阅读说明：本技术 一种钙法提钒尾渣无害化处理的方法 (Harmless treatment method for calcium-method vanadium extraction tailings ) 是由 陈炼 陈均 梁新腾 戈文荪 于 2021-09-07 设计创作，主要内容包括：本发明提供了一种钙法提钒尾渣无害化处理的方法,包括：在钙法提钒尾渣中配加一定量的碳质材料,在1500～1650℃的推板窑内进行脱水、脱硫和还原,通过碳对渣中的钒、铁等有价元素进行还原,得到含钒的铁块和炉渣,铁块可用于钢水合金化,炉渣可用作水泥生产,从而实现提钒尾渣的资源化利用和无害化处理。本发明能够有效利用提钒尾渣中的有价元素,使钒、铁等元素得到有效回收利用,实现工业废弃资源的绿色化利用,有利于资源的高效利用。本发明适用于采用钒渣以钙法提钒工艺生产钒制品的企业,解决了钒制品厂采用钙法提钒方法用钒渣生产钒制品后产生的尾渣资源化利用的问题。(The invention provides a harmless treatment method of tailings generated in vanadium extraction by a calcium method, which comprises the following steps: adding a certain amount of carbonaceous materials into the tailings of vanadium extraction by the calcium method, dehydrating, desulfurizing and reducing in a pushed slab kiln at 1500-1650 ℃, reducing valuable elements such as vanadium, iron and the like in the slag by carbon to obtain vanadium-containing iron blocks and slag, wherein the iron blocks can be used for alloying molten steel, and the slag can be used for producing cement, so that the resource utilization and harmless treatment of the tailings of vanadium extraction are realized. The method can effectively utilize valuable elements in the vanadium extraction tailings, so that the elements such as vanadium, iron and the like are effectively recycled, the green utilization of industrial waste resources is realized, and the high-efficiency utilization of the resources is facilitated. The method is suitable for enterprises producing vanadium products by adopting vanadium slag through a calcium method vanadium extraction process, and solves the problem of resource utilization of tailings generated after vanadium products are produced by vanadium slag through a calcium method vanadium extraction method in vanadium product factories.)

1. A calcium method vanadium extraction tailings harmless treatment method comprises the following steps:

mixing the tailings obtained by extracting vanadium by a calcium method with a carbonaceous material, and carrying out first heating treatment for dehydration and desulfurization to obtain dehydrated desulfurization tailings;

and carrying out second temperature-raising treatment reduction on the dehydrated and desulfurized tailings to obtain vanadium-containing molten iron and furnace slag.

2. The method according to claim 1, wherein the second temperature-raising treatment reduction process further comprises:

mixing the dehydrated and desulfurized tailings with a reducing agent to carry out second heating treatment reduction;

the reducing agent comprises: carbonaceous reducing agent and/or ferrosilicon.

3. The method according to claim 1, wherein the calcium vanadium extraction tailings comprise the following components:

4.4-5 wt% S;

8.5-10.4 wt% of CaO;

1.1 to 1.4 wt% of MgO;

4.2-5.0 wt% of MnO;

27.1 to 29.2 wt% of TFe;

11.1 to 12.8 wt% of SiO₂；

9.7-10.5 wt% of TiO₂；

1.7～2.2wt％V₂O₅；

1.4-1.8 wt% of Al₂O₃；

1.02-1.09 wt% of Cr₂O₃。

4. The method of claim 1, wherein the carbonaceous material is selected from one or both of the group consisting of petcoke and anthracite.

5. The method according to claim 1, wherein the mass of the carbonaceous material is 5-30% of the mass of the tailings of vanadium extraction by the calcium method.

6. The method according to claim 1, wherein the first temperature raising treatment is carried out at 1300 to 1500 ℃ for 30 to 180 min.

7. The method according to claim 1, characterized in that the water content in the dehydrated desulfurization tailings is < 1% by mass; the mass content of sulfur is less than 0.01 percent.

8. The method of claim 2, wherein the carbonaceous reductant is selected from one or both of the group consisting of petcoke and anthracite.

9. The method according to claim 2, wherein the mass of the reducing agent is 1-21% of the mass of the low-sulfur tailings.

10. The method according to claim 1, wherein the temperature of the second temperature-raising treatment is 1500 to 1700 ℃, and the treatment time is 15 to 30 min.

Technical Field

The invention belongs to the technical field of vanadium-titanium chemical industry, and particularly relates to a harmless treatment method of vanadium extraction tailings by a calcium method.

Background

Vanadium (V) is a transition metal element, and is stable in chemical property at normal temperature and active at high temperature. The valence electron structure of the vanadium atom is 3d³4s²Which are typical valence-changing elements, five valence electrons can participate in the bond formation, having +2, +3, +4, and +5 valence states. The stabilizing compounds of vanadium are different at different oxygen partial pressures and temperatures, and decreasing the oxygen partial pressure and increasing the temperature is beneficial to the stable existence of trivalent vanadium oxides. In addition to vanadium, there are a number of non-stoichiometric oxides which can be used in the general formula V_nO_2n-1(3. ltoreq. n. ltoreq.9) or a mixed oxide thereof. At V₂O₄And V₂O₅In between, known as V₃O₅、V₃O₇、V₄O₇、V₄O₉、V₅O₉、V₆O₁₁、V₆O₁₃And the like. Vanadium oxide mainly of V in industry₂O₃、VO₂And V₂O₅In which V is₂O₅This is particularly important.

