CN115725863B - Method for extracting vanadium from vanadium shale by segmented microwave roasting-stepwise alkaline leaching - Google Patents
Method for extracting vanadium from vanadium shale by segmented microwave roasting-stepwise alkaline leaching Download PDFInfo
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- CN115725863B CN115725863B CN202211464212.6A CN202211464212A CN115725863B CN 115725863 B CN115725863 B CN 115725863B CN 202211464212 A CN202211464212 A CN 202211464212A CN 115725863 B CN115725863 B CN 115725863B
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- 238000002386 leaching Methods 0.000 title claims abstract description 206
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 175
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000005261 decarburization Methods 0.000 claims abstract description 47
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- 239000002893 slag Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 8
- 239000003795 chemical substances by application 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
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 19
- 239000011707 mineral Substances 0.000 abstract description 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 238000000605 extraction Methods 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 7
- 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 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000004904 shortening Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 229910052900 illite Inorganic materials 0.000 description 5
- 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 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
- 238000005303 weighing Methods 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 239000002737 fuel gas Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229910001784 vanadium mineral 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 sectional 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 then carrying out sectional microwave roasting on the obtained crushed vanadium shale, wherein the sectional microwave roasting comprises preheating roasting, microwave decarburization roasting and microwave crystal breaking roasting; after sectional microwave roasting, the obtained roasting product is subjected to stepwise alkaline leaching to extract vanadium, specifically comprising microwave alkaline leaching and pressurized alkaline leaching, so as to obtain vanadium-rich noble liquid. According to the method, the time of microwave decarburization roasting is shortened and the decarburization efficiency is improved by the efficient selective heating characteristic of microwaves on the carbon; through the efficient selective heating characteristic of microwaves on vanadium shale, the lattice damage of the microwave crystal breaking roasting process on vanadium-containing minerals is enhanced, and the efficiency of the microwave crystal breaking roasting is further improved. The leaching process of the method adopts a microwave-pressurizing two-step leaching process, and the vanadium-rich noble liquid 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 segmented microwave roasting-stepwise alkaline leaching.
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 iron and steel industry, alloy, chemical industry, superconducting material, vanadium cell, etc. and its resource requirement is huge.
The 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 shale vanadium extraction, such as the patent CN111304465A, a method for extracting vanadium by stone coal decarburization-crystal breaking roasting reinforced acid leaching, the patent CN111304464A, a method for extracting vanadium by stone coal vanadium ore multistage roasting reinforced acid mixing curing, the patent CN114111359A, a stone coal vanadium ore cascade oxidation roasting vanadium extraction system and oxidation roasting method, and the patent CN111719054A, a comprehensive utilization method for stone coal vanadium ore oxidation crystal breaking roasting.
Although the shale vanadium extraction processes are related to the above-mentioned published patent, the existing roasting processes are only carried out at high temperature, and complete damage to the crystal lattice of the vanadium-containing mineral is difficult to achieve, so that the refractory vanadium shale is difficult to achieve good vanadium extraction effect.
The conventional alkaline leaching process is carried out at normal temperature and normal pressure, and has low leaching rate, large medicament consumption and long leaching time, so that the leaching efficiency is low.
The existing leaching technology is one-step leaching, other impurity metal ions are introduced into the solution while the leaching rate of vanadium is improved, and the subsequent purification difficulty is high.
Disclosure of Invention
The invention provides a method for extracting vanadium from vanadium shale by sectional microwave roasting and stepwise alkaline leaching, which aims to solve the problems of poor roasting effect, poor leaching effect and more impurity ions in leaching solution of refractory carbon-containing vanadium shale in the vanadium extraction process.
The invention applies the microwave heating technology to decarburization roasting and broken crystal roasting operation of the suspension roasting technology. The microwave decarburization roasting time is shortened and the decarburization efficiency is improved by the efficient selective heating characteristic of the microwave on the carbon; the efficient selective heating characteristic of the microwaves on the vanadium shale achieves the purposes of strengthening the lattice damage of vanadium-containing minerals, shortening the breaking and roasting time, improving the breaking and roasting efficiency and strengthening the decarburization effect in the suspension roasting process.
