CN113428896A - Method and device for preparing sodium vanadate by taking vanadium fine slag as raw material - Google Patents
Method and device for preparing sodium vanadate by taking vanadium fine slag as raw material Download PDFInfo
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- CN113428896A CN113428896A CN202110692386.7A CN202110692386A CN113428896A CN 113428896 A CN113428896 A CN 113428896A CN 202110692386 A CN202110692386 A CN 202110692386A CN 113428896 A CN113428896 A CN 113428896A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 142
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000002893 slag Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 55
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910000166 zirconium phosphate Inorganic materials 0.000 title claims abstract description 38
- 239000002994 raw material Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 99
- 238000002386 leaching Methods 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 238000007664 blowing Methods 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000002347 injection Methods 0.000 claims abstract description 9
- 239000007924 injection Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 56
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 51
- 239000011780 sodium chloride Substances 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003546 flue gas Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 235000002639 sodium chloride Nutrition 0.000 description 29
- 235000017550 sodium carbonate Nutrition 0.000 description 23
- 230000008569 process Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 210000004127 vitreous body Anatomy 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method and a device for preparing sodium vanadate by taking vanadium fine slag as a raw material, wherein the method comprises the following steps: drying and grinding the vanadium fine slag, removing metal iron to obtain a vanadium fine slag material, and mixing the vanadium fine slag material with a sodium salt additive to obtain a mixed material; carrying out pre-oxidation treatment on the mixed material under the conditions of rotary material turning and air blowing to obtain a pre-oxidized material; carrying out high-temperature roasting on the pre-oxidized material under the conditions of rotary material turning and oxygen injection to obtain clinker; leaching uncooled clinker to extract vanadium, thus obtaining the sodium vanadate; the method can fully promote the vanadium in the vanadium refined slag to be converted into sodium vanadate, and can effectively improve the vanadium conversion rate; in addition, the method can also effectively reduce the reaction temperature and reduce the energy consumption.
Description
Technical Field
The invention relates to the technical field of sodium vanadate preparation, in particular to a method and a device for preparing sodium vanadate by taking vanadium fine slag as a raw material.
Background
Vanadium is an important strategic material and occupies an important position in steel, electronics, chemical engineering, space navigation, atomic energy, navigation, construction, sports, medical treatment, power supply, ceramics and the like in national economy and national defense.
At present, the sodium vanadate is extracted from vanadium fine slag, which is generally obtained by grinding a vanadium raw material, mixing the ground vanadium raw material with a compound additive, performing high-temperature roasting reaction in a rotary kiln at 750-950 ℃ in the presence of oxygen-containing gas to obtain sodium vanadate salt dissolved in water, and leaching and extracting vanadium;
for example, chinese patent application No. 201710386380.0 discloses an oxygen-enriched roasting method for preparing sodium vanadate from vanadium-containing raw material, specifically discloses grinding vanadium-containing raw material to particle size less than 120 μm, mixing with composite additive, placing on reaction mixture bed composed of filler and injecting oxygen-containing gas, in rotary kiln with temperature of 750-; wherein the composite additive is prepared from the following components in a ratio of 40-60: 20-40: 10-30 parts of sodium chloride, sodium sulfate and sodium carbonate; however, the method has high roasting temperature in the sodium vanadate preparation process, needs high energy, and simultaneously enables the vanadium conversion rate in the vanadium raw material to be low, and the maximum vanadium conversion rate is only 95.3%; in addition, because the vanadium extraction efficiency in the prior art is low, the vanadium content in the vanadium tailings is high, and therefore, the vanadium tailings prepared in the prior art need to be used as raw materials for roasting to remove vanadium for many times, and further, the energy consumption is increased.
