CN115725863A - Method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching step by step - Google Patents
Method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching step by step Download PDFInfo
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- CN115725863A CN115725863A CN202211464212.6A CN202211464212A CN115725863A CN 115725863 A CN115725863 A CN 115725863A CN 202211464212 A CN202211464212 A CN 202211464212A CN 115725863 A CN115725863 A CN 115725863A
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- 238000002386 leaching Methods 0.000 title claims abstract description 202
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 186
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000005261 decarburization Methods 0.000 claims abstract description 48
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000000605 extraction Methods 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 15
- 239000011707 mineral Substances 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 5
- 238000010586 diagram Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004904 shortening Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- 229910052900 illite Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
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- 239000003345 natural gas Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000003034 coal gas Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005906 dihydroxylation reaction Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
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- 229910001784 vanadium mineral Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
A method for extracting vanadium from vanadium shale by segmented microwave roasting-step alkaline leaching belongs to the technical field of vanadium extraction from vanadium shale, and comprises the steps of crushing the vanadium shale, and performing segmented microwave roasting on the obtained finely ground vanadium shale, wherein the segmented microwave roasting comprises preheating roasting, microwave decarburization roasting and microwave crystal breaking roasting; and after the microwave roasting is carried out in a segmented mode, carrying out alkaline leaching on the obtained roasted product step by step to extract vanadium, wherein the alkaline leaching specifically comprises microwave alkaline leaching and pressurized alkaline leaching to obtain vanadium-rich pregnant solution. The method has the advantages that the microwave is used for selectively heating the carbon efficiently, so that the microwave decarburization roasting time is shortened, and the decarburization efficiency is improved; by means of the efficient selective heating characteristic of the microwave to the vanadium shale, the crystal lattice damage of the microwave crystal breaking roasting process to the vanadium-containing minerals is strengthened, and further the efficiency of the microwave crystal breaking roasting is improved. The method adopts a microwave-pressurization two-step leaching process in the leaching process, so that vanadium-rich pregnant solution with less impurity ions is obtained while the leaching rate is ensured.
Description
Technical Field
The invention relates to the technical field of vanadium extraction from vanadium shale, in particular to a method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching step by step.
Background
Vanadium is a rare metal element and is a national important strategic resource. Because of its excellent performance, it is widely used in various fields of steel industry, alloy, chemical industry, superconducting material, vanadium battery, etc. and has great resource demand.
Vanadium shale is also called stone coal, and is an important vanadium-containing resource with huge reserves in China. In the existing vanadium shale vanadium extraction process, blank roasting-acid leaching is an environment-friendly and effective vanadium extraction process. In order to improve the gas-solid reaction efficiency, the suspension roasting technology is applied to the field of vanadium extraction from shale, such as patents CN111304465A, namely a method for extracting vanadium by decarbonization-crystal breaking roasting and enhanced acid leaching of stone coal, CN111304464A, a method for extracting vanadium by multistage roasting, enhanced acid mixing, curing and vanadium extraction of stone coal vanadium ore, CN114111359A, a system and an oxidizing roasting method for extracting vanadium by step oxidizing roasting of stone coal vanadium ore, and CN111719054A, namely a comprehensive utilization method for oxidizing, crystal breaking and roasting of stone coal vanadium ore.
Although the patents disclosed above relate to shale vanadium extraction processes, these existing roasting processes are only performed at high temperature, and it is difficult to completely destroy the crystal lattice of the vanadium-containing mineral, and thus it is difficult to achieve a good vanadium extraction effect on the refractory vanadium shale.
The conventional alkaline leaching process is carried out at normal temperature and normal pressure, and has low leaching rate, large medicament consumption and longer leaching time, so the leaching efficiency is low.
The existing leaching process is one-step leaching, and other impurity metal ions are introduced into the solution while the vanadium leaching rate is improved, so that the subsequent purification difficulty is high.
