CN114350982B - Method for extracting vanadium and recycling leaching washing liquid by calcified roasting clinker - Google Patents
Method for extracting vanadium and recycling leaching washing liquid by calcified roasting clinker Download PDFInfo
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Abstract
The invention relates to the technical field of wet metallurgy of vanadium, and discloses a method for extracting vanadium from calcified roasting clinker and recycling leaching washing liquid. The method comprises the following steps: (1) Mixing and pulping the calcified roasting clinker with a pulping mother liquor, adding a leaching agent, and carrying out primary leaching to obtain vanadium-containing leaching solution and primary residues; (2) Washing the first-stage residues to obtain first-time washing filtrate and first-time washing residues; (3) Washing the first washing residues to obtain second washing filtrate and second washing residues, wherein the second washing filtrate is used as pulping mother liquor for recycling; (4) Adding the second washing residue into a second leaching agent for second leaching to obtain a second leaching solution and second residue; (5) Washing the second-stage residues to obtain a third washing filtrate and vanadium extraction tailings; (6) And mixing the secondary leaching solution and the third washing filtrate to obtain a secondary leaching mixed solution, wherein the secondary leaching mixed solution is used as a leaching agent for recycling. The method is simple and easy to use, and has high social and economic benefits.
Description
Technical Field
The invention relates to the technical field of wet metallurgy of vanadium, in particular to a method for extracting vanadium from calcified roasting clinker and recycling leaching washing liquid.
Background
The calcification roasting-acid leaching vanadium-extracting process of vanadium slag is to take calcium salt as additive, roasting the vanadium slag in high temperature oxidizing atmosphere to oxidize low-valence vanadium into pentavalent vanadium, generating water insoluble but acid soluble calcium vanadate, leaching the calcium vanadate into dilute sulfuric acid solution to obtain vanadium-containing solution, removing impurities and precipitating vanadium to obtain vanadium pentoxide product, and the vanadium precipitating wastewater can be returned for use after simple treatment.
After calcification roasting of the vanadium slag, vanadium in the slag has been substantially converted to pentavalent vanadate and is mainly present in vanadate, ferric oxide solid solution, pseudobrookite and silicate. Phase studies have shown that vanadium in the vanadate phase can be substantially completely dissolved during a single leaching (ph=2.8-3.5), whereas the dissolution rate of vanadium in iron oxide solid solutions, pseudobrookites and silicates is low. The residue after primary leaching is subjected to low-pH secondary leaching (or called deep leaching), so that solid solution of ferric oxide and pseudobrookite phases can be effectively destroyed, vanadium in the solid solution is dissolved, and the dissolution rate of the vanadium is improved. However, the reduction of leaching pH increases the dissolution rate of impurities such as iron and phosphorus in the slag, and simultaneously involves the problem of economical and effective utilization of secondary low-vanadium high-impurity solution.
Patent CN 109338103B discloses a method for extracting vanadium by countercurrent acid leaching of calcified roasting clinker, which realizes the gradual leaching of vanadium by controlling the pH value of the three-stage leaching process or the leaching end point to be 2.8-3.5, 1.8-3.5 and 0.7-1.5 respectively; and then the leaching washing filtrate of each stage is returned to the previous stage to realize the utilization of the low-concentration vanadium-containing solution. The method can effectively improve the leaching rate of vanadium (reaching more than 90 percent), but has more process control points (the leaching pH of each stage, the filtrate pH and the vanadium concentration need to be controlled), the three-stage leaching needs to be controlled to be between 0.7 and 1.5, and the final leaching liquid pH is between 1.4 and 2.2, and is difficult to realize in actual operation.
Disclosure of Invention
The invention aims to solve the problem of poor vanadium extraction effect of vanadium slag in the prior art, and provides a method for extracting vanadium and recycling leaching washing liquid by using calcified roasting clinker.
In order to achieve the above object, the present invention provides a method for extracting vanadium and recycling leaching washing liquid by using calcified roasting clinker, the method comprising the steps of:
(1) Mixing calcified roasting clinker with pulping mother liquor, pulping, adding a leaching agent for primary leaching, controlling the pH value of a system in the primary leaching process to be 2.8-3.5, and filtering after the primary leaching is finished to obtain vanadium-containing leaching solution and primary residues; wherein the liquid-solid ratio of the beating mother liquor to the calcified roasting clinker is 0.6-3mL/g, and the liquid-solid ratio of the leaching agent to the calcified roasting clinker is 1-2mL/g;
(2) Washing the primary residue obtained in the step (1) by adopting a washing liquid to obtain a primary washing filtrate and a primary washing residue;
(3) Washing the first washing residues obtained in the step (2) by adopting a washing liquid to obtain a second washing filtrate and second washing residues, and returning the second washing filtrate as pulping mother liquor to the step (1) for recycling;
(4) Adding the second washing residue obtained in the step (3) into a second leaching agent for second leaching, controlling the pH value of a system in the second leaching process to be 0.8-1, and filtering after the second leaching is finished to obtain second leaching liquid and second residue;
(5) Washing the secondary residue obtained in the step (4) by adopting a washing liquid to obtain a third washing filtrate and vanadium extraction tailings;
(6) Mixing the secondary leaching solution obtained in the step (4) with the third washing filtrate obtained in the step (5) to obtain a secondary leaching mixed solution, and returning the secondary leaching mixed solution as a leaching agent to the step (1) for recycling;
wherein in step (2), the liquid-solid ratio of the washing liquid to the calcified calcined clinker is 0.1-0.4mL/g;
in the step (3), the liquid-solid ratio of the washing liquid to the calcified roasting clinker is 0.6-3mL/g.
Preferably, in the step (1), the calcified calcined clinker has a vanadium content of 5-15 wt% and a phosphorus content of 0.1 wt% or less.