Disclosure of Invention
The invention aims to provide a method and a device for preparing sodium vanadate by taking refined vanadium slag as a raw material, wherein the method can fully promote vanadium in the refined vanadium slag to be converted into sodium vanadate, and can effectively improve the vanadium conversion rate; in addition, the method can also effectively reduce the reaction temperature and reduce the energy consumption.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the first aspect of the invention provides a method for preparing sodium vanadate by using vanadium refined slag as a raw material, which comprises the following steps:
(a) drying and grinding the vanadium fine slag, removing metal iron to obtain a vanadium fine slag material, and mixing the vanadium fine slag material with a sodium salt additive to obtain a mixed material, wherein the content of MFe in the vanadium fine slag material is not more than 5%;
(b) carrying out pre-oxidation treatment on the mixed material under the conditions of rotary material turning and air blowing to obtain a pre-oxidized material;
(c) carrying out high-temperature roasting on the pre-oxidized material under the conditions of rotary material turning and oxygen injection to obtain clinker, wherein the high-temperature roasting temperature is 620-720 ℃;
(d) leaching uncooled clinker to extract vanadium, and obtaining the sodium vanadate.
Preferably, the mass ratio of the vanadium fine slag material to the sodium salt additive is 1: 0.07-0.3.
Preferably, the mesh size of the vanadium fine slag material is not less than 120 meshes.
Preferably, the sodium salt additive consists of sodium chloride and sodium carbonate, and the mass ratio of the sodium chloride to the sodium carbonate is 1: 0.4-2.
Preferably, the pre-oxidation treatment temperature is 150-600 ℃, and the time is 0.5-4 h.
Preferably, in the step (b), the rotating speed of the rotary stirring is 0.4-1.2 r/min; the pressure of the blowing air is 0.01-1.6 Mpa, and the mixed material per ton is 0.5-50 m3Blowing air with the blowing amount per hour.
Preferably, the high-temperature roasting time is 20-60 min.
Preferably, in the step (c), the rotating speed of the rotary stirring is 0.4-1.2 r/min; the pressure of the injected oxygen is 0.01-1.6 MPa, and the pre-oxidized material per ton is 0.5-10 m3The oxygen is injected according to the injection amount/h.
The invention provides a device for producing sodium vanadate based on the method, which comprises a rotary kiln, a leaching device and a flue gas purification system, wherein the leaching device and the flue gas purification system are respectively connected with the rotary kiln;
one end of the rotary kiln is provided with an air inlet, a feed inlet and a first air outlet, the other end of the rotary kiln is provided with a burner, a discharge outlet and a second air outlet, a first air nozzle is arranged on the side wall of the rotary kiln and at the end part close to the feed inlet, a second air nozzle is arranged at the end part far away from the feed inlet, the first air nozzle is connected with an air pipeline through the air inlet, and the second air nozzle is connected with an oxygen pipeline through the air inlet; the feed inlet is connected with the raw material bin through a spiral conveyer, the first gas outlet and the second gas outlet are respectively connected with the flue gas purification system through a draught fan, and the discharge port is connected with the leaching device.
Preferably, the leaching device comprises a motor, a speed reducer, a leaching tank and a stirring paddle;
the motor is connected with the stirring paddle through the speed reducer, and the stirring paddle is positioned in the leaching tank;
the device comprises a leaching tank, and is characterized in that a feed opening, a water filling opening and an exhaust opening are formed in the top of the leaching tank, the exhaust opening is connected with a condenser, a liquid inlet is formed in the bottom of the side wall of the leaching tank, and a liquid outlet is formed in the upper portion of the side wall of the leaching tank.
Preferably, the side wall of the leaching tank is provided with a lining plate.
Compared with the prior art, the invention has the beneficial effects that at least:
in the high-temperature roasting process, if the MFe content is too high, the MFe reacts with oxygen to easily cause local high temperature so as to agglomerate materials, and further contact between the vanadium fine slag and the oxygen is influenced, so that the vanadium conversion rate is reduced; according to the method, the content of MFe in the vanadium fine slag is not more than 0.5% by deironing the vanadium fine slag, and the iron powder which is not completely removed is oxidized by preoxidation treatment, so that the reaction of MFe and oxygen is eliminated in the high-temperature roasting process, local high temperature is not caused, further material agglomeration is avoided, the contact area of the vanadium fine slag and oxygen is effectively increased, and the vanadium conversion rate is increased.