Disclosure of Invention
The invention provides a method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching step by step, and aims to solve the problems of poor roasting effect, poor leaching effect and more impurity ions in a leaching solution of carbon-containing vanadium shale difficult to leach in the vanadium extraction process.
The invention applies the microwave heating technology to decarburization roasting and crystal breaking roasting operation of the suspension roasting process. The microwave decarburization roasting time is shortened and the decarburization efficiency is improved by virtue of the efficient selective heating characteristic of microwaves on carbon; the aims of strengthening the crystal lattice damage of the vanadium-containing mineral, shortening the crystal breaking roasting time, improving the crystal breaking roasting efficiency and strengthening the decarburization effect in the suspension roasting process are fulfilled by the efficient selective heating characteristic of the microwave to the vanadium shale.
The invention adopts microwave and pressurization means to enhance the leaching efficiency of the roasted product, and realizes the purposes of reducing the dosage of the leaching solution and shortening the leaching time; and by a microwave-pressurization two-step leaching process, vanadium-rich pregnant solution with less impurity ions is obtained while the leaching rate is ensured.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching in steps, which comprises the following steps:
s1, crushing:
the vanadium shale crushing process comprises a crushing process and an ore grinding process; after crushing, obtaining the finely ground vanadium shale with the grain diameter of-0.045 mm accounting for 70-85%;
in the S1, the crushing process is: crushing the vanadium shale raw ore to the granularity of 0.8-8 mm to obtain crushed ore;
the feeding granularity of the vanadium shale raw ore is within the range of 5 mm-250 mm.
The crusher used for crushing is preferably one of a jaw crusher, an impact crusher or a high-pressure roller mill.
The grinding machine adopted by the ore grinding is preferably one of a semi-automatic grinding machine, an overflow ball mill or a stirring mill.
Further, filtering the ore grinding product, and scattering the ore grinding product after the water content is less than or equal to 10% to obtain finely ground vanadium shale for sectional microwave roasting;
s2: staged microwave roasting
The segmented microwave roasting comprises preheating roasting, microwave decarburization roasting and microwave crystal breaking roasting;
(1) Preheating and roasting:
preheating and roasting the finely ground vanadium shale, wherein the preheating and roasting temperature is 600-650 ℃, the retention time is 20-35 s, and the preheated vanadium shale with the preheating temperature of 380-480 ℃ is obtained;
the preheating roasting can remove the adsorption water in the milled vanadium shale.
In the step (1) of S2, the fuel gas used for preheating is preferably one of natural gas and coal gas.
(2) Microwave decarbonizing roasting
Performing microwave decarburization roasting on preheated vanadium shale, applying a microwave field during the microwave decarburization roasting to generate electromagnetic energy for rapidly heating the material, introducing air during the microwave decarburization roasting, and adjusting roasting air amount to 6m 3 /h～8m 3 The microwave decarburization roasting temperature is controlled to be 580-630 ℃, and the microwave decarburization roasting time is 15-35 min, so that decarburized vanadium shale is obtained;
in step S2 (2), the carbonaceous materials in the vanadium shale have strong wave-absorbing ability, so that the carbonaceous materials are rapidly heated and combusted in the microwave field, thereby shortening the microwave decarburization roasting time and improving the decarburization efficiency. In addition, the carbonaceous gangue mineral quartz has much stronger wave absorbing capability, so that different substances have larger temperature difference, and further expansion stress difference and even microcracks are formed. This both contributes to the improvement of the roasting efficiency and the subsequent leaching efficiency. As most of the carbonaceous material is removed by combustion, the vanadium is enriched in the ash. The suspended material in the furnace is heated uniformly, and sintering caused by local high temperature can be prevented. The process can also remove part of crystallized water and volatile components from the raw ore to form the decarburized vanadium shale with uniform and stable properties. And feeding the decarburized vanadium shale to the next section of microwave crystal-breaking roasting operation.
And in the step (2) of S2, air is introduced from the bottom, so that the material is in a suspension state, and the decarburization effect is improved.
