阅读说明：本技术 一种钙法提钒尾渣中有价元素钒和铁的零排放生产方法 (Zero-emission production method for valuable elements vanadium and iron in tailings obtained by calcium method vanadium extraction ) 是由 戈文荪 梁新腾 陈炼 郝建璋 于 2021-08-19 设计创作，主要内容包括：本发明提供了一种钙法提钒尾渣中有价元素钒和铁的零排放生产方法,包括以下步骤：A)将钙法提钒尾渣进行脱硫处理,得到选别铁料；B)将选别铁料进行熔融还原后再进行调渣处理,得到低钒铁块；C)将所述低钒铁块进行钒合金化。本发明具有操作简单和清洁化绿色的生产特点,完全符合国家环保要求,钙法提钒尾渣中有价元素钒与铁回收效果好,生产成本低,同时,还可实现全流程渣排量零排放,利国利民。(The invention provides a zero-emission production method of valuable elements vanadium and iron in tailings obtained by calcium-method vanadium extraction, which comprises the following steps: A) desulfurizing the tailings obtained by extracting vanadium by a calcium method to obtain a selected iron material; B) carrying out melting reduction on the selected iron material, and then carrying out slag mixing treatment to obtain a low-vanadium iron block; C) and carrying out vanadium alloying on the low-vanadium iron block. The method has the characteristics of simple operation and clean green production, completely meets the national environmental protection requirement, has good recovery effect of valuable elements vanadium and iron in the tailings of vanadium extraction by the calcium method and low production cost, and can realize zero discharge of slag in the whole process and benefit the nation and people.)

1. A zero-emission production method of valuable elements vanadium and iron in tailings obtained by calcium-method vanadium extraction comprises the following steps:

A) desulfurizing the tailings obtained by extracting vanadium by a calcium method to obtain a selected iron material;

B) carrying out melting reduction on the selected iron material, and then carrying out slag mixing treatment to obtain a low-vanadium iron block;

C) and carrying out vanadium alloying on the low-vanadium iron block.

2. The zero-emission production method of claim 1, wherein the desulfurization treatment has a desulfurization rate of more than 90% and a sulfur content of less than 0.3%.

3. The zero-emission production method of claim 1, wherein the slag modifier for slag modification comprises 40-50 parts by weight of calcium oxide, 30-50 parts by weight of aluminum oxide and 5-15 parts by weight of sodium salt.

4. The zero-emission production method of claim 1 or 3, wherein the amount of the slag modifier used in the slag modifying treatment is 100-500 kg/furnace.

5. The zero-emission production process of claim 1, wherein the smelting-reduced medium is selected from one or both of coke and coal.

6. The zero-emission production method of claim 1, wherein the temperature of the melting reduction is 1600-1700 ℃, and the time is 1-4 h.

7. The zero-emission production method of claim 1, wherein the low-vanadium iron nuggets have a composition comprising: [C] 3.5-5.0%, [ V ] 1.5-4.5%, [ Si ] and Mn ] 0.8-1.2%, and [ S ] and [ P ] less than 0.05%, the balance being Fe.

8. The zero-emission production method of claim 1, wherein the vanadium content in the vanadium alloyed steel is 0.02 to 0.08 wt%.

Technical Field

The invention relates to the technical field of solid waste treatment of deep processing of vanadium products, in particular to a zero-emission production method of valuable elements vanadium and iron in tailings obtained by calcium-method vanadium extraction.

Background

Vanadium is a valuable element and has wide application in the fields of metallurgy, aerospace, medical treatment and the like. The extraction and deep processing of the vanadium are beneficial to the nation and the people. In industrial production, the vanadium extraction process mainly comprises two processes of blast furnace ironmaking, converter vanadium extraction, vanadium slag deep processing to obtain vanadium products and stone-based vanadium extraction process. The two processes have the common problem of low vanadium yield (only about 44%). Therefore, in order to improve the vanadium yield, the metallurgist has conducted many studies, and although the metallurgy researchers have achieved a certain effect, the improvement is not great. There are many methods for extracting valuable element vanadium from vanadium-containing iron ore concentrate, but the recycling difficulty of sodium-containing iron salt materials generated in the existing patent is very high, and the method is particularly difficult to prevent and treat the corrosion hazard of furnace lining.