Vanadium has excellent strength, hardness and anti-fatigue effect, and is widely applied to the fields of steel, chemical industry, aviation and the like. About 84 percent of vanadium is used for dissolving steel as an alloy element into the steel to form VC and VN, refining crystal grains, inhibiting the development of bainite and pearlite, increasing the martensite strength, thereby improving the hardness, the strength, the toughness and the abrasion resistance of the steel, and the produced product takes ferrovanadium and VN as main crystal grains. The vanadium is used for the non-ferrous alloy, mainly for structural materials represented by V-Al series alloy, such as excellent high-temperature aviation structural materials Ti-6Al-4V, Ti-8Al-1V-Mo and Ti-6Al-6V-2Sn and other alloys. The vanadium product used in the chemical field mainly comprises V₂O₅、NH₄VO₃、V₂O₃、VOCl₃And VCl₄And the like, as catalysts, colorants, electrode materials for large-capacity batteries. It is worth mentioning that due to the multi-valence state of vanadium, vanadium is used as the anode material of lithium battery or developed into energy storage such as super capacitorThe device has the advantages of quick charging, high specific energy, low price and the like, and has a bright application prospect. In addition, about 2% of vanadium products are also used in the fields of medicine, protective materials, thin film materials and the like. The existing research shows that the vanadium compound has the function of insulin-like, can promote the synthesis of liver glycogen and muscle glycogen, inhibit the decomposition of the liver glycogen into glucose, promote the synthesis of fat and inhibit the decomposition of the fat. In summary, vanadium and vanadium products are widely used as additives to improve material properties or accelerate the progress of chemical reactions.

The existing industrial production vanadium extraction process mainly comprises two processes of blast furnace ironmaking, converter vanadium extraction and vanadium slag deep processing to obtain vanadium products and a stone coal vanadium extraction process. The vanadium extraction process from vanadium slag also comprises two processes of sodium-modified vanadium extraction and calcification vanadium extraction, wherein the calcification vanadium extraction process comprises the steps of oxidizing and roasting the vanadium slag and lime, treating the obtained clinker by sulfuric acid to obtain vanadium-containing solution and tailings, wherein the obtained tailings contain a large amount of CaSO₄The water content is as high as more than 30%, so the utilization difficulty is extremely high, the environmental protection risk is high, and the method is one of the problems to be solved in the utilization of vanadium resources.

Disclosure of Invention

In view of the above, the invention aims to provide a harmless treatment method for calcium-method vanadium extraction tailings, and the treatment method provided by the invention can make better resource utilization of the calcium-method vanadium extraction tailings.

The invention provides a harmless treatment method of tailings generated in vanadium extraction by a calcium method, which comprises the following steps:

mixing the tailings obtained by extracting vanadium by a calcium method with a carbonaceous material, and carrying out first heating treatment for dehydration and desulfurization to obtain dehydrated desulfurization tailings;

and carrying out second temperature-raising treatment reduction on the dehydrated and desulfurized tailings to obtain vanadium-containing molten iron and furnace slag.

Preferably, the second temperature-raising treatment reduction process further includes:

mixing the dehydrated and desulfurized tailings with a reducing agent to carry out second heating treatment reduction;

the reducing agent comprises: carbonaceous reducing agent and/or ferrosilicon.

Preferably, the calcium method vanadium extraction tailings comprise the following components:

4.4-5 wt% S;

8.5-10.4 wt% of CaO;

1.1 to 1.4 wt% of MgO;

4.2-5.0 wt% of MnO;

27.1 to 29.2 wt% of TFe;

11.1 to 12.8 wt% of SiO₂；

9.7-10.5 wt% of TiO₂；

1.7～2.2wt％V₂O₅；

1.4-1.8 wt% of Al₂O₃；

1.02-1.09 wt% of Cr₂O₃。

Preferably, the carbonaceous material is selected from one or more of coke and anthracite.

Preferably, the mass of the carbonaceous material is 5-30% of that of the tailings obtained by calcium method vanadium extraction.

Preferably, the temperature of the first temperature rise treatment is 1300-1500 ℃, and the treatment time is 30-180 min.

Preferably, the mass content of water in the dehydrated and desulfurized tailings is less than 1 percent; the mass content of sulfur is less than 0.01 percent.

Preferably, the carbonaceous reducing agent is selected from one or two of the group consisting of petcoke and anthracite.

Preferably, the mass of the reducing agent is 1-21% of the mass of the low-sulfur tailings.

Preferably, the temperature of the second temperature rise treatment is 1500-1700 ℃, and the treatment time is 15-30 min.

