阅读说明：本技术 钒渣钙化熟料连续浸出提钒方法 (Continuous leaching vanadium extraction method for vanadium slag calcified clinker ) 是由 申彪 彭毅 彭宏亮 叶露 张瑶 于 2020-12-02 设计创作，主要内容包括：本发明涉及湿法冶金提钒方法领域,尤其是一种使钒渣钙化焙烧熟料酸性浸出流程高效,熟料中钒的浸出效果稳定的钒渣钙化熟料连续浸出提钒方法,包括如下步骤：a、将钙化焙烧熟料和浸出剂按质量比例1:1.5～1:4同时且连续加入到造浆搅拌槽内；b、在持续搅拌并混合均匀条件下,将混合浆料输入到快速浸出反应槽内并加酸浸出；c、将快速浸出反应槽内浸出的料浆输入到回转式连续浸出装置内,并持续加酸维持浆料pH恒定浸出；d、将回转式连续浸出装内持续流出的料浆进行固液分离,得到酸性含钒溶液和浸出残渣；e、洗涤步骤d所得的浸出残渣,得到洗涤滤液以及最终的提钒尾渣。本发明尤其适用于钒渣钙化熟料连续浸出提钒工艺之中。(The invention relates to the field of hydrometallurgy vanadium extraction methods, in particular to a method for continuously leaching vanadium from a vanadium slag calcified clinker, which has the advantages that the acid leaching process of the vanadium slag calcified roasting clinker is efficient, and the leaching effect of vanadium in the clinker is stable, and the method comprises the following steps: a. simultaneously and continuously adding the calcified roasting clinker and the leaching agent into a pulping and stirring tank according to the mass ratio of 1: 1.5-1: 4; b. under the conditions of continuous stirring and uniform mixing, inputting the mixed slurry into a rapid leaching reaction tank and adding acid for leaching; c. inputting the slurry leached from the rapid leaching reaction tank into a rotary continuous leaching device, and continuously adding acid to maintain the pH of the slurry to be constant for leaching; d. carrying out solid-liquid separation on the slurry continuously flowing out of the rotary continuous leaching device to obtain an acidic vanadium-containing solution and leaching residues; e. and d, washing the leaching residue obtained in the step d to obtain a washing filtrate and the final vanadium extraction tailings. The invention is especially suitable for the continuous leaching vanadium extraction process of the vanadium slag calcified clinker.)

1. The method for continuously leaching and extracting vanadium from the calcified clinker of vanadium slag is characterized by comprising the following steps:

a. simultaneously and continuously adding the calcified roasting clinker and the leaching agent into a pulping and stirring tank according to the mass ratio of 1: 1.5-1: 4;

b. under the conditions of continuous stirring and uniform mixing, inputting the mixed slurry into a rapid leaching reaction tank and adding acid for leaching;

c. inputting the slurry leached from the rapid leaching reaction tank into a rotary continuous leaching device, and continuously adding acid to maintain the pH of the slurry to be constant for leaching;

d. carrying out solid-liquid separation on the slurry continuously flowing out of the rotary continuous leaching device to obtain an acidic vanadium-containing solution and leaching residues;

e. and d, washing the leaching residue obtained in the step d to obtain a washing filtrate and the final vanadium extraction tailings.

2. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1, wherein: in the step a, the leaching agent is clean water or washing filtrate in the step e.

3. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1 or 2, characterized in that: the calcified roasting clinker in the step a is a material obtained by roasting vanadium slag and a calcium salt additive.

4. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1 or 2, characterized in that: the acid in step b is sulfuric acid or hydrochloric acid.

5. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1 or 2, characterized in that: in the step b, the retention time of the slurry in the rapid leaching reaction tank is 5-60 min.

6. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1 or 2, characterized in that: in the step b, the pH value range of the slurry in the rapid leaching reaction tank is 2.5-3.5.

7. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1 or 2, characterized in that: in the step c, adding acid to maintain the pH value of the slurry to be 2.6-3.2.

8. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1 or 2, characterized in that: in the step d, the concentration of the acidic vanadium-containing solution TV obtained by solid-liquid separation is 15-50 g/L.

9. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1 or 2, characterized in that: in step e, the water used for washing is clear water or a dilute acid solution.

10. The method for continuously leaching and extracting vanadium from the vanadium slag calcified clinker as claimed in claim 1 or 2, characterized in that: in the step e, the content of the washed vanadium extraction tailings TV is 0.5-2.0%.

Technical Field

The invention relates to the field of hydrometallurgy vanadium extraction methods, in particular to a method for continuously leaching vanadium from a vanadium slag calcification clinker.

Background

The existing leaching method has the problems of high environmental protection treatment difficulty, high investment, high production cost of vanadium oxide, low resource utilization rate and the like. The roasting clinker of the traditional sodium-modified vanadium extraction process is generally leached continuously by hot water, the roasting clinker of the process is particularly leached intermittently by sulfuric acid, the intermittent leaching is to add calcified roasting clinker and leaching agent into a single leaching and stirring tank, add sulfuric acid to maintain constant pH under the condition of continuous stirring until the leaching reaction is completed, and then filter and separate to obtain vanadium extraction tailings and acidic vanadium-containing solution. The intermittent leaching process reduces the effective utilization rate of equipment and limits the production efficiency. Taking the existing common processes of 'calcified roasting of vanadium slag, leaching of sulfuric acid and acid vanadium precipitation' as an example, the leaching rate of the on-site clinker is only about 92% for a long time, and particularly when the amount of the clinker leached by a single tank is increased to the designed capacity, the leaching rate is greatly reduced. Therefore, the amount of clinker leached in a single tank has to be reduced to ensure the leaching effect of the clinker on site, so that the leaching production efficiency is greatly limited, and the yield is reduced by more than 20% compared with the designed value. Meanwhile, a belt filter capable of continuous production is adopted for filtering and separating in the production line, and the belt filter cannot be well matched and connected with batch leaching production.

As for the related patent schemes, for example, chinese patent application 201310329193.0 provides a vanadium extraction leaching apparatus and a vanadium extraction leaching method, belonging to a batch vanadium extraction leaching method and apparatus for calcified roasted clinker; the Chinese patent application 201510811210.3 provides a method for improving the leaching rate of vanadium slag calcified roasting clinker, which is a method for improving the leaching rate by changing the stirring speed in the leaching process of the calcified roasting clinker; the Chinese patent application 201710414273.4 provides a method for continuously leaching vanadium slag calcified clinker, which is a leaching method that a single batch leaching agitation tank is connected in series and is controlled in a grading way. None of the above approaches addresses the corresponding drawbacks of batch leaching.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for continuously leaching and extracting vanadium from the calcified vanadium slag clinker, which has the advantages of high-efficiency acid leaching process of the calcified vanadium slag clinker and stable leaching effect of vanadium in the clinker.

The technical scheme adopted by the invention for solving the technical problems is as follows: the continuous vanadium leaching method for vanadium slag calcification clinker comprises the following steps: a. simultaneously and continuously adding the calcified roasting clinker and the leaching agent into a pulping and stirring tank according to the mass ratio of 1: 1.5-1: 4; b. under the conditions of continuous stirring and uniform mixing, inputting the mixed slurry into a rapid leaching reaction tank and adding acid for leaching; c. inputting the slurry leached from the rapid leaching reaction tank into a rotary continuous leaching device, and continuously adding acid to maintain the pH of the slurry to be constant for leaching; d. carrying out solid-liquid separation on the slurry continuously flowing out of the rotary continuous leaching device to obtain an acidic vanadium-containing solution and leaching residues; e. and d, washing the leaching residue obtained in the step d to obtain a washing filtrate and the final vanadium extraction tailings.

Further, in the step a, the leaching agent is clean water or washing filtrate in the step e.