Chinese patent publication No. CN103614565A discloses a process for extracting vanadium from steel tailings. The invention provides a process method with high recovery rate and stable recovery of vanadium and iron in steel slag aiming at the comprehensive utilization, value improvement and vanadium resource recovery of the steel slag with low vanadium content, and the recovery rate of vanadium and iron is more than 90%; the method comprises the following steps: A. preparing materials: taking low vanadium steel tailings (40-65%) as a raw material, and adding auxiliary materials A (14-20%) and coal B (15-46%) for use; B. adding all the ingredients into a submerged arc furnace for reduction smelting to obtain low-vanadium pig iron and reduced water granulated slag; C. and hot charging low-vanadium pig iron into a converter, adding a coolant to blow oxygen to extract vanadium, and obtaining vanadium slag and semisteel.

Chinese patent with publication number CN101838743A discloses a method for recovering iron, vanadium, chromium and gallium from vanadium extraction tailings, which comprises the following steps: mixing 100 parts of vanadium extraction tailings, 12-25 parts of reducing agent, 15-25 parts of calcium oxide and 2-4 parts of binder uniformly; b. pelletizing: pelletizing to obtain green pellets; c. primary reduction: reducing the green pellets at 1000-1200 ℃ to obtain metallized pellets; d. smelting and deep reduction: and smelting, separating and deeply reducing the metallized pellets at 1450-1600 ℃ to obtain furnace slag and pig iron containing vanadium, chromium and gallium.

Chinese patent publication No. CN102179292A discloses a method for separating and extracting iron, vanadium and titanium from vanadium titano-magnetite; the method specifically comprises the following steps: performing magnetic separation on the vanadium-titanium magnetite to obtain iron-vanadium concentrate and tailings; flotation of tailings to obtain titanium concentrate: titanium concentrate is roasted, enriched with titanium, subjected to impurity removal and magnetic separation, and further refined; mixing the impurity-removed titanium concentrate and the iron concentrate according to the beneficiation yield ratio, and adding a reducing agent and sodium carbonate to carry out reduced iron and vanadium smelting; the titanium slag obtained by reduction smelting is subjected to acid leaching for impurity removal to obtain TiO₂Not less than 92% of high-quality titanium slag products; and carrying out converter vanadium extraction on the vanadium-containing pig iron obtained by reduction smelting to obtain semisteel and vanadium slag.

Chinese patent publication No. CN1629326A discloses a method for extracting vanadium from vanadium-containing iron ore concentrate pellets; adding a proper amount of sodium salt into vanadium-containing iron concentrate powder for pelletizing and roasting to form sodium-modified pellets, performing water leaching treatment on the sodium-modified pellets to dissolve soluble sodium vanadate in water, adding sulfuric acid into the obtained sodium vanadate solution after the sodium vanadate solution is concentrated and qualified, mixing and stirring to ensure that V is dissolved in water₂O₅Precipitating, press filtering, oven drying to obtain powder or melting and casting into sheet V₂O₅And taking the pellet after vanadium extraction as an iron making raw material.

Although the method realizes effective extraction of vanadium in the vanadium extraction tailings, the process is complex and the environmental protection property is poor.

Disclosure of Invention

The invention aims to provide a zero discharge method of valuable elements vanadium and iron in the tailings of vanadium extraction by a calcium method, which can produce qualified low-vanadium pig iron products and can be used for vanadium alloying.

In view of the above, the application provides a zero-emission production method of valuable elements vanadium and iron in tailings obtained by calcium-method vanadium extraction, which comprises the following steps:

A) desulfurizing the tailings obtained by extracting vanadium by a calcium method to obtain a selected iron material;

B) carrying out melting reduction on the selected iron material, and then carrying out slag mixing treatment to obtain a low-vanadium iron block;

C) and carrying out vanadium alloying on the low-vanadium iron block.