The invention adopts microwave and pressurizing means to strengthen the leaching efficiency of the roasted product, thereby realizing the purposes of reducing the leaching liquid consumption and shortening the leaching time; and the vanadium-rich noble liquid with less part of impurity ions is obtained by a microwave-pressurizing two-step leaching process while the leaching rate is ensured.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a method for extracting vanadium from vanadium shale by segmented microwave roasting-stepwise alkaline leaching, which comprises the following steps:
S1, crushing:
The vanadium shale crushing process comprises a crushing process and an ore grinding process; after crushing, the ground vanadium shale with the particle size of-0.045 mm accounting for 70-85 percent is obtained;
In the step S1, the crushing process is as follows: crushing the raw ore of the vanadium shale to the granularity of 0.8-8 mm to obtain crushed ore;
The ore feeding granularity of the raw ore of the vanadium shale is in the range of 5 mm-250 mm.
The crusher used for crushing is preferably one of a jaw crusher, a counter-impact crusher or a high-pressure roller mill.
The grinding machine used for grinding is preferably one of a semi-autogenous grinding machine, an overflow type ball grinding machine or a stirring grinding machine.
Further, after the ground mineral products are filtered and the water content is less than or equal to 10%, scattering, and obtaining ground vanadium shale to be subjected to sectional microwave roasting;
S2: sectional microwave roasting
The sectional microwave roasting comprises preheating roasting, microwave decarburization roasting and microwave crystal breaking roasting;
(1) Preheating and roasting:
preheating and roasting the ground vanadium shale, wherein the preheating and roasting temperature is 600-650 ℃, and the residence time is 20-35 s, so that the preheated vanadium shale with the preheating temperature of 380-480 ℃ is obtained;
the preheating roasting can remove the adsorbed water in the ground 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
Carrying out microwave decarburization roasting on the preheated vanadium shale, applying a microwave field in the microwave decarburization roasting to generate electromagnetic energy to rapidly heat materials, introducing air in the microwave decarburization roasting process, adjusting the roasting air quantity to be 6m 3/h～8m3/h, controlling the microwave decarburization roasting temperature to be 580-630 ℃, and carrying out microwave decarburization roasting for 15-35 min to obtain decarburized vanadium shale;
In the step S2 (2), because the carbon in the vanadium shale has strong wave absorption capacity, the carbon can be quickly heated and burned in a microwave field, so that the microwave decarburization roasting time is shortened, and the decarburization efficiency is improved. In addition, the carbon is much stronger than the gangue mineral quartz in the ability to absorb the wave, so that a large temperature difference exists between different substances, and further expansion stress difference and even microcracks are formed. This is beneficial to improving roasting efficiency and subsequent leaching efficiency. As most of the carbonaceous material is removed by combustion, vanadium is enriched in the ash. The suspended material in the furnace is heated uniformly, and the sintering caused by local high temperature can be prevented. The process can also remove part of crystal water and volatile components in the raw ore to form decarbonized vanadium shale with uniform and stable properties. And the vanadium shale after decarburization is fed into the next stage of microwave crystal breaking roasting operation.
In the step (2) of the step 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:
Performing microwave crystal breaking roasting on the decarbonized vanadium shale, heating by microwaves in the microwave crystal breaking roasting process, introducing air and/or O 2 mixed gas into the bottom, controlling the roasting gas quantity to be 10m 3/h～12m3/h, controlling the microwave power to be 32 kW-48 kW, and obtaining a roasting product, wherein the microwave crystal breaking roasting temperature is 880-940 ℃ and the roasting time is 40-70 min;
In the step S2 (3), the mica and illite minerals undergo dehydroxylation reaction, the silicon oxygen octahedral structure where 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 the vanadium-containing minerals of Li Danlei have strong absorption capacity, the temperature of the minerals in a microwave field is rapidly increased, so that the heating time is shortened, and the dehydroxylation reaction and the lattice damage rate of the vanadium-containing minerals are enhanced. In addition, vanadium-containing minerals have much stronger absorption capacity than quartz, and a larger temperature difference exists between minerals during heating, so that expansion stress difference and even microcracks are formed. This is also advantageous for improving the breaking efficiency and subsequent leaching efficiency.