According to the method, the reaction temperature is effectively reduced by limiting the environment and the temperature of high-temperature roasting, and the problem of excessive side reactions at the existing roasting temperature (750-950 ℃) is solved, for example, sodium carbonate is easy to melt at the temperature, and silicon dioxide in vanadium refined slag reacts with sodium carbonate (the reaction equation is as follows, namely Na)2CO3+SiO2→Na2SiO3+CO2) The chemical reaction is carried out between 784-853 ℃, the highest peak is 835 ℃, liquid vitreous bodies are easy to form, and reaction materials are agglomerated, so that the vanadium fine slag is not easy to react with oxygen; in addition, the melting point temperature of sodium carbonate is 851 ℃, and the melting of soda ash is also not beneficial to the oxidation reaction of vanadium fine slag. However, the technical scheme of the application limits the high-temperature roasting environment and the temperature (620-720 ℃), so that the soda ash cannot be molten in the high-temperature roasting process,The side reaction (such as oxidation products of chromium) is reduced, the energy consumption is reduced, and the dissolution rate of silicon is greatly reduced, so that the agglomeration probability of reaction materials is reduced, the reaction contact area of the vanadium fine slag and oxygen is increased, and the conversion rate and the yield of vanadium are obviously increased.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a schematic structural diagram of an apparatus for producing sodium vanadate according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of the construction of a leaching apparatus according to an embodiment of the invention;
FIG. 3 is a distribution diagram of a first air nozzle of the rotary kiln of the present invention;
FIG. 4 is a distribution diagram of a second air nozzle of the rotary kiln of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail with reference to the following embodiments. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
At present, the high-temperature roasting temperature is higher, higher energy is needed and energy consumption is higher in the existing process of preparing sodium vanadate from vanadium-containing materials, and meanwhile, the existing method enables the vanadium conversion rate in vanadium raw materials to be lower.
In view of this, the embodiment of the present invention provides a method for preparing sodium vanadate from vanadium concentrate slag as a raw material, which includes the following steps:
(a) drying and grinding the vanadium fine slag, removing metal iron to obtain a vanadium fine slag material, and mixing the vanadium fine slag material with a sodium salt additive to obtain a mixed material, wherein the content of MFe in the vanadium fine slag material is not more than 0.5%;
(b) carrying out pre-oxidation treatment on the mixed material under the conditions of rotary material turning and air blowing to obtain a pre-oxidized material;
(c) carrying out high-temperature roasting on the pre-oxidized material under the conditions of rotary material turning and oxygen injection to obtain clinker, wherein the high-temperature roasting temperature is 620-720 ℃;
(d) leaching uncooled clinker to extract vanadium, and obtaining the sodium vanadate.
Research shows that the conversion rate of vanadium increases with the reduction of the granularity of the vanadium fine slag, but after the granularity of the vanadium fine slag is reduced to a certain degree (120-180 meshes, which is equivalent to 125-80 mu), the conversion rate does not change greatly, but the excessively fine granularity of the vanadium slag can cause large energy consumption of grinding materials, low yield and large material particle flying loss; on the other hand, the vanadium fine slag has too fine granularity and large surface activity, and the furnace burden is easy to sinter during roasting and is not beneficial to the extraction of vanadium; further, on the premise of ensuring the vanadium conversion rate, in order to reduce energy consumption, in one embodiment, the method specifically limits the mesh size of the vanadium fine slag material to be not less than 120 meshes; the limitation of the mesh size can guarantee the conversion rate of vanadium in the vanadium fine slag and avoid the problems caused by the over-fine granularity of the vanadium fine slag.