Preferably, the desulfurization rate of the desulfurization treatment is more than 90%, and the sulfur content is reduced to be less than 0.3%.

Preferably, the slag modifier for slag modifying treatment comprises 40-50 parts by weight of calcium oxide, 30-50 parts by weight of aluminum oxide and 5-15 parts by weight of sodium salt.

Preferably, the amount of the slag modifier for slag modifying treatment is 100-500 kg/furnace.

Preferably, the smelting reduced medium is selected from one or both of coke and coal.

Preferably, the temperature of the melting reduction is 1600-1700 ℃, and the time is 1-4 h.

Preferably, the low vanadium iron block comprises the following components: [C] 3.5-5.0%, [ V ] 1.5-4.5%, [ Si ] and Mn ] 0.8-1.2%, and [ S ] and [ P ] less than 0.05%, the balance being Fe.

Preferably, the vanadium content in the vanadium alloyed steel is 0.02-0.08 wt%.

The application provides a zero discharge method of valuable elements vanadium and iron in calcium-method vanadium extraction tailings, which comprises the steps of firstly carrying out desulfurization treatment on the calcium-method vanadium extraction tailings to obtain selected iron materials, carrying out slag mixing treatment after carrying out melting reduction on the selected iron materials to obtain low-vanadium iron blocks, and finally alloying the low-vanadium iron blocks; the method provided by the application can realize effective separation of slag iron, so that a high-quality low-vanadium iron block is produced, vanadium alloying is carried out on the low-vanadium iron block in the molten steel of the building steel, the vanadium content in the alloy steel reaches 0.02-0.08%, and the alloying cost per ton of steel can be reduced by 10-20 yuan.

Detailed Description

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.

The invention discloses a zero-emission production method for comprehensively recovering valuable elements vanadium and iron in calcium-method vanadium extraction tailings, which comprises the steps of firstly removing gypsum in the tailings by using a desulfurizing agent (sorting agent) from the calcium-method vanadium extraction tailings, enriching iron in the tailings to 35-50%, and enriching V₂O₅1.5 to 3.5 percent,the selected iron material is sent to a metallurgical furnace to be melted and reduced by a reducing agent, and in the later stage of melting, a slag regulating agent is added to carry out slag regulating treatment, so that the effective separation of slag and iron is realized, and high-quality low-vanadium iron blocks are produced; the low-vanadium iron block can be used for vanadium alloying in the smelting process of steel for building materials, and mainly comprises the following components: [ C ]]3.5％～5.0％，[V]1.5％～4.5％，[Si]、Mn]At about 1.0%, [ S ]]、[P]Less than 0.05%, less than 2.0% of impurities and the balance of iron; the selected gypsum and slag generated in the smelting process of the metallurgical furnace can be used as raw materials for producing cement, so that zero emission in the whole process is realized; the produced low-vanadium pig iron is subjected to molten steel vanadium alloying of building steel, the vanadium content in vanadium alloyed steel reaches 0.02-0.08%, and the alloying cost per ton of steel can be reduced by 10-20 yuan. Specifically, the embodiment of the invention discloses a zero-emission production method of valuable elements vanadium and iron in tailings obtained by calcium-method vanadium extraction, which comprises the following steps:

A) desulfurizing the tailings obtained by extracting vanadium by a calcium method to obtain a selected iron material;

B) carrying out melting reduction on the selected iron material, and then carrying out slag mixing treatment to obtain a low-vanadium iron block;

C) and carrying out vanadium alloying on the low-vanadium iron block.

In the application, firstly, the tailings of vanadium extraction by the calcium method are desulfurized to remove gypsum in the tailings of vanadium extraction by the calcium method, the desulfurization rate is over 90 percent, the iron content in the enriched tailings reaches 35 to 50 percent, and V is₂O₅1.5 to 3.5 percent, and the sulfur content is reduced from more than 4.0 percent to less than 0.3 percent. In the present application, the desulfurization agent for desulfurization treatment is a desulfurization agent well known to those skilled in the art, and the present application is not particularly limited.