The invention provides a harmless treatment method of vanadium extraction tailings by a calcium method, which comprises the steps of dehydrating, desulfurizing and reducing the vanadium extraction tailings in a pushed slab kiln or a rotary kiln, desulfurizing flue gas by adopting a flue gas desulfurization method, and reducing and recovering valuable elements such as vanadium, iron and the like in the tailings by using a carbonaceous reducing agent; and the obtained low-sulfur tailings are transferred into an electric furnace, the tailings are melted by an electrode and a carbonaceous reducing agent is added for reduction, the obtained iron blocks or molten iron can be used for alloying molten steel, and the slag can be used for producing cement, so that the resource utilization of the vanadium extraction tailings is realized. The treatment method provided by the invention can effectively utilize valuable elements in the vanadium extraction tailings, so that the elements such as vanadium, iron and the like are effectively recycled, the green utilization of industrial waste resources is realized, the efficient utilization of resources is facilitated, the harmless treatment of the tailings is solved, and benefits are created.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.

The invention provides a harmless treatment method of tailings generated in vanadium extraction by a calcium method, which comprises the following steps:

mixing the tailings obtained by extracting vanadium by a calcium method with a carbonaceous material, and carrying out first heating treatment for dehydration and desulfurization to obtain dehydrated desulfurization tailings;

and carrying out second temperature-raising treatment reduction on the dehydrated and desulfurized tailings to obtain vanadium-containing molten iron and furnace slag.

In the invention, the tailings of vanadium extraction by calcium method is obtained by oxidizing and roasting vanadium slag and lime, and treating the obtained clinker by sulfuric acid to obtain vanadium-containing solution and tailings, wherein the tailings are the tailings of vanadium extraction by calcium method and contain a large amount of CaSO₄The water content is also as high as 30%.

In the invention, the calcium method vanadium extraction tailings can comprise the following components:

4.4-5 wt% S;

8.5-10.4 wt% of CaO;

1.1 to 1.4 wt% of MgO;

4.2-5.0 wt% of MnO;

27.1 to 29.2 wt% of TFe;

11.1 to 12.8 wt% of SiO₂；

9.7-10.5 wt% of TiO₂；

1.7～2.2wt％V₂O₅；

1.4-1.8 wt% of Al₂O₃；

1.02-1.09 wt% of Cr₂O₃。

In the invention, the mass content of S is preferably 4.5-4.9%, more preferably 4.6-4.8%, and most preferably 4.7%; the mass content of CaO is preferably 9-10%, more preferably 9.3-9.7%, and most preferably 9.5%; the mass content of the MgO is preferably 1.2-1.3%; the MnO is preferably 4.3-4.8% by mass, more preferably 4.4-4.6% by mass and most preferably 4.5% by mass; the mass content of the TFe is preferably 27.5-29%, more preferably 28-28.5%, the TFe is metallic iron and is Fe₂O₃Iron oxides such as FeO, namely 27.1-29.2 wt% of Fe in the tailings of vanadium extraction by calcium method₂O₃And 27.1-29.2 wt% FeO; the SiO₂The mass content of (b) is preferably 11.5 to 12.5%, more preferably 11.8 to 12.2%, most preferably 12%; the TiO is₂The mass content of (b) is preferably 9.8-10.2%, more preferably 10%; the V is₂O₅The mass content of (b) is preferably 1.8-2%, more preferably 1.9%; the Al is₂O₃The mass content of (b) is preferably 1.5 to 1.7%, more preferably 1.6%; the Cr is₂O₃The content of (b) is preferably 1.03 to 1.08%, more preferably 1.04 to 1.07%, and most preferably 1.05 to 1.06%.

In the invention, the calcium method vanadium extraction tailings preferably further comprise: and (3) water.

In the present invention, the water is preferably 8 to 12% by mass, more preferably 9 to 11% by mass, and most preferably 10% by mass.

In the present invention, the carbonaceous material has a relatively high carbon content, and is preferably one or both of a coke briquette and anthracite.

In the invention, the mass of the carbonaceous material is preferably 5-30%, more preferably 10-25%, and most preferably 15-20% of the mass of the tailings of vanadium extraction by calcium method.

In the invention, the mass of the carbonaceous material is preferably 5-25%, more preferably 10-20%, and most preferably 15% of the mass of the tailings of vanadium extraction by calcium method.

In the invention, the mass of the carbonaceous material is preferably 10-20%, more preferably 12-18%, and most preferably 14-16% of the mass of the tailings of vanadium extraction by calcium method.

In the invention, the mass of the carbonaceous material is preferably 20-30%, more preferably 22-28%, and most preferably 24-26% of the mass of the tailings of vanadium extraction by calcium method.

In the present invention, the first temperature raising treatment and the second temperature raising treatment are preferably performed in a pusher kiln; preferably, the mixed substances are put into a graphite crucible and are placed into a pushed slab kiln for heating treatment.

In the invention, the temperature of the first temperature raising treatment is preferably 1300-1500 ℃, more preferably 1350-1450 ℃, and most preferably 1400 ℃.

In the invention, the temperature of the first temperature raising treatment (dehydration and desulfurization) is preferably 1300-1450 ℃, more preferably 1350-1400 ℃, and most preferably 1360-1380 ℃.