In the high-temperature roasting process, if the MFe content is too high, the MFe reacts with oxygen to easily cause local high temperature so as to agglomerate materials, and further contact between the vanadium fine slag and the oxygen is influenced, so that the vanadium conversion rate is reduced; according to the method, the content of MFe in the vanadium fine slag is not more than 0.5% by deironing the vanadium fine slag, and the iron powder which is not completely removed is oxidized by preoxidation treatment, so that the reaction of MFe and oxygen is eliminated in the high-temperature roasting process, local high temperature is not caused, further material agglomeration is avoided, the contact area of the vanadium fine slag and oxygen is effectively increased, and the vanadium conversion rate is increased.
In one embodiment, the pre-oxidation treatment temperature may be any value of 150 to 600 ℃, and the time may be any value of 0.5 to 4 hours. Further, in order to realize the pre-oxidation treatment better, the method is thatIn one embodiment, the rotating speed of the rotary stirring can be any value of 0.4-1.2 r/min; the pressure of the blowing air can be any value of 0.01-1.6 Mpa, and the mixed material per ton can be 0.5-50 m3Blowing air at any blowing amount per hour. By controlling the pre-oxidation treatment parameters, the residual iron powder in the vanadium fine slag material can be fully oxidized.
The type of the sodium salt additive in the above method of the present invention is not particularly limited, and a sodium salt additive that is conventional in the art may be used, for example, in one embodiment, the sodium salt additive is composed of sodium chloride and sodium carbonate, wherein the mass ratio of the sodium chloride to the sodium carbonate is any one of 1: 0.4 to (0.4-2), specifically 1: 0.4, 1: 1, and 1: 2; more preferably, in other embodiments, the mass ratio of the sodium chloride to the sodium carbonate is any one of 1: (1.5-2); in the sodium salt additive of the present invention, NaCl is a salt of an oxyacid which cannot be directly reacted with V2O5A salt forming reaction occurs. NaCl must be first decomposed into Na2O、Na2O is then the same as V2O5Soluble vanadate is generated. And Na2CO3Then, on the other hand, it is an oxygen-containing complex salt at the same V2O5Can generate salt-forming reaction (Na)2CO3+V2O5＝2NaVO3+CO2) (ii) a In addition, the melting point of NaCl is low, and when NaCl is used alone as an additive for roasting vanadium fine slag, the roasting temperature cannot be increased to a reasonable temperature. And meanwhile, NaCl can also be volatilized in a large amount in the roasting process, the NaCl content of the furnace charge is correspondingly reduced due to the volatilization of the NaCl, the shortage of additional dosage is shown, and if the adding amount of the NaCl is increased, sintering and large kiln ring formation in the furnace charge are easily caused, so that the NaCl is not suitable to be completely adopted as the additive. However, the volatile NaCl can loosen the furnace burden and enlarge the reaction surface, which is beneficial to the vanadium slag reaction and improves the conversion rate. In the above embodiments of the present application, Na is added2CO3Mainly, NaCl is added in a proper amount, and the vanadium conversion rate is obviously improved by compounding the NaCl and the NaCl.
In one embodiment, the mass ratio of the vanadium fine slag material to the sodium salt additive is any one of 1 to (0.07-0.3), and specifically may be 1 to 0.07, 1 to 0.1 or 1 to 0.3. Through the limitation of the raw material proportion, the conversion of vanadium in the vanadium fine slag can be better promoted.