Carrying out melting reduction on the obtained sorted iron material, and then carrying out slag mixing treatment to obtain a low-vanadium iron block; the smelting reduction is carried out in a metallurgical furnace of 5 t-30 t, the reduction medium of the smelting reduction can be selected from carbonaceous materials, more specifically one or two of coke and coal, the temperature of the smelting reduction is 1600-1700 ℃, and the time of the smelting reduction is 1-4 h. The slag modifier for slag modifying treatment specifically comprises 40-50 parts by weight of calcium oxide, 30-50 parts by weight of aluminum oxide and 5-15 parts by weight of sodium salt; more specifically, the calcium oxide accounts for 50 parts by weight, the aluminum oxide accounts for 40 parts by weight, the sodium salt accounts for 10 parts by weight, and the amount of the slag modifier is 100-500 kg/furnace. The effective separation of the iron slag is realized through the slag regulating treatment.

According to the invention, the obtained low-vanadium iron block can be used for vanadium alloying in the smelting process of steel for building materials, and comprises the following main components: [C] 3.5-5.0%, [ V ] 1.5-4.5%, [ Si ] and Mn ] 0.8-1.2%, and [ S ] and [ P ] less than 0.05%, the balance being Fe.

The method provided by the application can be continuously carried out or carried out intermittently, and the recovery rate of valuable elements in the tailings of vanadium extraction by the full-flow calcium method can reach: more than 85% of vanadium and more than 90% of iron; the gypsum selected in the method and the slag generated in the smelting process of the metallurgical furnace can be used as raw materials for producing cement, so that zero emission in the whole process is realized; the low-vanadium pig iron is used for molten steel vanadium alloying of building steel. The vanadium content in the alloyed steel reaches 0.02 to 0.08 percent. The alloying cost per ton of steel can be reduced by 10-20 yuan. Therefore, the method has the advantages of short process flow, low production cost, light environmental pollution, high vanadium recovery rate (more than 80%), high iron yield (more than 90%), obvious energy conservation and emission reduction and the like, and can realize the high-efficiency comprehensive utilization of vanadium-titanium-iron ore concentrate resources.

In order to further understand the invention, the following embodiments are used to describe the zero-emission production method of valuable elements vanadium and iron in the tailings after vanadium extraction by calcium method in detail, and the protection scope of the invention is not limited by the following embodiments.

Example 1

(1) Firstly, the calcium method vanadium extraction tailings are subjected to a desulfurizing agent to remove gypsum in the tailings, so that the desulfurization rate in the calcium method vanadium extraction tailings is over 90 percent, the iron content in the enriched tailings reaches 35 to 50 percent, and V is₂O₅1.5 to 3.5 percent, and the sulfur content is reduced from more than 4.0 percent to less than 0.3 percent;

(2) delivering the selected iron material to a 5t metallurgical furnace, and carrying out smelting reduction by adopting a reducing agent to produce high-quality low-vanadium iron blocks; the melting reduction medium can use carbon materials such as coke, coal and the like, the reduction temperature is 1650 ℃, and the reduction time is 1 h; in the later stage of smelting, 100kg of slag modifier (the main components of the slag modifier are 50 parts of calcium oxide, 40 parts of aluminum oxide and 10 parts of sodium salt) is added for slag modification treatment, so that the effective separation of slag and iron is realized;

(3) the low-vanadium iron block can be used for vanadium alloying in the smelting process of steel for building materials, and mainly comprises the following components: [C] 3.5%, [ V ] 5.0%, [ Si ] and Mn ] about 1.0%, less than 0.05%, less than 2.0% of impurities, and the balance of iron;

(4) the whole process operation can be carried out continuously or intermittently; the recovery rate of valuable elements in the tailings of vanadium extraction by the full-process calcium method can reach: more than 85% of vanadium and more than 90% of iron;

(5) the selected gypsum and the slag generated in the smelting process of the metallurgical furnace can be used as raw materials for producing cement, so that zero emission in the whole process is realized;

(6) the low-vanadium pig iron produced by the method is used for vanadium alloying of the molten steel of the building material steel, and the vanadium content in the alloy steel reaches 0.02-0.08%.

