阅读说明：本技术 一种高硅低钙类型的石煤新型提钒的选冶联合方法 (Novel vanadium extraction and dressing combined method for high-silicon low-calcium stone coal ) 是由 孙伟 王丽 胡岳华 孙宁 唐鸿鹄 吕斐 刘润清 杨越 韩海生 于 2019-08-15 设计创作，主要内容包括：一种高硅低钙类型的石煤新型提钒的选冶联合方法,步骤一、将高硅低钙类型的石煤原矿细磨得到石煤粉料；步骤二、将石煤粉料、富铁物料、含钙物料与碳粉按照100：5-15：5-15：5-15的质量比混匀,惰性气体保护下于1000-1300℃焙烧；步骤三、焙烧后的物料经磁选得到磁性富钒产品和非磁性尾渣；步骤四、将富钒产品和硫酸钠混合进行硫化焙烧；步骤五、将硫化焙烧后样品水浸后固液分离,得到富钒溶液及浸出渣。本发明中还原焙烧后磁选得到的非磁性渣可以作为水泥的原料,再次焙烧水浸后的富铁渣可以作为还原焙烧的原料,实现了提钒过程中铁物料的内循环,具有高效、经济环保以及钒浸出率高的特点。(A novel dressing and smelting combined method for extracting vanadium from high-silicon low-calcium stone coal comprises the following steps of firstly, finely grinding raw ore of the high-silicon low-calcium stone coal to obtain stone coal powder; step two, mixing the stone coal powder, the iron-rich material, the calcium-containing material and the carbon powder according to the ratio of 100: 5-15: 5-15: 5-15, and roasting at 1300 ℃ under the protection of inert gas; thirdly, magnetically separating the roasted material to obtain a magnetic vanadium-rich product and nonmagnetic tailings; step four, mixing the vanadium-rich product and sodium sulfate for sulfurizing roasting; and step five, soaking the vulcanized and roasted sample in water, and then carrying out solid-liquid separation to obtain a vanadium-rich solution and leaching residues. The non-magnetic slag obtained by magnetic separation after reduction roasting can be used as a raw material of cement, and the iron-rich slag obtained by secondary roasting and water leaching can be used as a raw material of reduction roasting, so that internal circulation of iron materials in the vanadium extraction process is realized, and the method has the characteristics of high efficiency, economy, environmental protection and high vanadium leaching rate.)

1. A combined method for selecting and smelting novel vanadium extraction from high-silicon low-calcium stone coal is characterized by comprising the following steps:

step one, grinding ore

Finely grinding the high-silicon low-calcium type stone coal raw ore to obtain stone coal powder;

step two, mixed sample roasting

Mixing stone coal powder, an iron-rich material, a calcium-containing material and carbon powder according to the proportion of 100: 5-15: 5-15: 5-15, and roasting at 1300 ℃ under the protection of inert gas;

step three, magnetic separation

Magnetically separating the roasted material to obtain a magnetic vanadium-rich product and nonmagnetic tailings;

step four, sulfuration roasting

Mixing the vanadium-rich product with sodium sulfate, and carrying out vulcanization roasting;

step five, leaching vanadium with water

And (3) soaking the vulcanized and roasted sample in water, and then carrying out solid-liquid separation to obtain a vanadium-rich solution and leaching residues.

2. The combined process of claim 1 for extracting vanadium from high-silicon low-calcium stone coal, which comprises the following steps: among the high-silicon low-calcium type stone coals: the content of silicon dioxide is more than 55 wt%, the content of calcium oxide is less than 1.5 wt%, and the content of vanadium pentoxide is more than 0.7 wt%.

3. The integrated process for the beneficiation and metallurgy of vanadium from high-silicon low-calcium type stone coal according to claim 1 or 2, characterized in that: in the first step, the stone coal raw ore is finely ground until the granularity is less than 200 meshes and accounts for 45-70%.

4. The integrated process for the beneficiation and metallurgy of vanadium from high-silicon low-calcium type stone coal according to claim 1 or 2, characterized in that: in the second step, the iron-rich material is at least one of iron oxide, iron powder and oolitic hematite; the calcium-containing material is at least one of calcium oxide and calcium carbonate.

5. The integrated process for the beneficiation and metallurgy of vanadium from high-silicon low-calcium type stone coal according to claim 1 or 2, characterized in that: in the second step, the inert gas is one or more of nitrogen and argon, and the roasting time is 2-4 h.

6. The integrated process for the beneficiation and metallurgy of vanadium from high-silicon low-calcium type stone coal according to claim 1 or 2, characterized in that: in the third step, the magnetic field intensity of the magnetic separation is 0.1-0.5T; the grade of vanadium in the magnetic vanadium-rich product is 10-16%; the non-magnetic tailings are directly used as a cement raw material.