The roasting temperature adopted by the method is only 620-720 ℃, so that the problem of excessive side reactions at the existing roasting temperature (750-950 ℃) is solved, for example, sodium carbonate is easy to melt at the temperature (750-950 ℃), and silicon dioxide in vanadium refined slag reacts with sodium carbonate (the reaction equation is as follows, Na is shown in the specification)2CO3+SiO2→Na2SiO3+CO2) The chemical reaction is carried out between 784-853 ℃, the highest peak is 835 ℃, liquid vitreous bodies are easy to form, and reaction materials are agglomerated, so that the vanadium fine slag is not easy to react with oxygen; in addition, the melting point temperature of the sodium carbonate is 851 ℃, and the melting of the soda ash is melted, so that the oxidation reaction of the vanadium fine slag is also not facilitated. However, according to the technical scheme, the high-temperature roasting environment and the temperature (620-720 ℃) are limited, so that the soda ash cannot be melted in the high-temperature roasting process, side reactions (such as oxidation products of chromium) are reduced, the energy consumption is reduced, the silicon dissolution rate is greatly reduced, the agglomeration probability of reaction materials is reduced, the reaction contact area of the vanadium fine slag and oxygen is increased, and the vanadium conversion rate and the yield are obviously increased.
In one embodiment, the high-temperature roasting time may be any value of 20 to 60 min; the rotating speed of the rotary stirring can be any value of 0.4-1.2 r/min; the pressure of the injected oxygen can be any value of 0.01-1.6 MPa, and the pre-oxidation material per ton can be 0.5-10 m3Blowing oxygen at any blowing amount in the/h; through the control of the high-temperature roasting parameters, the conversion of vanadium in the vanadium fine slag is promoted at the temperature of 620-720 ℃, side reactions are reduced, and the conversion rate and the yield of the vanadium are improved.
The solution used for leaching in the present invention is not strictly limited, and a leaching solution conventional in the art may be used; for example, a solution of water or sodium vanadate; in one embodiment, the mass ratio of the clinker to the leaching solution is 1 to (0.1-100), and may be 1: 1, 1: 10 or 1: 100.
In addition, in order to better leach sodium vanadate in clinker, uncooled clinker is directly leached, so that the temperature of a leaching solution can reach 500-700 ℃, the sodium vanadate in the clinker can be better leached at the temperature, and soluble metavanadate in the clinker is prevented from releasing oxygen to generate water-insoluble vanadium bronze (NaV)6O15And Na8V24O63) And is beneficial to improving the extraction rate of vanadium.
The embodiment of the invention also provides a device for producing sodium vanadate based on the method, as shown in fig. 1 and fig. 2, the device comprises a rotary kiln 1, and a leaching device 2 and a flue gas purification system 3 which are respectively connected with the rotary kiln 1;
one end of the rotary kiln 1 is provided with a gas inlet 11, a feed inlet 12 and a first gas outlet 13, the other end is provided with a burner 14, a discharge outlet 15 and a second gas outlet 16, the end part of the side wall of the rotary kiln 1 close to the feed inlet 12 is provided with a first gas nozzle 17, the end part far away from the feed inlet 12 is provided with a second gas nozzle 18, the first gas nozzle 17 is connected with the air pipeline 4 through the gas inlet 11, the second gas nozzle 18 is connected with the oxygen pipeline 5 through the gas inlet 11, as shown in fig. 3 and 4, the side wall of the rotary kiln 1 is respectively provided with three rows of first gas nozzles 17 and second gas nozzles 18, each row is at an angle of 120 degrees, in the rotation process of the rotary kiln 1, the opening and closing of the first gas nozzle 17 and the second gas nozzle 18 are controlled through a valve, specifically, when the first gas nozzle 17 or the second gas nozzle 18 rotates to the materials in the rotary kiln 1, the valve is opened, when the first air nozzle 17 or the second air nozzle 18 rotates to be far away from the materials in the rotary kiln 1, the valve is closed; the feed inlet 12 is connected with the raw material bin 7 through a spiral conveyer 6, the first gas outlet 13 and the second gas outlet 16 are respectively connected with the flue gas purification system 3 through an induced draft fan 8, the induced draft fan 8 is used for extracting gas in the rotary kiln 1, and the discharge outlet 15 is connected with the leaching device 2;
the leaching device 2 comprises a motor 21, a speed reducer 22, a leaching tank 23 and a stirring paddle 24;
the motor 21 is connected with a stirring paddle 24 through a speed reducer 22, and the stirring paddle 24 is positioned in the leaching tank 23;
the top of the leaching tank 23 is provided with a feed opening 25, a water filling opening 20 and an exhaust opening 26, the exhaust opening 26 is connected with a condenser 9, the condenser 9 is used for condensing water vapor overflowing from the exhaust opening 26, the bottom of the side wall of the leaching tank 23 is provided with a liquid inlet 27, and the upper part of the side wall of the leaching tank is provided with a liquid outlet 28; the side walls of the leaching tank 24 are provided with lining plates 29.