Example 2

(1) Firstly, the calcium method vanadium extraction tailings are subjected to a desulfurizing agent to remove gypsum in the tailings, so that the desulfurization rate in the calcium method vanadium extraction tailings is over 90 percent, the iron content in the enriched tailings reaches 35 to 50 percent, and V is₂O₅1.5 to 3.5 percent, and the sulfur content is reduced from more than 4.0 percent to less than 0.3 percent;

(2) the selected iron material is sent to a 15t metallurgical furnace and is melted and reduced by a reducing agent to produce high-quality low-vanadium iron blocks, the melting and reducing medium can use carbon materials such as coke, coal and the like, the reducing temperature is 1700 ℃, and the reducing time is 2.5 h; in the later stage of smelting, 300kg of slag modifier (the main components of the slag modifier are 50 parts of calcium oxide, 40 parts of aluminum oxide and 10 parts of sodium salt) is added for slag modification treatment, so that the effective separation of slag and iron is realized;

(3) the low-vanadium iron block can be used for vanadium alloying in the smelting process of steel for building materials, and mainly comprises the following components: [C] 4.0%, [ V ] 3.0%, [ Si ] and Mn ] are about 1.0%, [ S ] and [ P ] are less than 0.05%, impurities are less than 2.0%, and the balance is iron;

(4) the whole process operation can be carried out continuously or intermittently; the recovery rate of valuable elements in the tailings of vanadium extraction by the full-process calcium method can reach: more than 85% of vanadium and more than 90% of iron;

(5) the selected gypsum and the slag generated in the smelting process of the metallurgical furnace can be used as raw materials for producing cement, so that zero emission in the whole process is realized;

(6) the low-vanadium pig iron produced by the method is used for vanadium alloying of the molten steel of the building material steel, and the vanadium content in the alloy steel reaches 0.02-0.08%.

Example 3

(1) Firstly, the calcium method vanadium extraction tailings are adopted to remove gypsum in the tailings by adopting a self-developed specific desulfurizer, so that the desulfurization rate in the calcium method vanadium extraction tailings is over 90 percent, the iron content in the enriched tailings reaches 35 to 50 percent, and V is₂O₅1.5 to 3.5 percent, and the sulfur content is reduced from more than 4.0 percent to less than 0.3 percent;

(2) the selected iron material is sent to a 30t metallurgical furnace and is melted and reduced by a reducing agent to produce high-quality low-vanadium iron blocks, the melting and reducing medium can use carbon materials such as coke, coal and the like, the reducing temperature is 1600 ℃, and the reducing time is 4 hours; in the later stage of smelting, 500kg of slag modifier (the main components of the slag modifier are 50 parts of calcium oxide, 40 parts of aluminum oxide and 10 parts of sodium salt) is added for slag modification treatment, so that the effective separation of slag and iron is realized;

(3) the low-vanadium iron block can be used for vanadium alloying in the smelting process of steel for building materials, and mainly comprises the following components: [C] 4.5%, [ V ] 1.5%, [ Si ] and Mn ] about 1.0%, less than 0.05% of [ S ] and [ P ], less than 2.0% of impurities and the balance of iron;

(4) the whole process operation can be carried out continuously or intermittently; the recovery rate of valuable elements in the tailings of vanadium extraction by the full-process calcium method can reach: more than 85% of vanadium and more than 90% of iron;

(5) the selected gypsum and the slag generated in the smelting process of the metallurgical furnace can be used as raw materials for producing cement, so that zero emission in the whole process is realized;

(6) the low-vanadium pig iron produced by the method is used for vanadium alloying of the molten steel of the building material steel, and the vanadium content in the alloy steel reaches 0.02-0.08%.

The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.