Further, the calcified roasting clinker in the step a is a material obtained by roasting vanadium slag and a calcium salt additive.

Further, the acid in step b is sulfuric acid or hydrochloric acid.

Further, in the step b, the retention time of the slurry in the rapid leaching reaction tank is 5-60 min.

Further, in the step b, the pH value of the slurry in the rapid leaching reaction tank is in a range of 2.5-3.5.

Further, in step c, adding acid to maintain the pH value of the slurry within the range of 2.6-3.2.

Further, in the step d, the concentration of the acidic vanadium-containing solution TV obtained by solid-liquid separation is 15-50 g/L.

Further, in step e, the water used for washing is clear water or a dilute acid solution.

Further, in the step e, the washed vanadium extraction tailings TV is 0.5% -2.0%.

The invention has the beneficial effects that: the invention realizes the optimization of the process by a continuous leaching mode, wherein the leaching production efficiency is effectively improved and the leaching rate of vanadium in the clinker is ensured to be stable by a method of continuously leaching the calcified roasted clinker by vanadium slag. The invention is especially suitable for the continuous leaching vanadium extraction process of the vanadium slag calcified clinker.

Drawings

FIG. 1 is a schematic flow diagram of the present invention.

Detailed Description

The continuous vanadium leaching method for vanadium slag calcification clinker comprises the following steps: a. simultaneously and continuously adding the calcified roasting clinker and the leaching agent into a pulping and stirring tank according to the mass ratio of 1: 1.5-1: 4; b. under the conditions of continuous stirring and uniform mixing, inputting the mixed slurry into a rapid leaching reaction tank and adding acid for leaching; c. inputting the slurry leached from the rapid leaching reaction tank into a rotary continuous leaching device, and continuously adding acid to maintain the pH of the slurry to be constant for leaching; d. carrying out solid-liquid separation on the slurry continuously flowing out of the rotary continuous leaching device to obtain an acidic vanadium-containing solution and leaching residues; e. and d, washing the leaching residue obtained in the step d to obtain a washing filtrate and the final vanadium extraction tailings.

In order to further optimize the relevant process in step a, thereby obtaining better treatment effect, the scheme is preferably as follows: firstly, in the step a, the leaching agent is clean water or washing filtrate in the step e. And secondly, the calcified roasting clinker in the step a is a material obtained by roasting vanadium slag and a calcium salt additive. Preferably, the calcified roasted clinker can be continuously and quantitatively fed through the matching of facilities such as spiral feeding, vibration feeding and the like and a storage bin. The leaching agent can be continuously and quantitatively fed through facilities such as a quantitative pump, a flowmeter and the like.

Likewise, in order to further optimize the related process in step b, thereby obtaining better treatment effect, such a scheme is preferred: firstly, the acid in the step b is sulfuric acid or hydrochloric acid. And step b, the retention time of the slurry in the rapid leaching reaction tank is 5-60min, wherein the comprehensive leaching efficiency and effect factors are preferably 10-20 min. Thirdly, in the step b, the pH value range of the slurry in the rapid leaching reaction tank is 2.5-3.5, wherein 3.0 +/-0.2 is preferred. In practice, the leach slurry is preferably rapidly reacted with the acid and uniformly dispersed, preferably with agitation to create "turbulence" at the surface of the liquid.

As a method for optimizing the related process in step c so as to obtain better treatment effect, the following scheme is preferred: in step c, adding acid to maintain the pH of the slurry within the range of 2.6-3.2, preferably 2.8 + -0.1. The rotary continuous leaching device is preferably cylindrical, preferably has more than 2 compartments, and the cylinder wall is provided with a lifting plate which is driven to rotate by a variable frequency motor. The rotating speed of the rotary leaching device is preferably 5-100rpm, preferably 20-40 rpm. In addition, the residence time of the leached slurry in the rotary leaching device is preferably 20-100min, and under the condition of comprehensive leaching effect and leaching efficiency, 30-60min is preferred.