In the present invention, the temperature of the first temperature raising treatment is preferably 1400 to 1500 ℃, more preferably 1420 to 1480 ℃, and most preferably 1440 to 1460 ℃.

In the present invention, the time of the first temperature raising treatment is preferably 30 to 180min, more preferably 50 to 160min, more preferably 70 to 140min, more preferably 90 to 120min, and most preferably 100 to 110 min.

In the present invention, the first temperature-raising treatment time is preferably 30 to 60min, more preferably 40 to 50min, and most preferably 45 min.

In the present invention, the time of the first temperature-raising treatment (dehydration and desulfurization) is preferably 30 to 120min, more preferably 50 to 100min, and most preferably 60 to 80 min.

In the present invention, the time of the first temperature-raising treatment (dehydration and desulfurization) is preferably 60 to 180min, more preferably 80 to 160min, more preferably 100 to 140min, and most preferably 120 min.

In the invention, the first temperature rise treatment is preferably to raise the temperature of the front 1/3 section of the pushed slab kiln to 1400-1500 ℃ for dehydration and desulfurization, and the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln is controlled within 30-60 min.

In the invention, the mass content of water in the dehydrated desulfurization tailings is preferably less than 1 percent; the sulfur content is preferably < 0.01% by mass.

In the present invention, the method for preparing the low sulfur tailings preferably comprises:

the method comprises the steps of putting the calcium method vanadium extraction tailings into a rotary kiln, adding carbonaceous materials with high carbon content, such as coke or anthracite, of which the weight is 5% -25% of that of the calcium method vanadium extraction tailings, raising the temperature in the rotary kiln to 1300-1450 ℃ for dehydration and desulfurization, controlling the treatment time of the vanadium extraction tailings in the rotary kiln to be 30-120 min, and ensuring that the moisture content in the low-sulfur tailings is less than 1% and the sulfur content is less than 0.01%.

In the present invention, the method for preparing the low sulfur tailings preferably comprises:

the method comprises the steps of putting calcium-method vanadium extraction tailings into a pushed slab kiln, adding carbonaceous materials with high carbon content such as coke or anthracite and the like, wherein the weight of the carbonaceous materials is 10% -20% of that of the calcium-method vanadium extraction tailings, raising the temperature in the pushed slab kiln to 1400-1500 ℃ for dehydration and desulfurization, controlling the treatment time of the vanadium extraction tailings in the pushed slab kiln to be 60-180 min, and ensuring that the moisture content and the sulfur content in the low-sulfur tailings are less than 1 wt% and less than 0.01 wt%.

In the invention, the flue gas generated in the dehydration and desulfurization processes is preferably subjected to desulfurization treatment by a flue gas desulfurization method, and the obtained gypsum is preferably used for cement production.

In the present invention, it is preferable that the second temperature-raising reduction process further includes:

mixing the dehydrated and desulfurized tailings with a reducing agent to carry out second heating treatment reduction;

the reducing agent comprises: carbonaceous reducing agent and/or ferrosilicon.

In the present invention, the carbonaceous reducing agent is preferably a carbonaceous material having a relatively high carbon content, and is more preferably one or two selected from the group consisting of coke and anthracite.

In the present invention, the mass of the reducing agent (carbonaceous reducing agent) is preferably 1 to 21%, more preferably 5 to 20%, more preferably 10 to 15%, and most preferably 12 to 13% of the mass of the low-sulfur tailings.

In the present invention, the ferrosilicon is preferably 3 to 10% by mass, more preferably 4 to 8% by mass, more preferably 5 to 7% by mass, and most preferably 6% by mass of the low-sulfur tailings.

In the present invention, the reduction is preferably carried out in an electric furnace; the reduction is preferably carried out by melting the low-sulfur tailings by means of electrodes and adding ferrosilicon.

In the invention, the valuable elements such as vanadium, iron and the like in the low-sulfur tailings are reduced and recovered; the vanadium-containing iron block with economic benefit is obtained by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like.

In the invention, the temperature of the second temperature raising treatment is preferably 1500-1700 ℃, more preferably 1550-1650 ℃, and most preferably 1600 ℃.

In the present invention, the temperature of the second temperature raising treatment (reduction) is preferably 1500 to 1600 ℃, more preferably 1520 to 1580 ℃, and most preferably 1540 to 1560 ℃.

In the invention, the temperature of the second temperature rise treatment is preferably 1500-1650 ℃, more preferably 1550-1600 ℃, and most preferably 1570-1580 ℃.

In the present invention, the time of the second temperature raising treatment is preferably 15 to 30min, and more preferably 20 to 25 min.

In the invention, the second temperature raising treatment is preferably carried out by raising the temperature to 1500-1650 ℃ in the middle 1/6 section of the pushed slab kiln, obtaining vanadium-containing molten iron with economic benefit by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like, realizing layering of the molten iron and slag, and controlling the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln to be 15-30 min.

In the present invention, the second temperature-raising treatment (reduction) method preferably includes:

transferring the low-sulfur tailings obtained by calcium-method vanadium extraction tailings after treatment of the rotary kiln into an electric furnace through a slag pot, electrifying to melt the low-sulfur tailings, heating to 1500-1700 ℃, and adding carbonaceous materials with high carbon content, such as coke or anthracite, wherein the weight of the carbonaceous materials is 1-21% of that of the low-sulfur tailings; the vanadium-containing iron block with economic benefit is obtained by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like.