7. The integrated process for the beneficiation and metallurgy of vanadium from high-silicon low-calcium type stone coal according to claim 1 or 2, characterized in that: in the fourth step, the mass ratio of the vanadium-rich product to the sodium sulfate is 100: 25-30; the temperature of the sulfuration roasting is 700-900 ℃, and the time is 2-4 h.

8. The integrated process for the beneficiation and metallurgy of vanadium from high-silicon low-calcium type stone coal according to claim 1 or 2, characterized in that: in the fifth step, the solid-liquid ratio of the water leaching is 1: (2-3) g/ml, the temperature is 80-85 ℃, and the time is 1-2 h.

9. The integrated process for the beneficiation and metallurgy of vanadium from high-silicon low-calcium type stone coal according to claim 1 or 2, characterized in that: and step five, returning the leached slag to the step two to be used as an iron-rich material for recycling.

10. The integrated process for the beneficiation and metallurgy of vanadium from high-silicon low-calcium type stone coal according to claim 1 or 2, characterized in that: after the treatment of the first step to the fifth step, the extraction rate of vanadium is not lower than 90 percent.

Technical Field

The invention belongs to the technical field of vanadium extraction from stone coal, and particularly relates to a novel selection and metallurgy combined method for extracting vanadium from high-silicon low-calcium stone coal.

Background

The vanadium resources in China are mainly stored in vanadium titano-magnetite and stone coal vanadium ore, the storage capacity of the stone coal is 618.8 hundred million tons, and the stone coal contains V₂O₅About 1.18 hundred million tons is V in the vanadium titano-magnetite in China₂O₅2.7 times of the reserve. The storage capacity of the stone coal only in the Hunan region is 187.2 million tons, which accounts for about 30 percent of the storage capacity of the whole country, the total economic value exceeds trillion yuan, and the extraction of vanadium from the stone coal becomes an important development direction for utilizing vanadium resources in China. V in stone coal₂O₅The content is greatly different in each region, generally 0.13-1.00%, less than 0.50% accounts for more than 60%, and more than 1% of rich ore only accounts for 2.8%. Under the current technical and economic conditions, the stone coal has industrial exploitation and utilization value when the vanadium-containing grade reaches more than 0.80-0.85%. The beneficiation method can enrich vanadium in stone coal in individual areas by about 1-2 times, but the universality is not strong, and the stone coal ore in many places has poor beneficiation effect due to extremely fine disseminated particle size of vanadium minerals, so that effective enrichment cannot be obtained. If a new technology is developed, the low-grade stone coal vanadium ore can be efficiently enriched, and the method has great significance for the development of the vanadium ore industry in China.

Disclosure of Invention

In order to overcome the technical defects of the prior art, the invention aims to provide a novel vanadium extraction and selection combined method for high-silicon low-calcium stone coal, which is efficient, environment-friendly and high in leaching rate, so that the enrichment ratio of vanadium in the high-silicon low-calcium stone coal is greatly improved, tailings can be directly used as building materials, iron oxide of a byproduct can be returned to a process system for recycling, no tailings are discharged, and the method is economical and environment-friendly.

In order to achieve the purpose, the invention adopts the following technical scheme:

a novel vanadium separation and metallurgy combined method for high-silicon low-calcium stone coal comprises the following steps:

step one, grinding ore

Finely grinding the high-silicon low-calcium type stone coal raw ore to obtain stone coal powder;

step two, mixed sample roasting

Mixing stone coal powder, an iron-rich material, a calcium-containing material and carbon powder according to the proportion of 100: 5-15: 5-15: 5-15, and roasting at 1300 ℃ under the protection of inert gas;

step three, magnetic separation

Magnetically separating the roasted material to obtain a magnetic vanadium-rich product (mainly vanadium iron spinel) and nonmagnetic tailings;

step four, sulfuration roasting

Mixing the vanadium-rich product with sodium sulfate, and carrying out vulcanization roasting;

step five, leaching vanadium with water

And (3) soaking the vulcanized and roasted sample in water, and then carrying out solid-liquid separation to obtain a vanadium-rich solution and leaching slag (iron-rich slag).

Preferably, in the high-silicon low-calcium type stone coal: the content of silicon dioxide is more than 55 wt%, the content of calcium oxide is less than 1.5 wt%, and the content of vanadium pentoxide is more than 0.7 wt%.

Preferably, in the first step, the stone coal raw ore is finely ground until the granularity is less than 200 meshes and accounts for 45-70%.