(3) Microwave crystal breaking roasting:
carrying out microwave crystal breaking roasting on the decarburized vanadium shale, wherein in the microwave crystal breaking roasting process, microwave heating is adopted, and air and/or O are introduced into the bottom 2 The amount of the mixed gas is controlled to be 10m 3 /h～12m 3 The microwave power is 32kW to 48kW, the microwave crystal breaking roasting temperature is 880 ℃ to 940 ℃, and the roasting time is 40min to 70min, so that a roasted product is obtained;
in the step (3) of the step S2, the mica and illite minerals are subjected to dehydroxylation reaction, the silicon-oxygen octahedral structure where the vanadium ions in the crystal lattice are located is unstable, and the constraint of the mineral crystal lattice on vanadium is weakened. It should be noted that, because mica and illite vanadium-containing minerals have strong wave-absorbing ability, they will be heated up rapidly in microwave field, thereby shortening the heating up time, strengthening dehydroxylation reaction of vanadium-containing minerals and crystal lattice destruction rate. In addition, the vanadium-containing minerals have stronger wave-absorbing capability than quartz, and large temperature difference also exists between the minerals during heating, so that expansion stress difference is formed, and even microcracks are formed. This also contributes to the improvement of the crystal breaking efficiency and the subsequent leaching efficiency.
S3: step-by-step alkaline leaching vanadium extraction
Carrying out alkaline leaching on the roasted product step by step to extract vanadium, wherein the alkaline leaching specifically comprises microwave alkaline leaching and pressurized alkaline leaching;
(1) Microwave alkaline leaching:
carrying out microwave alkaline leaching on the roasted product, applying microwave in the leaching process, wherein the microwave power is 7 kW-12 kW, and the alkaline leaching is carried out according to the liquid-solid ratio: 1g of roasted product (2-3) mL, leaching temperature of 65-85 ℃, 5-15% of alkali in the alkaline leaching solution by mass percent of the roasted product, leaching time of 40-80 min to obtain microwave alkaline leaching mixed solution, and performing solid-liquid separation to obtain microwave leaching residue and first vanadium-rich pregnant solution.
After microwave alkaline leaching, the leaching rate of vanadium in the shale can reach 60-80%, and the alkaline leaching solution obtained after vanadium precipitation of the separated first vanadium-rich pregnant solution can be recycled.
In the step (1) of the step S3, the microwave heater for the more soluble material in the raw ore is used for heating the material and the sodium hydroxide solution, so that the leaching time can be shortened, and the vanadium leaching rate can be increased.
(2) Pressure alkaline leaching:
the microwave leaching residue is subjected to pressurized alkaline leaching operation, sodium hydroxide is used as a leaching agent to react with high-valence vanadium oxide, the dissolution of vanadium in raw ore is realized, the pressure of pressurized alkaline leaching is ensured to be 1.0-1.8 MPa in the leaching process, and the leaching solution is pressurized according to the liquid-solid ratio: 1g of microwave leaching residue = (1.5-2) mL, the leaching temperature is 160-190 ℃, the mass percent of a leaching agent in the pressurized leaching solution accounts for 10-20% of the microwave leaching residue, the leaching time is 40-90 min, pressurized alkaline leaching mixed liquor is obtained, and the final leaching residue and a second vanadium-rich pregnant solution are obtained after solid-liquid separation.
In the pressure alkaline leaching, the leaching rate of vanadium in the shale is 20-30%, the separated second vanadium-rich pregnant solution can be recycled after vanadium precipitation, and the content of impurities in the obtained second vanadium-rich pregnant solution is less than 0.40g/L.
By adopting the method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching step by step, the total leaching rate of vanadium is 85-95%.
The invention relates to a method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching step by step, which has the key points that:
1. the invention applies the microwave heating technology to the microwave decarburization roasting operation of the suspension roasting process. By utilizing the efficient selective heating characteristic of microwave to carbon, the microwave decarburization roasting time is shortened, and the decarburization efficiency is improved.