In the present invention, the second temperature-raising treatment (reduction) method preferably includes:

transferring low-sulfur tailings obtained by calcium-method vanadium extraction tailings after treatment of the pushed slab kiln into an electric furnace through a slag pot, electrifying to melt the low-sulfur tailings, heating to 1500-1600 ℃, and adding ferrosilicon with the weight of 3-10% of the low-sulfur tailings; the vanadium-containing iron block with economic benefit is obtained by utilizing the reduction effect of silicon on elements such as iron, vanadium and the like.

In the present invention, it is preferable that the mass content of iron in the slag is less than 0.1% and the reduction is stopped after the mass content of vanadium is less than 0.05% in the second temperature-raising treatment (reduction).

In the present invention, after obtaining the vanadium-containing molten iron, the method preferably further comprises:

and cooling the vanadium-containing molten iron to obtain an iron block.

In the invention, the cooling method is preferably that the rear half section of the pushed slab kiln is not heated, the temperature of the crucible is naturally cooled down, and the crucible is taken out of the pushed slab kiln and then is subjected to slag-iron separation to obtain iron blocks and slag.

In the present invention, the iron nuggets are preferably used for steel-making alloying; the slag is preferably used for cement production.

In the invention, the vanadium-containing molten iron is preferably cast to obtain vanadium-containing iron blocks for molten steel alloying.

In the present invention, the slag is preferably water quenched for use in cement production.

In the invention, the tail gas generated by the temperature rise treatment by adopting the pushed slab kiln is preferably desulfurized in the whole process.

In the invention, the harmless treatment method of the tailings obtained by calcium method vanadium extraction preferably comprises the following steps:

fully mixing calcium vanadium extraction tailings with carbonaceous materials with high carbon content, such as coke or anthracite and the like, which account for 20-30% of the weight of the calcium vanadium extraction tailings, placing the mixture into a graphite crucible and placing the mixture into a pushed slab kiln, raising the temperature of the front 1/3 section of the pushed slab kiln to 1400-1500 ℃ for dehydration and desulfurization, controlling the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln to be 30-60 min, and ensuring that the moisture content and the sulfur content in the tailings are less than 1% and 0.01%;

the temperature of the middle 1/6 section of the pushed slab kiln is raised to 1500-1650 ℃, vanadium-containing molten iron with economic benefit is obtained by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like, the molten iron and the slag are layered, and the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln is controlled to be 15-30 min;

the latter half section of the pushed slab kiln is not heated, the temperature of the crucible is naturally cooled down, the crucible is taken out of the pushed slab kiln for slag-iron separation, the slag is used for cement production, and the iron blocks are used for steel-making alloying;

and desulfurizing the tail gas obtained by the pushed slab kiln treatment in the whole process.

The treatment method provided by the invention can effectively utilize valuable elements in the vanadium extraction tailings, so that the elements such as vanadium, iron and the like are effectively recycled, the green utilization of industrial waste resources is realized, the efficient utilization of resources is facilitated, the harmless treatment of the tailings is solved, and benefits are created.

The components of the tailings obtained by extracting vanadium by the calcium method adopted in the following embodiments of the invention comprise: s4.6 wt%, CaO9.7wt%, MgO 1.4 wt%, MnO 4.5 wt%, TFe 28.6 wt%, SiO₂ 12.1wt％、TiO₂ 9.8wt％、V₂O₅ 2.0wt％、Al₂O₃ 1.6wt％、Cr₂O₃ 1.06wt％。

Example 1

Fully mixing the calcium-method vanadium extraction tailings and 20 wt% of the calcium-method vanadium extraction tailings, placing the mixture into a graphite crucible, placing the graphite crucible into a pushed slab kiln, raising the temperature of the front 1/3 section of the pushed slab kiln to 1400 ℃ for dehydration and desulfurization, and controlling the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln to be 60min so as to ensure that the moisture content in the tailings is less than 1% and the sulfur content in the tailings is less than 0.01%; the temperature of the middle 1/6 section of the pushed slab kiln is raised to 1650 ℃, vanadium-containing molten iron with economic benefit is obtained by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like, the layering of the molten iron and slag is realized, and the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln is controlled to be 30 min; the latter half section of the pushed slab kiln is not heated, the temperature of the crucible is naturally cooled, the slag and iron separation is carried out after the crucible is taken out of the pushed slab kiln, the slag is used for producing cement, and the iron blocks are used for alloying in steelmaking. And desulfurizing the tail gas obtained by the pushed slab kiln treatment in the whole process.

And detecting the contents of C and V in the iron block by using a direct-reading spectrometer, wherein the detection result is that the mass content of C in the iron block is 5.21% and the mass content of V in the iron block is 3.11%.

The yield of vanadium in the slag was 90.9% (mineral detection).