S3: stepwise alkaline leaching of vanadium
The roasting product is subjected to stepwise alkaline leaching to extract vanadium, and the method specifically comprises microwave alkaline leaching and pressurized alkaline leaching;
(1) Microwave alkaline leaching:
carrying out microwave alkaline leaching on the roasted product, applying microwaves in the leaching process, wherein the microwave power is 7 kW-12 kW, and carrying out alkaline leaching according to the liquid-solid ratio: the roasting product is (2-3) mL, 1g, the leaching temperature is 65-85 ℃, the alkali in the alkaline leaching solution accounts for 5-15% of the mass of the roasting product, the leaching time is 40-80 min, the microwave alkaline leaching mixed solution is obtained, and the solid-liquid separation is carried out, so that the microwave leaching slag and the first vanadium-rich noble solution are obtained.
After microwave alkaline leaching, the operation leaching rate of vanadium in shale can reach 60% -80%, and the separated first vanadium-rich noble liquid can be recycled after vanadium precipitation.
In the step (1) of the step S3, a microwave heater for the material which is more soluble 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 improved.
(2) Pressurized alkaline leaching:
The microwave leaching slag is fed into a pressurized alkaline leaching operation, sodium hydroxide is used as a leaching agent to react with high-valence vanadium oxide, so that the leaching of vanadium in raw ores 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 liquid is pressurized according to the liquid-solid ratio: 1g of microwave leaching slag= (1.5-2), the leaching temperature is 160-190 ℃, the leaching agent in the pressurized leaching liquid accounts for 10-20% of the mass percent of the microwave leaching slag, the leaching time is 40-90 min, the pressurized alkaline leaching mixed liquid is obtained, and the final leaching slag and the second vanadium-rich noble liquid are obtained after solid-liquid separation.
In the pressurized alkaline leaching, the operation leaching rate of vanadium in shale is 20% -30%, the obtained pressurized leaching liquid can be recycled after vanadium deposition of the separated second vanadium-rich noble liquid, and the impurity content in the obtained second vanadium-rich noble liquid is less and is lower than 0.40g/L.
By adopting the method for extracting vanadium from the vanadium shale by segmented microwave roasting and stepwise alkaline leaching, the total leaching rate of vanadium is 85-95%.
The invention relates to a method for extracting vanadium from vanadium shale by segmented microwave roasting-stepwise alkaline leaching, which has the key points that:
1. The invention applies the microwave heating technology to the microwave decarburization roasting operation of the suspension roasting technology. The high-efficiency selective heating characteristic of microwaves on the carbon is utilized, 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 technology. The efficient selective heating characteristic of the microwaves on the vanadium shale is utilized, so that the purposes of strengthening the lattice damage of vanadium-containing minerals, shortening the roasting time and improving the vanadium leaching rate of roasting products are achieved.
3. The invention adopts microwave and pressurizing means to strengthen the alkaline leaching efficiency of the roasted product, thereby realizing the purposes of reducing the dosage of alkaline liquor and shortening the leaching time. The vanadium-rich noble liquid with less part of impurity ions is obtained by the microwave-pressurizing two-step leaching process while the leaching rate is ensured. Solves the problems of poor roasting effect, poor leaching effect and more impurity ions in leaching solution of refractory carbon-containing vanadium shale in the vanadium extraction process.