In addition, to reduce the content of nitrogen oxides in the flue gas, in one embodiment, the combustion gas used by the burner 14 is natural gas, coal gas, and oxygen; by adopting the pure oxygen burner 14 and no secondary air, the gas at the two ends of the rotary kiln 1 can be introduced into the flue gas purification system 3 through the induced draft fan 8, so that the emission concentration of the nitrogen oxide in the flue gas in the rotary kiln 1 is lower than 20mg/NM3(ii) a In the prior art, a large amount of secondary air enters the rotary kiln 1, and oxynitride is generated after the gas is combusted by the combustor 14, so that the emission of nitrogen oxide in flue gas reaches 200mg/NM3。
The technical solution of the present invention will be described in further detail below with reference to specific examples.
The following examples used the following starting materials:
vanadium fine slag: comprises the following components in percentage by weight: v2O5 13.5％、MFe 13％、TiO2 10.6％、MnO 9.1％、SiO2 14％、P 0.28％、CaO 4.6％、Cr2O3 8.2％；
Sodium chloride: is purchased in the market;
sodium carbonate: is commercially available.
Example 1
The embodiment is a method for preparing sodium vanadate by taking vanadium fine slag as a raw material, which comprises the following steps:
(a) drying and grinding the vanadium fine slag to a grain size of not less than 120 meshes, removing metallic iron by an automatic continuous dry type electromagnetic iron remover to obtain a vanadium fine slag material, and mixing the vanadium fine slag material with a sodium salt additive to obtain a mixed material, wherein the content of MFe in the vanadium fine slag material is 2.43%, the mass ratio of the vanadium fine slag material to the sodium salt additive is 1: 0.07, the sodium salt additive is composed of sodium chloride and sodium carbonate, and the mass ratio of the sodium chloride to the sodium carbonate is 1: 1.5;
(b)carrying out pre-oxidation treatment on the mixed material under the conditions of 0.4r/min rotary material turning and 0.5Mpa air blowing to obtain a pre-oxidized material, wherein the pre-oxidation treatment temperature is 300-600 ℃, the time is 0.5h, and the mixed material per ton is 20m3Blowing air at the blowing amount of/h;
(c) carrying out high-temperature roasting on the pre-oxidized material under the conditions of 0.4r/min rotary stirring and 0.5MPa oxygen injection to obtain clinker, wherein the high-temperature roasting temperature is 680-720 ℃, the high-temperature roasting time is 20min, and the pre-oxidized material per ton is 50m3Blowing oxygen at a blowing amount of/h;
(d) directly mixing uncooled clinker with water for leaching, and extracting vanadium to obtain sodium vanadate, wherein the mass ratio of the clinker to the water is 1: 10.