Example 2

Fully mixing the calcium-method vanadium extraction tailings and anthracite coal accounting for 30 percent of the weight of the calcium-method vanadium extraction tailings, putting the mixture into a graphite crucible, placing the mixture into a pushed slab kiln, raising the temperature of the front 1/3 section of the pushed slab kiln to 1500 ℃ for dehydration and desulfurization, controlling the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln to be 30min, and ensuring that the moisture content in the tailings is less than 1 percent and the sulfur content in the tailings is less than 0.01 percent; the temperature of the middle 1/6 section of the pushed slab kiln is raised to 1500 ℃, vanadium-containing molten iron with economic benefits is obtained by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like, the layering of the molten iron and furnace slag is realized, and the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln is controlled to be 15 min; the latter half section of the pushed slab kiln is not heated, the temperature of the crucible is naturally cooled, the slag and iron separation is carried out after the crucible is taken out of the pushed slab kiln, the slag is used for producing cement, and the iron blocks are used for alloying in steelmaking. And desulfurizing the tail gas obtained by the pushed slab kiln treatment in the whole process.

The mass contents of C and V in the iron nuggets obtained in example 2 of the present invention were measured according to the method of example 1, and the results of the measurements were that the mass content of C in the iron nuggets was 5.18%, the mass content of V was 3.07%, and the yield of vanadium in the slag was 88.4%.

Example 3

Fully mixing calcium vanadium extraction tailings and carbonaceous materials with high coke-butyl carbon content and 25 wt% of the calcium vanadium extraction tailings, placing the mixture into a graphite crucible, placing the graphite crucible into a pushed slab kiln, raising the temperature of the front 1/3 section of the pushed slab kiln to 1450 ℃ for dehydration and desulfurization, controlling the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln to be 40min, and ensuring that the moisture content and the sulfur content in the tailings are less than 1% and less than 0.01%; the temperature of the middle 1/6 section of the pushed slab kiln is raised to 1600 ℃, vanadium-containing molten iron with economic benefit is obtained by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like, the layering of the molten iron and furnace slag is realized, and the treatment time of the vanadium extraction tailings in the section of the pushed slab kiln is controlled to be 20 min; the latter half section of the pushed slab kiln is not heated, the temperature of the crucible is naturally cooled, the slag and iron separation is carried out after the crucible is taken out of the pushed slab kiln, the slag is used for producing cement, and the iron blocks are used for alloying in steelmaking. And desulfurizing the tail gas obtained by the pushed slab kiln treatment in the whole process.

The mass contents of C and V in the iron nuggets obtained in example 3 of the present invention were measured according to the method of example 1, and the results of the measurements were that the mass content of C in the iron nuggets was 4.93%, the mass content of V was 2.98%, and the yield of vanadium in the slag was 88.1%.

Example 4

Putting the tailings obtained by calcium-method vanadium extraction into a rotary kiln, adding the coke which is 5 percent of the weight of the tailings obtained by calcium-method vanadium extraction, raising the temperature in the rotary kiln to 1450 ℃ for dehydration and desulfurization, and controlling the treatment time of the tailings obtained by vanadium extraction in the rotary kiln to be 120min to ensure that the moisture content in the obtained low-sulfur tailings is less than 1 wt% and the sulfur content in the obtained low-sulfur tailings is less than 0.01 wt%; flue gas is desulfurized by adopting a flue gas desulfurization method in the treatment process of the rotary kiln, and the obtained gypsum is used for cement production;

transferring the calcium method vanadium extraction tailings treated by the rotary kiln into an electric furnace through a slag pot, electrifying to melt the tailings, heating the tailings to 1700 ℃, adding coke dices accounting for 21 percent of the weight of the tailings, and obtaining vanadium-containing iron blocks with economic benefits by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like; in the electric furnace smelting process, when the iron content in the obtained slag is less than 0.1 wt% and the vanadium content is less than 0.05 wt%, stopping electrifying, discharging the obtained molten iron into a molten iron tank, and casting into blocks to obtain vanadium-containing iron blocks; the liquid slag is used for cement production after water quenching.

According to the method of the embodiment 1, the components of the vanadium-containing iron block obtained in the embodiment 4 of the invention are detected, and the detection result is as follows: 4.23 wt% of [ C ] and 3.10 wt% of [ V ] in the vanadium-containing iron block, and the yield of vanadium in the slag is 90.3%.

Example 5

The method comprises the following steps of putting the calcium method vanadium extraction tailings into a rotary kiln, adding anthracite coal accounting for 25% of the weight of the calcium method vanadium extraction tailings, raising the temperature in the rotary kiln to 1300 ℃ for dehydration and desulfurization, and controlling the treatment time of the vanadium extraction tailings in the rotary kiln to be 30min to ensure that the moisture content and the sulfur content in the obtained low-sulfur tailings are less than 1 wt% and less than 0.01 wt%; flue gas is desulfurized by adopting a flue gas desulfurization method in the treatment process of the rotary kiln, and the obtained gypsum is used for cement production;

transferring the calcium-method vanadium extraction tailings treated by the rotary kiln into an electric furnace through a slag pot, electrifying to melt low-sulfur tailings, heating to 1500 ℃, adding anthracite accounting for 1% of the weight of the low-sulfur tailings, and obtaining vanadium-containing iron blocks with economic benefits by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like; in the electric furnace smelting process, when the iron content in the obtained slag is less than 0.1 wt% and the vanadium content is less than 0.05 wt%, stopping electrifying, discharging the obtained molten iron into a molten iron tank, and casting into blocks to obtain vanadium-containing iron blocks; the liquid slag is used for cement production after water quenching.