Preferably, in the second step, the iron-rich material is at least one of iron oxide, iron powder and oolitic hematite.

Preferably, in the second step, the calcium-containing material is at least one of calcium oxide and calcium carbonate.

Preferably, in the second step, the inert gas is one or more of nitrogen and argon, and the roasting time is 2-4 h.

Preferably, in the third step, the magnetic field intensity of the magnetic separation is 0.1-0.5T.

Preferably, in the third step, the grade of vanadium in the magnetic vanadium-rich product is 10-16%.

Preferably, in the third step, the nonmagnetic tailings are directly used as cement raw materials.

Preferably, in the fourth step, the mass ratio of the vanadium-rich product to the sodium sulfate is 100: 25-30.

Preferably, in the fourth step, the temperature of the sulfurizing roasting is 700-.

Preferably, in the fifth step, the leaching solid-liquid ratio of the water leaching is 1: (2-3) g/ml, the temperature is 80-85 ℃, and the time is 1-2 h.

Preferably, in the fifth step, the leached slag (iron-rich slag) is returned to the second step to be recycled as the iron-rich material.

Preferably, after the treatment of the steps one to five, the extraction rate of the vanadium is not lower than 90%.

The technical principle of the invention is as follows:

in the stone coal raw ore of the invention, vanadium exists in a trivalent and quadrivalent state, and is firmly combined in a similar form in a silicon-oxygen tetrahedron structure of the clay ore, although calcium vanadate is generated near 900 ℃ by adding a calcium-containing material, the molar ratio SiO is within 1000-₂/(CaO+SiO₂)>At 0.5, calcium vanadate and silicon-oxygen tetrahedron are decomposed, calcium oxide and silicon dioxide which hinders the combination of ferrovanadium generate CaSiOx with high melting point, x is 3/4/5, and the temperature interval is also the optimal temperature for the combination of vanadium and the added iron-rich material. When the added calcium-containing material is combined with the silica tetrahedron, the wrapped vanadium is opened, the released vanadium is combined with the iron to generate magnetic ferrovanadium spinel, crystal grains continuously grow during roasting, the ferrovanadium is wrapped by the silica tetrahedron again even if the temperature is reduced, and the vanadium can be enriched by simple ore grinding and magnetic separationAnd (4) collecting.

Fe₂O₃+C+V₂O₃+V₂O₄→FeO+V₂O₃+VO

CaO+SiO₂→CaSiO_x(x＝3/4/5)

Fe₂O₃+FeO+V₂O₃+VO→FeV₂O₄+Fe₂VO₄

FeV₂O₄+Fe₂VO₄+Na₂SO₄→Na₃VO₄+Fe₂O₃+SO₂+SO₃

SO₂+SO₃+H₂O→H₂SO₃+H₂SO₄

Aiming at high-silicon low-calcium type stone coal, an iron-rich material, a calcium-containing material and carbon powder are added, a vanadium phase is regulated and controlled by a reduction roasting method, the calcium-containing material is combined with silicon in the stone coal to generate calcium silicate, the phase conversion rate of vanadium is increased, a vanadium-containing mica mineral is converted into a vanadium iron spinel mineral, the vanadium iron spinel is selected by a magnetic separation method, the smelting grade of vanadium is obviously improved, the grade of vanadium in a magnetic vanadium-rich product obtained by magnetic separation is up to 10-16%, and meanwhile, non-magnetic tailings can be directly used as building materials; and then carrying out vulcanization roasting on the vanadium iron spinel ore to convert the vanadium iron spinel ore into soluble vanadate and iron oxide, wherein the iron oxide can be returned to a process system to be used as a raw material for stone coal reduction roasting, and the vanadate can leach vanadium through simple water leaching, so that the balance of iron materials in the whole stone coal vanadium extraction process is realized, and the stone coal zero-tailing discharge is also realized.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention greatly improves the enrichment ratio of vanadium in the high-silicon low-calcium stone coal, and the enrichment ratio can reach more than 20 times.

2. The stone coal in the invention has large magnetic separation and tailing discarding quantity and no pollution, and can be directly used as building materials.

3. The magnetic vanadium-rich product (mainly ferrovanadium spinel) is prepared by a sulfuration roasting method, vanadium is converted into soluble sodium vanadate after roasting, and iron oxide as a byproduct can be returned to a process system for recycling, so that the process is free from tail slag discharge, economic and environment-friendly.

4. The method can ensure that the leaching rate of vanadium in the stone coal reaches more than 90 percent, and is environment-friendly, energy-saving and efficient.

Detailed Description

The invention is further described with reference to specific embodiments, without limiting its scope.