Example 2
The embodiment is a method for preparing sodium vanadate by taking vanadium fine slag as a raw material, which comprises the following steps:
(a) drying and grinding the vanadium fine slag to a grain size of not less than 120 meshes, removing metallic iron by an automatic continuous dry type electromagnetic iron remover to obtain a vanadium fine slag material, and mixing the vanadium fine slag material with a sodium salt additive to obtain a mixed material, wherein the content of MFe in the vanadium fine slag material is 4.28%, the mass ratio of the vanadium fine slag material to the sodium salt additive is 1: 0.3, the sodium salt additive consists of sodium chloride and sodium carbonate, and the mass ratio of the sodium chloride to the sodium carbonate is 1: 2;
(b) carrying out pre-oxidation treatment on the mixed material under the conditions of 1.2r/min rotary material turning and 1.6Mpa blowing air to obtain a pre-oxidized material, wherein the pre-oxidation treatment temperature is 150-300 ℃, the time is 4 hours, and the mixed material per ton is 50m3Blowing air at the blowing amount of/h;
(c) carrying out high-temperature roasting on the pre-oxidized material under the conditions of 1.2r/min rotary material turning and 1.6MPa oxygen injection to obtain clinker, wherein the high-temperature roasting temperature is 620-680 ℃, the high-temperature roasting time is 60min, and the pre-oxidized material per ton is 10m3Blowing oxygen at a blowing amount of/h;
(d) directly mixing uncooled clinker with water for leaching, and extracting vanadium to obtain sodium vanadate, wherein the mass ratio of the clinker to the water is 1: 100.
Example 3
The embodiment is a method for preparing sodium vanadate by taking vanadium fine slag as a raw material, which comprises the following steps:
(a) drying and grinding the vanadium fine slag to a grain size not less than 120 meshes, removing metallic iron by an automatic continuous dry type electromagnetic iron remover to obtain a vanadium fine slag material, and mixing the vanadium fine slag material with a sodium salt additive to obtain a mixed material, wherein the content of MFe in the vanadium fine slag material is 4.43%, the mass ratio of the vanadium fine slag material to the sodium salt additive is 1: 0.1, the sodium salt additive consists of sodium chloride and sodium carbonate, and the mass ratio of the sodium chloride to the sodium carbonate is 1: 1.8;
(b) carrying out pre-oxidation treatment on the mixed material under the conditions of 1r/min rotary material turning and 1.0Mpa air blowing to obtain a pre-oxidized material, wherein the pre-oxidation treatment temperature is 300-400 ℃, the time is 2 hours, and the mixed material per ton is 30m3Blowing air at the blowing amount of/h;
(c) carrying out high-temperature roasting on the pre-oxidized material under the conditions of 1r/min rotary material turning and 1.0MPa oxygen injection to obtain clinker, wherein the high-temperature roasting temperature is 650-700 ℃, the high-temperature roasting time is 40min, and each ton of the pre-oxidized material is 8m3Blowing oxygen at a blowing amount of/h;
(d) directly mixing uncooled clinker with water for leaching, and extracting vanadium to obtain sodium vanadate, wherein the mass ratio of the clinker to the water is 1: 50.
Comparative example 1
The comparative example is a method for preparing sodium vanadate from vanadium fine slag as a raw material, and the method is basically the same as the method in example 3, except that in the step (a), after metal iron is removed by an automatic continuous dry electromagnetic iron remover, the content of MFe in the vanadium fine slag material is 6.67%.
Comparative example 2
The comparative example is a method for preparing sodium vanadate from vanadium fine slag as a raw material, and the method is basically the same as the method in example 3 except that the injected oxygen is replaced by injected air in the step (c).
Comparative example 3
This comparative example is a process for the preparation of sodium vanadate from vanadium concentrate slag, which is essentially identical to the process of example 3, except that in step (d) the clinker is cooled to 100 ℃ and then leached by mixing with water.