2. The invention applies the microwave heating technology to the crystal breaking roasting operation of the suspension roasting process. By utilizing the efficient selective heating characteristic of the microwave to the vanadium shale, the aims of strengthening the crystal lattice damage of the vanadium-containing mineral, shortening the roasting time and improving the vanadium leaching rate of a roasted product are fulfilled.
3. The invention adopts microwave and pressurizing means to enhance the alkaline leaching efficiency of the roasted product, and achieves the purposes of reducing the dosage of alkaline liquor and shortening the leaching time. By a microwave-pressurization two-step leaching process, the leaching rate is ensured, and part of vanadium-rich pregnant solution with less impurity ions is obtained. Solves the problems of poor roasting effect, poor leaching effect and more impurity ions in the leaching solution of the carbon-containing vanadium shale which is difficult to leach in the vanadium extraction process.
The invention provides a method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching in steps, which has the following beneficial effects:
(1): the microwave heating technology is applied to the microwave decarburization roasting and the crystal breaking roasting operation of the suspension roasting process. The efficient selective heating characteristic of microwave to carbon is utilized, the microwave decarburization roasting time is shortened, and the decarburization efficiency is improved; by utilizing the efficient selective heating characteristic of the microwave to the vanadium shale, the aims of strengthening the crystal lattice damage of the vanadium-containing mineral, shortening the roasting time and improving the vanadium leaching rate of a roasted product are fulfilled.
(2): the invention adopts microwave and pressurizing means to strengthen the alkaline leaching efficiency of the roasted product, and realizes the purposes of reducing the dosage of alkaline liquor and shortening the leaching time. And by a microwave-pressurization two-step leaching process, vanadium-rich pregnant solution with less impurity ions is obtained while the leaching rate is ensured. Solves the problems of poor roasting effect, poor leaching effect and more impurity ions in the leaching solution of the carbon-containing vanadium shale which is difficult to leach in the vanadium extraction process.
Drawings
FIG. 1 is a schematic diagram of a process of sectional microwave roasting-stepwise alkaline leaching of vanadium shale.
FIG. 2 is a schematic diagram showing the change of materials in the preheating roasting device.
FIG. 3 is a schematic diagram of the material change of the microwave decarburization roasting device.
FIG. 4 is a schematic diagram showing the material change of the microwave crystal-breaking roasting device.
FIG. 5 is a schematic diagram of the material change of the microwave alkaline leaching device.
Detailed Description
The technical scheme in the patent implementation is clearly and completely described with reference to the attached drawings. It should be noted that the examples described herein are for further explanation and illustration only, and are not intended to limit the scope of the application. All other embodiments, which can be derived by a person skilled in the art without making creative efforts, based on the present invention, belong to the protection scope of the present patent.
In the following embodiments, a schematic diagram of a method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching in steps is shown in fig. 1, and includes fig. 2, which is a schematic diagram of changes of materials of a preheating roasting device, fig. 3, which is a schematic diagram of changes of materials of a microwave decarburization roasting device, fig. 4, which is a schematic diagram of changes of materials of a microwave crystal breaking roasting device, and fig. 5, which is a schematic diagram of changes of materials of a microwave alkaline leaching device.
Example 1
In this example, the vanadium shale raw ore is obtained from a place in Sichuan, raw ore V 2 O 5 0.82% of C, 10.62% of TFe, 1.52% of SiO 2 The content is 52.65%, and quartz and vanadium-containing illite are main constituent minerals. The examples were developed as follows:
(1) Crushing: the raw ore is crushed to 0.8 mm-8 mm by a high-pressure roller mill and then is ground to-0.045 mm accounting for 75% by a stirring mill. The ground ore product is filtered (water content is 5 percent), scattered and fed into a segmented microwave roasting system.
(2) Preheating and roasting: the gas (natural gas in this embodiment) is burned in the combustion station at the lower part of the preheating roasting device, and air is introduced to heat the furnace body to 650 ℃, and the material change diagram of the device is shown in fig. 2. The fine ore stays in the furnace for about 25 seconds and is further preheated. The fine ore is heated to 420 ℃, and the preheated vanadium shale material without the adsorption water is fed to the microwave decarburization roasting operation.