The invention provides a method for extracting vanadium from vanadium shale by segmented microwave roasting-stepwise alkaline leaching, which has the beneficial effects that:
(1): the microwave heating technology is applied to the microwave decarburization roasting and crystal breaking roasting operation of the suspension roasting process. The high-efficiency selective heating characteristic of microwaves on the carbon is utilized, so that the microwave decarburization roasting time is shortened, and the decarburization efficiency is improved; the efficient selective heating characteristic of the microwaves on the vanadium shale is utilized, so that the purposes of strengthening the lattice damage of vanadium-containing minerals, shortening the roasting time and improving the vanadium leaching rate of roasting products are achieved.
(2): The invention adopts microwave and pressurizing means to strengthen the alkaline leaching efficiency of the roasted product, thereby realizing the purposes of reducing the dosage of alkaline liquor and shortening the leaching time. And the vanadium-rich noble liquid with less part of impurity ions is obtained by a microwave-pressurizing two-step leaching process while the leaching rate is ensured. Solves the problems of poor roasting effect, poor leaching effect and more impurity ions in leaching solution of refractory carbon-containing vanadium shale in the vanadium extraction process.
Drawings
FIG. 1 is a schematic diagram of a vanadium shale sectional microwave roasting-step alkaline leaching process.
FIG. 2 is a schematic diagram of material change of 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 of 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 implementation of the patent is clearly and completely described with reference to the accompanying 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 their application. All other embodiments, which can be obtained by a person skilled in the art without making any inventive effort, are within the scope of protection of the present patent.
In the following examples, a schematic diagram of a method for extracting vanadium from vanadium shale by stage microwave roasting-stage alkaline leaching is shown in fig. 1, including a schematic diagram of a preheating roasting device material change, a schematic diagram of a microwave decarburization roasting device material change, a schematic diagram of a microwave crystal breaking roasting device material change, and a schematic diagram of a microwave alkaline leaching device material change in fig. 5.
Example 1
In the example, the raw ore of vanadium shale is obtained from Sichuan, the raw ore has V 2O5 content of 0.82%, C content of 10.62%, TFe content of 1.52%, siO 2 content of 52.65%, and quartz and vanadium-containing illite are main constituent minerals. The examples were developed as follows:
(1) Crushing: crushing raw ore to 0.8-8 mm by a high-pressure roller mill, and grinding to-0.045 mm accounting for 75% by a stirring mill. The ground mineral products are filtered (the water content is 5 percent) and scattered and then fed into a sectional microwave roasting system.
(2) Preheating and roasting: the fuel gas (natural gas in this embodiment) is burnt in a burning 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 powder ore stays in the furnace for about 25s and is further preheated. The powder ore is heated to 420 ℃, and the preheated vanadium shale material from which the adsorbed water is removed is subjected to microwave decarburization roasting operation.
(3) Microwave decarbonizing and roasting: the preheated vanadium shale is fed into microwave decarburization roasting operation, and the material change of the microwave decarburization device is shown in figure 3. The temperature in the furnace chamber is controlled at 630 ℃ by adjusting the microwave heater, and air is introduced into the lower part of the microwave decarburization device, wherein the air quantity is 7m 3/h. And reacting the decarbonized vanadium shale in the equipment for 20min, and then feeding the vanadium shale into microwave crystal breaking roasting operation.
(4) Microwave crystal breaking roasting: the decarbonized 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 35kW, introducing mixed gas of air and O 2, introducing the air volume to be 11m 3/h (according to the volume ratio, the air is O 2 =3:1), controlling the temperature in the furnace body to be 920 ℃, and continuously reacting for 40min. And (5) feeding the roasting product into microwave alkaline leaching operation to obtain the roasting product.
(5) Microwave alkaline leaching: and 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 carrying out alkaline leaching solution according to the liquid-solid ratio: the calcined product was 2 mL/1 g, and an aqueous sodium hydroxide solution was prepared as an alkaline leaching solution, and the calcined product was added to the alkaline leaching solution. The power of the microwave generator in the leaching process is 8kW, the leaching temperature is 75 ℃, and the leaching time is 45min. The operation leaching rate of vanadium is about 70%, and the material change in the microwave alkaline leaching device is shown in fig. 5.