Examples of the experiments
Respectively preparing sodium vanadate according to the methods in the example 3 and the comparative examples 1 to 3; respectively calculating the vanadium conversion rate in the vanadium fine slag, the chromium oxidation rate in the vanadium fine slag, the vanadium tailing band loss and the total vanadium content in the leached vanadium tailing;
vanadium in the vanadium tailings is divided into soluble vanadium and insoluble vanadium, the insoluble vanadium is generally unreacted vanadium, and the band loss refers to soluble vanadium (namely sodium vanadate) carried away by the vanadium tailings,
the calculation results are shown in table 1:
TABLE 1 index for sodium vanadate prepared by different methods
As can be seen from the data in Table 1:
according to the technical scheme, the vanadium conversion rate can be better improved and the chromium oxidation rate is reduced through the limitation of a specific process, so that the side reaction is reduced, in addition, the vanadium tailing band loss can be effectively reduced, and the vanadium loss is reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (10)
1. A method for preparing sodium vanadate by taking vanadium fine slag as a raw material is characterized by comprising the following steps:
(a) drying and grinding the vanadium fine slag, removing metal iron to obtain a vanadium fine slag material, and mixing the vanadium fine slag material with a sodium salt additive to obtain a mixed material, wherein the content of MFe in the vanadium fine slag material is not more than 5%;
(b) carrying out pre-oxidation treatment on the mixed material under the conditions of rotary material turning and air blowing to obtain a pre-oxidized material;
(c) carrying out high-temperature roasting on the pre-oxidized material under the conditions of rotary material turning and oxygen injection to obtain clinker, wherein the high-temperature roasting temperature is 620-720 ℃;
(d) leaching uncooled clinker to extract vanadium, and obtaining the sodium vanadate.
2. The method according to claim 1, wherein the mass ratio of the vanadium fine slag material to the sodium salt additive is 1: 0.07-0.3.
3. The method as claimed in claim 1 or 2, wherein the sodium salt additive is composed of sodium chloride and sodium carbonate, and the mass ratio of the sodium chloride to the sodium carbonate is 1: 0.4-2.
4. The method according to claim 1, wherein the pre-oxidation treatment temperature is 150 to 600 ℃ and the time is 0.5 to 4 hours.
5. The method according to claim 1, wherein in the step (b), the rotating speed of the rotary stirring material is 0.4-1.2 r/min; the pressure of the blowing air is 0.01-1.6 Mpa, and the mixed material per ton is 0.5-50 m3Blowing air with the blowing amount per hour.
6. The method according to claim 1, wherein the high-temperature roasting time is 20-60 min.
7. The method according to claim 1, wherein in the step (c), the rotating speed of the rotary stirring material is 0.4-1.2 r/min; the pressure of the injected oxygen is 0.01-1.6 MPa, and the pre-oxidized material per ton is 0.5-10 m3The oxygen is injected according to the injection amount/h.
8. The device for producing sodium vanadate based on the method of any one of claims 1 to 7, which is characterized by comprising a rotary kiln, and a leaching device and a flue gas purification system which are respectively connected with the rotary kiln;
one end of the rotary kiln is provided with an air inlet, a feed inlet and a first air outlet, the other end of the rotary kiln is provided with a burner, a discharge outlet and a second air outlet, a first air nozzle is arranged on the side wall of the rotary kiln and at the end part close to the feed inlet, a second air nozzle is arranged at the end part far away from the feed inlet, the first air nozzle is connected with an air pipeline through the air inlet, and the second air nozzle is connected with an oxygen pipeline through the air inlet; the feed inlet is connected with the raw material bin through a spiral conveyer, the first gas outlet and the second gas outlet are respectively connected with the flue gas purification system through a draught fan, and the discharge port is connected with the leaching device.
9. The apparatus according to claim 8, wherein the leaching apparatus comprises a motor, a speed reducer, a leaching tank and a stirring paddle;
the motor is connected with the stirring paddle through the speed reducer, and the stirring paddle is positioned in the leaching tank;
the device comprises a leaching tank, and is characterized in that a feed opening, a water filling opening and an exhaust opening are formed in the top of the leaching tank, the exhaust opening is connected with a condenser, a liquid inlet is formed in the bottom of the side wall of the leaching tank, and a liquid outlet is formed in the upper portion of the side wall of the leaching tank.
10. The apparatus according to claim 9, wherein the side walls of the leaching tank are provided with lining plates.
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