(3) And (3) microwave decarburization roasting: the preheated vanadium shale is fed into the microwave decarburization roasting operation, and the material change of the microwave decarburization device is shown in figure 3. Regulating microwave heater to control temperature in the furnace chamber at 630 deg.C, and introducing air into the lower part of the microwave decarbonizing device at air flow of 7m 3 H is used as the reference value. The decarburized vanadium shale reacts in the equipment for 20min and then is subjected to microwave crystal breaking roasting operation.
(4) Microwave crystal breaking and roasting: the decarburized vanadium shale is fed into a microwave crystal breaking roasting device, and the material change is shown in figure 4. Setting the power of a microwave heater at 35kW, and introducing air and O 2 The gas inlet amount of the mixed gas of (2) is 11m 3 H (by volume, air: O) 2 = 3:1), control furnaceThe reaction was continued for 40min at an in vivo temperature of 920 ℃. And (4) subjecting the roasted product to microwave alkaline leaching operation to obtain the roasted product.
(5) Microwave alkaline leaching: sodium hydroxide is used as a leaching agent to react with high-valence vanadium oxide, so that the dissolution of vanadium in the raw ore is realized. Weighing sodium hydroxide accounting for 9% of the mass fraction of the roasted product, and then according to the liquid-solid ratio, alkali leaching: the roasted product is 2mL. The power of a microwave generator in the leaching process is 8kW, the leaching temperature is 75 ℃, and the leaching time is 45min. The leaching rate of vanadium in the operation is about 70%, and the material change in the microwave alkaline leaching device is shown in figure 5.
(6) Pressure alkaline leaching: and (5) feeding the microwave leaching residues into a pressurized alkaline leaching operation. Ensuring the pressure in the reaction kettle to be 1.2MPa in the leaching process, weighing sodium hydroxide accounting for 15% of the mass fraction of the roasted product, and then pressurizing the leaching solution according to the liquid-solid ratio: 1.5mL of microwave leaching residue, 1.1g of sodium hydroxide aqueous solution is prepared as a pressurized leaching solution, and the microwave leaching residue is added into the pressurized leaching solution, wherein the leaching temperature is 170 ℃, and the leaching time is 60min. The working leaching rate of vanadium in shale is 23%. Finally, the vanadium leaching rate of the process reaches 93.21 percent.
Example 2
In the example, the vanadium shale raw ore is taken from some places in Shaanxi, and V in the raw ore 2 O 5 0.83% of C, 18.16% of TFe, 3.54% of SiO 2 61.87%, quartz and vanadium-containing illite and vanadium-containing sericite are the main minerals, wherein the vanadium mineral is mainly represented in the illite and the sericite in a similar manner, and the content of the vanadium mineral is 88%. The example of the microwave crystal breaking roasting vanadium extraction process was developed as follows:
(1) Crushing: the raw ore is crushed to 1 mm-6 mm by a jaw crusher and then is ground to-0.045 mm accounting for 70% by a ball machine. The ground ore product is filtered (the water content is 9 percent), scattered and fed into a segmented microwave roasting system.
(2) Preheating and roasting: introducing coal gas and air into the preheating roasting device for combustion, and heating the furnace to 630 ℃. The fine ore stays in the furnace for about 20 seconds and is thus preheated. The fine ore is heated to 450 ℃, and the preheated vanadium shale material without adsorption water is fed to the microwave decarburization roasting operation.
(3) And (3) microwave decarburization roasting: the preheated vanadium shale is fed into the microwave decarburization roasting operation, and the material change of the microwave decarburization roasting device is shown in figure 3. The temperature in the furnace chamber is controlled at 600 ℃ by adjusting the microwave heater, and air is introduced into the lower part of the microwave decarburization device, wherein the air flow is 8m 3 H is used as the reference value. The decarburized vanadium shale reacts in the equipment for 25min and then is subjected to microwave crystal-breaking roasting operation.