According to the method of the embodiment 1, the vanadium-containing iron block prepared in the embodiment 5 of the invention is subjected to component detection, and the detection result is that [ C ] is 3.89 wt% and [ V ] is 2.94 wt% in the vanadium-containing iron block, and the vanadium yield in the slag is 87.2%.

Example 6

Putting the tailings obtained by calcium-method vanadium extraction into a rotary kiln, adding the coke dices accounting for 15% of the weight of the tailings obtained by calcium-method vanadium extraction, raising the temperature in the rotary kiln to 1350 ℃ for dehydration and desulfurization, and controlling the treatment time of the tailings obtained by vanadium extraction in the rotary kiln to be 100min to ensure that the moisture content in the obtained low-sulfur tailings is less than 1 wt% and the sulfur content in the obtained low-sulfur tailings is less than 0.01 wt%; flue gas is desulfurized by adopting a flue gas desulfurization method in the treatment process of the rotary kiln, and the obtained gypsum is used for cement production;

transferring the calcium-method vanadium extraction tailings treated by the rotary kiln into an electric furnace through a slag pot, electrifying to melt low-sulfur tailings, heating to 1600 ℃, adding anthracite accounting for 11% of the weight of the low-sulfur tailings, and obtaining vanadium-containing iron blocks with economic benefits by utilizing the reduction effect of carbon on elements such as iron, vanadium and the like; in the electric furnace smelting process, when the iron content in the obtained slag is less than 0.1 wt% and the vanadium content is less than 0.05 wt%, stopping electrifying, discharging the obtained molten iron into a molten iron tank, and casting into blocks to obtain vanadium-containing iron blocks; the liquid slag is used for cement production after water quenching.

According to the method of the embodiment 1, the vanadium-containing iron block prepared in the embodiment 6 of the invention is subjected to component detection, and the detection result is that [ C ] is 4.33 wt% and [ V ] is 2.87 wt% in the vanadium-containing iron block, and the vanadium yield in the slag is 87.8%.

Example 7

Putting the calcium method vanadium extraction tailings into a pushed slab kiln, adding the coke accounting for 10 percent of the weight of the calcium method vanadium extraction tailings, raising the temperature in the pushed slab kiln to 1500 ℃ for dehydration and desulfurization, and controlling the treatment time of the vanadium extraction tailings in the pushed slab kiln to be 180min to ensure that the moisture content in the obtained low-sulfur tailings is less than 1 wt% and the sulfur content in the obtained low-sulfur tailings is less than 0.01 wt%; the flue gas is desulfurized by adopting a flue gas desulfurization method in the pushed slab kiln treatment process, and the obtained gypsum is used for cement production;

transferring the calcium-method vanadium extraction tailings treated by the pushed slab kiln into an electric furnace through a slag pot, electrifying to melt the tailings, heating to 1600 ℃, and adding ferrosilicon 15 percent of the weight of the tailings to reduce elements such as iron, vanadium and the like to obtain a vanadium-containing iron block with economic benefit; in the electric furnace smelting process, when the iron content in the obtained slag is less than 0.1 wt% and the vanadium content is less than 0.05 wt%, stopping electrifying, discharging the obtained molten iron into a molten iron tank, and casting into blocks to obtain vanadium-containing iron blocks; the liquid slag is used for cement production after water quenching.

According to the method of the embodiment 1, the components of the vanadium-containing iron block obtained in the embodiment 7 of the invention are detected, and the detection result is as follows: 3.23 wt% and 3.04 wt% of vanadium-containing iron blocks, and 88.1% of vanadium in the slag.

Example 8

The method comprises the following steps of putting calcium-method vanadium extraction tailings into a pushed slab kiln, adding anthracite coal accounting for 20% of the weight of the calcium-method vanadium extraction tailings, raising the temperature in the pushed slab kiln to 1400 ℃ for dehydration and desulfurization, and controlling the treatment time of the vanadium extraction tailings in the pushed slab kiln to be 60min to ensure that the moisture content in the obtained low-sulfur tailings is less than 1 wt% and the sulfur content in the obtained low-sulfur tailings is less than 0.01 wt%; the flue gas is desulfurized by adopting a flue gas desulfurization method in the pushed slab kiln treatment process, and the obtained gypsum is used for cement production;

transferring the calcium-method vanadium extraction tailings treated by the pushed slab kiln into an electric furnace through a slag pot, electrifying to melt the tailings, heating to 1500 ℃, and adding ferrosilicon with 3% of the weight of the tailings to reduce elements such as iron, vanadium and the like to obtain vanadium-containing iron blocks with economic benefits; in the electric furnace smelting process, when the iron content in the obtained slag is less than 0.1 wt% and the vanadium content is less than 0.05 wt%, stopping electrifying, discharging the obtained molten iron into a molten iron tank, and casting into blocks to obtain vanadium-containing iron blocks; the liquid slag is used for cement production after water quenching.