(6) Pressurized alkaline leaching: the microwave leaching slag is fed into pressurized alkaline leaching operation. The leaching process ensures that the pressure in the reaction kettle is 1.2MPa, the sodium hydroxide accounting for 15% of the mass fraction of the roasted product is weighed, and then the leaching solution is pressurized according to the liquid-solid ratio: the microwave leaching residue is 1.5 mL/1 g, sodium hydroxide aqueous solution is prepared as pressurized leaching solution, the microwave leaching residue is added into the pressurized leaching solution, the leaching temperature is 170 ℃, and the leaching time is 60min. The operation 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 raw ore of vanadium shale is taken from a place of Shaanxi, the raw ore contains 0.83% of V 2O5, 18.16% of C, 3.54% of TFe, 61.87% of SiO 2, quartz and vanadium-containing illite and vanadium-containing sericite are main mineral components, wherein the vanadium mineral is mainly homomorphically assigned in illite and sericite, and the content reaches 88%. The microwave crystal breaking roasting vanadium extraction process of the example is developed according to the following steps:
(1) Crushing: crushing raw ore to 1-6 mm by a jaw crusher, and grinding to-0.045 mm accounting for 70% by a ball mill. The ground mineral product is filtered (the water content is 9%), scattered and then fed into a sectional microwave roasting system.
(2) Preheating and roasting: the gas and air are introduced into the preheating roasting device for combustion, and the furnace is heated to 630 ℃. The powder ore stays in the furnace for about 20s and is further preheated. The powder ore is heated to 450 ℃, and the preheated vanadium shale material from which the adsorbed water is removed is subjected to microwave decarburization roasting operation.
(3) Microwave decarbonizing and roasting: the preheated vanadium shale is fed into 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 quantity is 8m 3/h. And reacting the decarbonized vanadium shale in the equipment for 25min, and then feeding the vanadium shale into microwave crystal breaking roasting operation.
(4) Microwave crystal breaking roasting: the decarbonized 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, introducing mixed gas of air and O 2, introducing air volume to be 12m 3/h (according to the volume ratio, air: O 2 =3:1), controlling the temperature in the oven body to be 930 ℃, and continuously reacting for 60min to obtain a roasting product.
(5) Microwave alkaline leaching: weighing sodium hydroxide accounting for 5% of the mass fraction of the roasted product, and then carrying out alkaline leaching solution according to the liquid-solid ratio: the calcined product was 2 mL/1 g, and an aqueous sodium hydroxide solution was prepared as an alkaline leaching solution, and the calcined product was added to the alkaline leaching solution. The power of a microwave generator in the leaching process is 7kW, the leaching temperature is 65 ℃, the leaching time is 60min, the microwave alkaline leaching mixed solution is obtained, and the solid-liquid separation is carried out, so that the microwave leaching slag and the first vanadium-rich noble solution are obtained. The operation leaching rate of vanadium is 67.21%, and the material change in the microwave alkaline leaching device is shown in figure 5.
(6) Pressurized alkaline leaching: and (3) feeding the separated microwave leaching residues 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 leaching liquid according to the liquid-solid ratio: the microwave leaching residue is 2 mL/1 g, sodium hydroxide aqueous solution is prepared as pressurized leaching solution, the microwave leaching residue is added into the pressurized leaching solution, the leaching temperature is 160 ℃, and the leaching time is 70min. The operation leaching rate of vanadium in shale is 23.58%. Finally, the vanadium leaching rate of the process is 90.79%.
Example 3
In the example, vanadium shale is taken from a certain Gansu province, raw ore V 2O5 content 0.93%, C content 11.21%, TFe content 2.32%, siO 2 content 54.35%, and quartz and vanadium-containing illite are main constituent minerals. The examples were developed as follows:
(1) Crushing: crushing raw ore to 0.8-8 mm by a high-pressure roller mill, and grinding to-0.045 mm accounting for 79% by a semi-autogenous mill. The ground product is filtered (water content 10%) and fed into a staged microwave roasting system.