(4) Microwave crystal breaking and roasting: the decarburized vanadium shale is fed into a microwave crystal-breaking roasting device, and the material change is shown in figure 4. Setting the power of a microwave heater to be 38kW, and introducing air and O 2 The gas mixture is introduced into the reactor at a flow rate of 12m 3 H (by volume, air: O) 2 = 3:1), controlling the temperature in the furnace body to 930 ℃, and continuously reacting for 60min to obtain the roasted product.
(5) Microwave alkaline leaching: weighing sodium hydroxide accounting for 5% of the mass fraction of the roasted product, and then according to the liquid-solid ratio, carrying out alkali leaching: the roasted product is 2mL. In the leaching process, the power of a microwave generator is 7kW, the leaching temperature is 65 ℃, the leaching time is 60min, a microwave alkaline leaching mixed solution is obtained, and solid-liquid separation is carried out to obtain microwave leaching residue and a first vanadium-rich pregnant solution. The operational leaching rate of vanadium is 67.21%, and the material change in the microwave alkaline leaching device is shown in figure 5.
(6) Pressure alkaline leaching: and (4) feeding the separated microwave leaching residue into a pressurized alkaline leaching operation. Ensuring the pressure in the reaction kettle to be 1.0MPa, weighing sodium hydroxide accounting for 15% of the mass fraction of the roasted product, and then pressurizing the leaching solution according to the liquid-solid ratio: and (3) preparing a sodium hydroxide aqueous solution as a pressurized leaching solution for microwave leaching residue of 2mL, adding the microwave leaching residue into the pressurized leaching solution, wherein the leaching temperature is 160 ℃, and the leaching time is 70min. The working leaching rate of vanadium in shale is 23.58%. Finally, the vanadium leaching rate of the process is 90.79%.
Example 3
In this case, the vanadium shale is taken from some place in Gansu province, and the raw ore V 2 O 5 0.93% of C, 11.21% of TFe, 2.32% of SiO 2 The content is 54.35 percent, and quartz and vanadium-containing illite are main constituent minerals. Example is as followsThe following steps are developed:
(1) Crushing: the raw ore is crushed to 0.8-8 mm by a high-pressure roller mill and then is ground to-0.045 mm which accounts for 79% by a semi-autogenous mill. The ground ore product is filtered (water content is 10%) and fed into a sectional microwave roasting system.
(2) Preheating and roasting: the natural gas is combusted in a combustion station at the lower part of the preheating roasting device, and air is introduced to heat the interior of the furnace body to 640 ℃. The fine ore stays in the furnace for about 35 seconds and is further preheated. The fine ore is heated to 410 ℃, and the preheated vanadium shale material without adsorption water is fed to the microwave decarburization roasting operation.
(3) And (3) microwave decarburization roasting: the preheated vanadium shale is fed into the microwave decarburization roasting operation, and the material change of the microwave decarburization roasting device is shown in figure 3. The temperature in the furnace chamber is controlled at 640 ℃ by adjusting the microwave heater, and air is introduced into the lower part of the microwave decarburization device, wherein the air flow is 8m 3 H is used as the reference value. The decarburized vanadium shale reacts in the equipment for 35min and then is subjected to microwave crystal breaking roasting operation.
(4) Microwave crystal breaking and roasting: the decarburized vanadium shale is fed into a microwave crystal breaking roasting device, and the material change is shown in figure 4. Setting the power of a microwave heater to 33kW, and introducing air and O 2 The gas mixture is introduced into the reactor with the gas flow of 10m 3 H (by volume, air: O) 2 = 3:1), the temperature in the furnace body is controlled at 940 ℃, and the reaction is continued for 70min, so as to obtain the roasted product.