According to the method of the embodiment 1, the vanadium-containing iron block prepared in the embodiment 8 of the invention is subjected to component detection, and the detection result is that [ C ]4.08 wt% and [ V ]3.14 wt% in the vanadium-containing iron block and the vanadium yield in the slag is 89.6%.

Example 9

Putting the calcium method vanadium extraction tailings into a pushed slab kiln, adding the coke accounting for 15% of the weight of the calcium method vanadium extraction tailings, raising the temperature in the pushed slab kiln to 1450 ℃ for dehydration and desulfurization, and controlling the treatment time of the vanadium extraction tailings in the pushed slab kiln to be 100min to ensure that the moisture content in the obtained low-sulfur tailings is less than 1 wt% and the sulfur content in the obtained low-sulfur tailings is less than 0.01 wt%; the flue gas is desulfurized by adopting a flue gas desulfurization method in the pushed slab kiln treatment process, and the obtained gypsum is used for cement production;

transferring the calcium-method vanadium extraction tailings treated by the pushed slab kiln into an electric furnace through a slag pot, electrifying to melt the tailings, heating to 1550 ℃, and adding ferrosilicon accounting for 8 percent of the weight of the tailings to reduce elements such as iron, vanadium and the like to obtain a vanadium-containing iron block with economic benefit; in the electric furnace smelting process, when the iron content in the obtained slag is less than 0.1 wt% and the vanadium content is less than 0.05 wt%, stopping electrifying, discharging the obtained molten iron into a molten iron tank, and casting into blocks to obtain vanadium-containing iron blocks; the liquid slag is used for cement production after water quenching.

According to the method of the embodiment 1, the vanadium-containing iron block prepared in the embodiment 9 of the invention is subjected to component detection, and the detection result is that [ C ]3.93 wt% and [ V ]2.91 wt% in the vanadium-containing iron block and the vanadium yield in the slag is 87.5%.

According to the embodiments, a certain amount of carbonaceous materials are added into the tailings of vanadium extraction by the calcium method, dehydration, desulfurization and reduction are carried out in a pushed slab kiln at 1500-1650 ℃, valuable elements such as vanadium, iron and the like in the slag are reduced by carbon, vanadium-containing iron blocks and slag are obtained, the iron blocks can be used for alloying molten steel, and the slag can be used for producing cement, so that the resource utilization and harmless treatment of the tailings of vanadium extraction are realized. The method can effectively utilize valuable elements in the vanadium extraction tailings, so that the elements such as vanadium, iron and the like are effectively recycled, the green utilization of industrial waste resources is realized, and the high-efficiency utilization of the resources is facilitated. The method is suitable for enterprises producing vanadium products by adopting vanadium slag through a calcium method vanadium extraction process, and solves the problem of resource utilization of tailings generated after vanadium products are produced by vanadium slag through a calcium method vanadium extraction method in vanadium product factories.

The invention provides a method for recycling tailings generated in vanadium extraction by a calcium method, which comprises the following steps: adding a certain amount of carbonaceous materials into the tailings of vanadium extraction by the calcium method, dehydrating and desulfurizing in a rotary kiln at 1300-1450 ℃, desulfurizing the flue gas by a flue gas desulfurization method, transferring the obtained low-sulfur tailings into an electric furnace, melting the tailings by an electrode and adding a carbonaceous reducing agent for reduction to obtain vanadium-containing iron blocks and slag, wherein the iron blocks can be used for alloying molten steel, and the slag can be used for producing cement, so that the resource utilization of the vanadium-extraction tailings is realized. The invention solves the problem of recycling tailings generated after vanadium products are produced by vanadium slag by a calcium method vanadium extraction method in a vanadium product factory, provides a method for recycling the tailings generated by the calcium method vanadium extraction, and is suitable for enterprises which use the vanadium slag as a raw material and adopt a calcium method vanadium extraction process to produce the vanadium products.

The invention provides a method for recovering valuable resources of tailings generated in vanadium extraction by a calcium method, which comprises the following steps: adding a certain amount of carbonaceous materials into calcium-method vanadium extraction tailings, dehydrating and desulfurizing in a pushed slab kiln at 1400-1500 ℃, desulfurizing flue gas by adopting a flue gas desulfurization method, transferring the obtained low-sulfur tailings into an electric furnace, melting the tailings by using an electrode, adding ferrosilicon to reduce valuable elements such as vanadium, iron and the like in the tailings, and obtaining vanadium-containing iron blocks and slag, wherein the iron blocks can be used for molten steel alloying, and the slag can be used for cement production, so that the resource utilization of the vanadium extraction tailings is realized. The invention solves the problem of recycling tailings generated after vanadium products are produced by vanadium slag by a calcium method vanadium extraction method in a vanadium product factory, provides a method for recycling the tailings generated by the calcium method vanadium extraction, and is suitable for enterprises which use the vanadium slag as a raw material and adopt a calcium method vanadium extraction process to produce the vanadium products.

While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.