(2) Preheating and roasting: natural gas is burnt in a combustion station at the lower part of the preheating roasting device, and air is introduced to heat the inside of the furnace body to 640 ℃. The powder ore stays in the furnace for about 35s and is further preheated. The powder ore is heated to 410 ℃, and the preheated vanadium shale material from which the adsorbed water is removed is subjected to microwave decarburization roasting operation.
(3) Microwave decarbonizing and roasting: the preheated vanadium shale is fed into 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 quantity is 8m 3/h. And reacting the decarbonized vanadium shale in the equipment for 35min, and then feeding the vanadium shale into microwave crystal breaking roasting operation.
(4) Microwave crystal breaking roasting: the decarbonized 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 33kW, introducing mixed gas of air and O 2, introducing the gas volume to be 10m 3/h (according to the volume ratio, the air is O 2 =3:1), controlling the temperature in the oven body to be 940 ℃, and continuously reacting for 70min to obtain a roasting product.
(5) Microwave alkaline leaching: weighing sodium hydroxide accounting for 5% of the mass fraction of the roasted product, and then carrying out alkaline leaching solution according to the liquid-solid ratio: the calcined product was 2 mL/1 g, and an aqueous sodium hydroxide solution was prepared as an alkaline leaching solution, and the calcined product was added to the alkaline leaching solution. The power of a microwave generator in the leaching process is 8kW, the leaching temperature is 85 ℃, and the leaching time is 80min, so that microwave leaching slag and first vanadium-rich noble liquid are obtained. The operation leaching rate of vanadium is 66.84%, and the material change in the microwave alkaline leaching device is shown in figure 5.
(6) Pressurized alkaline leaching: and (3) feeding the separated microwave leaching residues 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 leaching liquid according to the liquid-solid ratio: the microwave leaching residue is 2 mL/1 g, sodium hydroxide aqueous solution is prepared as pressurized leaching solution, the microwave leaching residue is added into the pressurized leaching solution, the leaching temperature is 160 ℃, and the leaching time is 70min. The operation 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 ℃, the total microwave roasting gas quantity is 11.3m 3/h, and other conditions are kept unchanged. Finally, the total leaching rate of vanadium 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 ℃, the total microwave roasting gas quantity is 10.6m 3/h, and other conditions are kept unchanged. 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 ℃, the total microwave roasting gas quantity is 12m 3/h, and other conditions are kept unchanged. Finally, the total leaching rate of vanadium was 94.98%.
Comparative example 1
After the raw ore of the vanadium shale is crushed, preheating and direct microwave roasting are carried out, severe sintering occurs, and the total leaching rate of vanadium is only 67.45%.
Comparative example 2
After the raw ore of the vanadium shale is crushed, preheated and subjected to sectional microwave roasting, the vanadium in the refractory vanadium shale cannot be leached efficiently by direct alkaline leaching, and the total leaching rate of the vanadium is only 78.94%.