(5) Microwave alkaline leaching: weighing sodium hydroxide accounting for 5% of the mass fraction of the roasted product, and then according to the liquid-solid ratio, alkali leaching: the roasted product is 2mL. In the leaching process, the power of a microwave generator is 8kW, the leaching temperature is 85 ℃, and the leaching time is 80min, so that the microwave leaching residue and the first vanadium-rich pregnant solution are obtained. The operational leaching rate of vanadium is 66.84%, and the material change in the microwave alkaline leaching device is shown in figure 5.
(6) Pressure alkaline leaching: and (4) feeding the separated microwave leaching residue into a pressurized alkaline leaching operation. Ensuring the pressure in the reaction kettle to be 1.0MPa, weighing sodium hydroxide accounting for 15% of the mass fraction of the roasted product, and then pressurizing the leaching solution according to the liquid-solid ratio: and (3) preparing a sodium hydroxide aqueous solution as a pressurized leaching solution for microwave leaching residue of 2mL, adding the microwave leaching residue into the pressurized leaching solution, wherein the leaching temperature is 160 ℃, and the leaching time is 70min. The working leaching rate of vanadium in shale is 26.51%. Finally, the vanadium leaching rate of the process is 93.35%.
Example 4
The difference from example 1 is that: the microwave decarburization roasting temperature is 625 ℃, the microwave crystal breaking roasting temperature is 906 ℃, and the total gas amount of the microwave roasting is 11.3m 3 The other conditions were kept constant. Finally, the total vanadium leaching rate was 92.64%.
Example 5
The difference from example 2 is that: the microwave decarburization roasting temperature is 610 ℃, the microwave crystal breaking roasting temperature is 898 ℃, and the total gas amount of the microwave roasting is 10.6m 3 The other conditions were kept constant. Finally, the total leaching rate of vanadium was 89.43%.
Example 6
The difference from example 3 is that: the microwave decarburization roasting temperature is 580 ℃, the microwave crystal breaking roasting temperature is 930 ℃, and the total gas amount of the microwave roasting is 12m 3 The other conditions were kept constant. Finally, the total vanadium leaching rate is 94.98%.
Comparative example 1
After the vanadium shale raw ore is crushed, preheated and directly roasted by microwave, serious sintering occurs, and the total leaching rate of vanadium is only 67.45%.
Comparative example 2
After the vanadium shale raw ore is crushed, preheated, subjected to segmented microwave roasting and directly leached by alkali, the vanadium in the vanadium shale which is difficult to leach cannot be leached efficiently, and the total leaching rate of the vanadium is only 78.94%.
Claims (10)
1. A method for extracting vanadium from vanadium shale by segmented microwave roasting-step-by-step alkaline leaching is characterized in that the vanadium shale is crushed, and the obtained finely ground vanadium shale is subjected to segmented microwave roasting, wherein the segmented microwave roasting comprises preheating roasting, microwave decarburization roasting and microwave crystal breaking roasting; and after the microwave roasting is carried out in a segmented mode, carrying out alkaline leaching on the obtained roasted product step by step to extract vanadium, wherein the alkaline leaching specifically comprises microwave alkaline leaching and pressurized alkaline leaching to obtain vanadium-rich pregnant solution.