As a method for optimizing the related processes in step d to obtain better treatment effect, the following scheme is preferred: in the step d, the concentration of the acidic vanadium-containing solution TV obtained by solid-liquid separation is 15-50 g/L.

As a method for optimizing the related process in step e to obtain better treatment effect, the following scheme is preferred: in the step e, the water used for washing is clear water or a dilute acid solution, the residue washing effect is good when the dilute acid solution with the pH value of 1.5-3 is used, and the washed vanadium extraction tailings TV is preferably 0.5% -2.0%.

Examples

Example 1

Calcified roasted clinker (TV 8.46%, V)⁵⁺7.44 percent) and clean water are continuously added into a slurry making tank according to the mass ratio of 1:3, mixed slurry is obtained by stirring, the slurry flows into a rapid reaction tank to be continuously stirred, 64 percent of sulfuric acid is continuously added, the leaching pH value of the slurry is controlled to be 3.0 +/-0.1, the retention time is 20min, the slurry flows into a rotary continuous leaching device again, the rotary device is provided with 4 compartments and has the rotating speed of 30rpm, 30 percent of sulfuric acid is continuously added to ensure that the leaching pH value of the slurry is 2.8 +/-0.05, the retention time is 60min, the discharged leached slurry is subjected to solid-liquid separation to obtain an acidic vanadium-containing solution TV of 26.01g/L, the residue is washed by a sulfuric acid solution with the pH value of 3.0 to obtain the residue of 1.25 percent, and the leaching rate of vanadium is calculated to be 96.91 percent.

Example 2

Calcified roasted clinker (TV 9.17%, V)⁵⁺8.36%) and clean water according to a mass ratio of 1:2.5, continuously adding the materials into a slurry making tank, stirring to obtain mixed slurry, continuously stirring the slurry in a rapid reaction tank, continuously adding 50% sulfuric acid, controlling the leaching pH value of the slurry to be 2.9 +/-0.1, keeping the time for 15min, then flowing the slurry into a rotary continuous leaching device, wherein the rotary device is provided with 4 compartments and rotates at 40rpm, continuously adding 40% sulfuric acid to ensure that the leaching pH value of the slurry is 2.8 +/-0.05, keeping the time for 50min, performing solid-liquid separation on the discharged leached slurry to obtain an acidic vanadium-containing solution TV of 32.33g/L, washing residues with a sulfuric acid solution of which the pH value is 2.8 to obtain residues TV of 1.18%, and calculating to obtain the vanadium leaching rate of 96.56%.

Example 3

Calcified roasted clinker (7.99% TV, V)⁵⁺7.12%) and clean water are continuously added into a slurry making tank according to the mass ratio of 1:4, mixed slurry is obtained by stirring, the slurry flows into a rapid reaction tank to be continuously stirred, 55% of sulfuric acid is continuously added, the leaching pH value of the slurry is controlled to be 3.0 +/-0.1, the retention time is 30min, the slurry flows into a rotary continuous leaching device, the rotary device is provided with 4 compartments and rotates at 15rpm, 40% of sulfuric acid is continuously added to ensure that the leaching pH value of the slurry is 2.8 +/-0.05, the retention time is 80min, the discharged leached slurry is subjected to solid-liquid separation to obtain 23.88g/L of acidic vanadium-containing solution TV, the residue is washed by using a sulfuric acid solution with the pH value of 3.0 to obtain 1.17% of residue, and the leaching rate of vanadium is calculated to be 96.94%.

The invention adopts continuous acid leaching process and equipment to perform laboratory test verification on the clinker obtained by calcifying and roasting vanadium slag, and the result shows that the leaching efficiency can be greatly improved by implementing continuous leaching, and the leaching rate of vanadium in the clinker can be stabilized to be more than 96%. If the technology is implemented on the production line of the new clean production process applied by the applicant, the on-site leaching production can be realized by simple technology modification, so that the on-site leaching production efficiency is improved. The technology is simple and easy to implement, the field process flow has strong feasibility, and the application prospect is very wide.