Claims (4)
1. A method for vanadium shale sectional microwave roasting-step alkaline leaching vanadium is characterized in that after the vanadium shale is crushed, the obtained crushed vanadium shale is subjected to sectional microwave roasting, and the sectional microwave roasting comprises preheating roasting, microwave decarburization roasting and microwave crystal breaking roasting; after sectional microwave roasting, carrying out stepwise alkaline leaching on the obtained roasting product, wherein the step alkaline leaching specifically comprises microwave alkaline leaching and pressurized alkaline leaching to obtain vanadium-rich noble liquid;
the method comprises the following steps:
S1, crushing:
The vanadium shale crushing process comprises a crushing process and an ore grinding process; after crushing, obtaining ground vanadium shale with the particle size of-0.045 mm accounting for 70% -85%, and carrying out sectional microwave roasting on the obtained ground vanadium shale;
S2: sectional microwave roasting
The sectional microwave roasting comprises preheating roasting, microwave decarburization roasting and microwave crystal breaking roasting;
(1) Preheating and roasting:
Preheating and roasting the ground vanadium shale, wherein the preheating and roasting temperature is 600-650 ℃, and the residence time is 20-35 s, so that the preheated vanadium shale with the preheating temperature of 380-480 ℃ is obtained;
(2) Microwave decarbonizing roasting
Carrying out microwave decarburization roasting on the preheated vanadium shale, applying a microwave field in the microwave decarburization roasting to generate electromagnetic energy to rapidly heat materials, introducing air in the microwave decarburization roasting process, adjusting the roasting air quantity to be 6m 3/h~8m3/h, controlling the microwave decarburization roasting temperature to be 580-630 ℃, and carrying out microwave decarburization roasting for 15-35 min to obtain decarburized vanadium shale; the air is introduced from the bottom, so that the material is in a suspension state;
(3) Microwave crystal breaking roasting:
Performing microwave crystal breaking roasting on the decarbonized vanadium shale, heating by microwaves in the microwave crystal breaking roasting process, introducing air and O 2 mixed gas into the bottom, controlling the roasting gas quantity to be 10m 3/h~12m3/h, controlling the microwave power to be 32 kW-48 kW, and obtaining a roasting product, wherein the microwave crystal breaking roasting temperature is 880-940 ℃ and the roasting time is 40-70 min;
S3: stepwise alkaline leaching of vanadium
The roasting product is subjected to stepwise alkaline leaching to extract vanadium, and the method specifically comprises microwave alkaline leaching and pressurized alkaline leaching;
(1) Microwave alkaline leaching:
Carrying out microwave alkaline leaching on the roasted product, applying microwaves in the leaching process, wherein the microwave power is 7 kW-12 kW, and carrying out alkaline leaching according to the liquid-solid ratio: 1g of roasting product (2-3 mL), wherein the leaching temperature is 65-85 ℃, the alkali in alkaline leaching solution accounts for 5-15% of the mass of the roasting product, the leaching time is 40-80 min, a microwave alkaline leaching mixed solution is obtained, and solid-liquid separation is carried out to obtain microwave leaching slag and a first vanadium-rich noble solution;
(2) Pressurized alkaline leaching:
The microwave leaching slag is fed into a pressurized alkaline leaching operation, sodium hydroxide is used as a leaching agent to react with high-valence vanadium oxide, so that the leaching of vanadium in raw ores 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 liquid is pressurized according to the liquid-solid ratio: 1g of microwave leaching slag= (1.5-2), wherein the leaching temperature is 160-190 ℃, the leaching agent in the pressurized leaching liquid accounts for 10-20% of the mass percent of the microwave leaching slag, the leaching time is 40-90 min, the pressurized alkaline leaching mixed liquid is obtained, and the final leaching slag and the second vanadium-rich noble liquid are obtained after solid-liquid separation;
In the step (1) of the step S3, after microwave alkaline leaching, the operation leaching rate of vanadium in shale can reach 60% -70%;
In the step (2) of the step S3, the operation leaching rate of vanadium in shale is 20% -30% in the pressurized alkaline leaching;
According to the method for extracting vanadium from vanadium shale by segmented microwave roasting and stepwise alkaline leaching, the total leaching rate of vanadium is 85% -95%.
2. The method for vanadium shale fractional microwave roasting-fractional alkaline leaching vanadium according to claim 1, wherein in S1, the crushing process is as follows: crushing the raw ore of the vanadium shale to the granularity of 0.8-8 mm to obtain crushed ore.
3. The method for vanadium shale fractional microwave roasting-fractional alkaline leaching vanadium according to claim 1, wherein the crusher used for crushing is one of a jaw crusher, a counter-impact crusher or a high-pressure roller mill.
4. The method for vanadium shale fractional microwave roasting-fractional alkaline leaching vanadium according to claim 1, wherein the mill used for grinding is one of a semi-autogenous mill, an autogenous mill and an overflow type ball mill.
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