2. A method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching step by step is characterized by comprising the following steps:
s1, crushing:
the vanadium shale crushing process comprises a crushing process and an ore grinding process; after crushing, obtaining the milled vanadium shale with the grain size of-0.045 mm accounting for 70-85%, and carrying out segmented microwave roasting on the obtained milled vanadium shale;
s2: staged microwave roasting
The segmented microwave roasting comprises preheating roasting, microwave decarburization roasting and microwave crystal breaking roasting;
(1) Preheating and roasting:
preheating and roasting the levigated vanadium shale to obtain preheated vanadium shale with the preheating temperature of 380-480 ℃;
(2) Microwave decarbonizing roasting
Performing microwave decarburization roasting on preheated vanadium shale, applying a microwave field during the microwave decarburization roasting to generate electromagnetic energy for rapidly heating the material, introducing air during the microwave decarburization roasting, and adjusting roasting air amount to 6m 3 /h～8m 3 The microwave decarburization roasting temperature is controlled to be 580-630 ℃, and the microwave decarburization roasting time is 15-35 min, so that decarburized vanadium shale is obtained;
(3) Microwave crystal breaking and roasting:
carrying out microwave crystal breaking roasting on the decarburized vanadium shale, wherein in the microwave crystal breaking roasting process, microwave heating is adopted, and air and/or O are introduced into the bottom 2 The amount of the mixed gas is controlled to be 10m 3 /h～12m 3 The microwave power is 32kW to 48kW, the microwave crystal breaking roasting temperature is 880 ℃ to 940 ℃, and the roasting time is 40min to 70min, so that a roasted product is obtained;
s3: step-by-step alkaline leaching vanadium extraction
Carrying out alkaline leaching on the roasted product step by step to extract vanadium, wherein the alkaline leaching specifically comprises microwave alkaline leaching and pressurized alkaline leaching;
(1) Microwave alkaline leaching:
carrying out microwave alkaline leaching on the roasted product, applying microwave in the leaching process, wherein the microwave power is 7 kW-12 kW, and the alkaline leaching is carried out according to the liquid-solid ratio: 1g of roasted product (2-3) mL, leaching temperature of 65-85 ℃, 5-15% of alkali in the alkaline leaching solution by mass percent of the roasted product, leaching time of 40-80 min to obtain microwave alkaline leaching mixed solution, and performing solid-liquid separation to obtain microwave leaching residue and first vanadium-rich pregnant solution;
(2) Pressure alkaline leaching:
the microwave leaching residue is fed into a pressurized alkaline leaching operation, sodium hydroxide is used as a leaching agent to react with high-valence vanadium oxide, the dissolution of vanadium in raw ore is realized, the pressure of the pressurized alkaline leaching is ensured to be 1.0-1.8 MPa in the leaching process, and the leaching solution is pressurized according to the liquid-solid ratio: 1g of microwave leaching residue (= (1.5-2)) mL, the leaching temperature is 160-190 ℃, the mass percent of a leaching agent in the pressurized leaching solution in the microwave leaching residue is 10-20%, the leaching time is 40-90 min, pressurized alkaline leaching mixed liquor is obtained, and the final leaching residue and the second vanadium-rich pregnant solution are obtained after solid-liquid separation.
3. The method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching in steps according to claim 2, wherein in S1, the crushing process is as follows: and crushing the vanadium shale raw ore to the granularity of 0.8-8 mm to obtain crushed ore.
4. The method for extracting vanadium from vanadium shale by stage microwave roasting and alkaline leaching in steps according to claim 2, wherein the crusher used for crushing is one of a jaw crusher, an impact crusher or a high-pressure roller mill.
5. The method for vanadium shale sectional microwave roasting-step alkaline leaching vanadium according to claim 2, characterized in that the ore grinding mill is one of a semi-autogenous mill, an overflow ball mill or a stirring mill.
6. The method for extracting vanadium from vanadium shale according to claim 2, wherein in the step (1) of S2, the preheating roasting temperature is 600-650 ℃, and the retention time is 20-35S.
7. The method for extracting vanadium from vanadium shale according to claim 2, wherein air is introduced into the step (2) of S2 from the bottom, so that the materials are in a suspended state.
8. The method for extracting vanadium from vanadium shale according to claim 2, characterized in that in the step (1) of the step S3, after the microwave alkaline leaching, the leaching rate of vanadium in shale can reach 60% -80%.
9. The method for extracting vanadium from vanadium shale according to claim 2, wherein in the step (2) of the step S3, the operational leaching rate of vanadium in shale is 20-30% in the pressure alkaline leaching.
10. The method for vanadium shale extraction by steps of microwave roasting and alkali leaching vanadium according to any one of claims 1 to 9, wherein the vanadium shale extraction by steps of microwave roasting and alkali leaching vanadium has a vanadium total leaching rate of 85 to 95 percent.
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