20-100wt%; S3, separating the mixture of magnetic solid vanadium spinel and molten silicate under magnetic field conditions to obtain magnetic solid vanadium spinel and molten silicate respectively; S4, the obtained molten silicate is cooled and added to a converter as a coolant to achieve iron recovery; S5, reducing the obtained magnetic solid vanadium spinel to obtain ferrovanadium alloy; or, S6. The obtained magnetic solid vanadium spinel is subjected to roasting-water immersion-precipitation-hydrothermal treatment to obtain VO2 material containing Na ions; or the magnetic solid vanadium spinel is subjected to roasting-chlorination treatment to obtain VOCl3 gas.

2. The method for effectively utilizing converter vanadium slag according to claim 1, characterized in that: In step S2, ultrasonic enhanced heating is used in the initial mixing stage of the slag, and the ultrasonic intensity is set to 20-40 kHz; microwave enhanced heating is used in the middle stage of the reaction, and the microwave frequency is set to 2.45 GHz; and magnetic field is used to enhance the reaction process in the late stage of the reaction, and the magnetic field intensity is set to 0.1-0.5T.

3. The method for effectively utilizing converter vanadium slag according to claim 1, characterized in that: The dephosphorizing agent includes one or a combination of CaO, CaCO3, Na2CO3, MgO, Al2O3, and CaF2, and the coolant includes silicate.

4. The method for effectively utilizing converter vanadium slag according to claim 1, characterized in that: In step S2, the temperature is set to 1000-1600°C, and the flow rate of CO2-O2 gas is 0-12m / ton of vanadium slag. 3 , materials containing high-valent oxides include MnO2, Mn2O3, Fe3O4, Fe2VO4, CeO2, and nanoscale core-shell structure Fe2O3@CeO2.

5. The method for effectively utilizing converter vanadium slag according to claim 4, characterized in that: The high-valent oxide material is a combination of MnO2 or Mn2O3, Fe3O4 or Fe2VO4; or a combination of MnO2 or Mn2O3, Fe3O4 or Fe2VO4 and CeO2; or a nano-scale core-shell structure Fe2O3@CeO2.

6. The method for effectively utilizing converter vanadium slag according to claim 1, characterized in that: In step S3, the magnetic solid vanadium spinel and the molten silicate mixture are separated at a temperature of 1000-1600°C.

7. The method for effectively utilizing converter vanadium slag according to claim 1, characterized in that: In step S5, the reduction temperature of the magnetic solid vanadium spinel is 800-1400°C, and the reducing agent is carbon, methane or CO.

8. The method for effectively utilizing converter vanadium slag according to claim 1, characterized in that: In step S6, in the roasting-chlorination treatment process of the magnetic solid vanadium spinel, the roasting additive is Na2CO3, NaOH or CaCO3; the chlorinating agent is CrCl3, FeCl3 or AlCl3.

9. The method for effectively utilizing converter vanadium slag according to claim 1, characterized in that: In step S1, the amount of the dephosphorizing agent added is 10-40 kg / ton of vanadium-containing molten iron, and the amount of the coolant added is 10-70 kg / ton of vanadium-containing molten iron.

10. The method for effectively utilizing converter vanadium slag according to claim 1, characterized in that: In step S3, the magnetic field strength is set at 0.1-0.5T.

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