Preferably, in step (1), the calcified clinker has a particle size of < 0.125mm.
Preferably, in step (1), the primary leaching time is 40-90min.
Preferably, in step (1), the temperature of the primary leach is in the range 20-60 ℃.
Preferably, in step (4), the liquid to solid ratio of the secondary leaching agent to the second wash residue is from 0.6 to 1mL/g.
Preferably, in step (4), the time of the secondary leaching is 5-30min.
Preferably, in step (4), the temperature of the secondary leach is in the range 20-50 ℃.
Preferably, in step (5), the liquid-solid ratio of the washing liquid to the calcified calcined clinker is 0.4-1mL/g.
Preferably, the washing liquid and the secondary leaching agent are both aqueous solutions with the pH value of 2-9 and the P content less than or equal to 0.03 g/L.
The method has the advantages of simple and easy process, wide application range, low cost and high social and economic benefits.
Drawings
FIG. 1 is a process flow diagram of the calcified roasting clinker vanadium extraction and leaching wash liquor recycling of the invention.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for extracting vanadium and recycling leaching washing liquid by using calcified roasting clinker, the process flow chart of which is shown in figure 1, and the method comprises the following steps:
(1) Mixing calcified roasting clinker with pulping mother liquor, pulping, adding a leaching agent for primary leaching, controlling the pH value of a system in the primary leaching process to be 2.8-3.5, and filtering after the primary leaching is finished to obtain vanadium-containing leaching solution and primary residues; wherein the liquid-solid ratio of the beating mother liquor to the calcified roasting clinker is 0.6-3mL/g, and the liquid-solid ratio of the leaching agent to the calcified roasting clinker is 1-2mL/g;
(2) Washing the primary residue obtained in the step (1) by adopting a washing liquid to obtain a primary washing filtrate and a primary washing residue;
(3) Washing the first washing residues obtained in the step (2) by adopting a washing liquid to obtain a second washing filtrate and second washing residues, and returning the second washing filtrate as pulping mother liquor to the step (1) for recycling;
(4) Adding the second washing residue obtained in the step (3) into a second leaching agent for second leaching, controlling the pH value of a system in the second leaching process to be 0.8-1, and filtering after the second leaching is finished to obtain second leaching liquid and second residue;
(5) Washing the secondary residue obtained in the step (4) by adopting a washing liquid to obtain a third washing filtrate and vanadium extraction tailings;
(6) Mixing the secondary leaching solution obtained in the step (4) with the third washing filtrate obtained in the step (5) to obtain a secondary leaching mixed solution, and returning the secondary leaching mixed solution as a leaching agent to the step (1) for recycling;
wherein in step (2), the liquid-solid ratio of the washing liquid to the calcified calcined clinker is 0.1-0.4mL/g;
in the step (3), the liquid-solid ratio of the washing liquid to the calcified roasting clinker is 0.6-3mL/g.
In the invention, in the step (1), the calcified roasting clinker is obtained by calcified high-temperature roasting of vanadium slag generated in the vanadium extraction process of the vanadium-containing molten iron converter.
In a preferred embodiment, the calcified clinker has a vanadium content of 5-15 wt.% and a phosphorus content of 0.1 wt.% or less. Specifically, the content of vanadium in the calcified calcined clinker may be 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% or 15 wt%.
In a preferred embodiment, the calcified clinker has a particle size of < 0.125mm.
In a specific embodiment, in the step (1), the pulping mother liquor is an acidic aqueous solution with a pH value of 2-6 and a P content of less than 0.08 g/L.
In a specific embodiment, in the step (1), the leaching agent is an acidic aqueous solution with a pH value of 0.8-6, a P content of less than 1g/L and a Fe content of less than 5 g/L.
In the invention, in the step (1), the pulping mother liquor can be obtained by lime neutralization treatment of wastewater generated in the vanadium precipitation process of the vanadium slag calcification roasting-acid leaching vanadium process, and can also be obtained from APV washing filtrate, so long as the pH value is 2-6, and the P content is less than 0.08g/L of acidic aqueous solution.
In the invention, in the step (1), the leaching agent can be obtained by lime neutralization treatment of wastewater generated in the vanadium precipitation process of the vanadium slag calcification roasting-acid leaching vanadium process, and can also be obtained from APV washing filtrate, so long as the pH value is 0.8-6, the P content is less than 1g/L, and the Fe content is less than 5 g/L.
In particular embodiments, in step (1), the liquid-to-solid ratio of the beating mother liquor and the calcified calcined clinker may be 0.6mL/g, 0.8mL/g, 1mL/g, 1.2mL/g, 1.4mL/g, 1.6mL/g, 1.8mL/g, 2mL/g, 2.2mL/g, 2.4mL/g, 2.6mL/g, 2.8mL/g, or 3mL/g.
In particular embodiments, in step (1), the liquid to solid ratio of the leaching agent to the calcified calcined clinker may be 1mL/g, 1.1mL/g, 1.2mL/g, 1.3mL/g, 1.4mL/g, 1.5mL/g, 1.6mL/g, 1.7mL/g, 1.8mL/g, 1.9mL/g, or 2mL/g.
In the invention, in the step (1), sulfuric acid is adopted to control the pH value of the system in the primary leaching process to be 2.8-3.5.
In particular embodiments, in step (1), the pH of the system during the primary leaching may be 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4 or 3.5.
Preferably, in step (1), the primary leaching time is 40-90min. Specifically, the primary leaching time may be 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min or 90min.
Preferably, in step (1), the temperature of the primary leach is in the range 20-60 ℃.
In the invention, the vanadium-containing leaching solution obtained in the step (1) is used for preparing a vanadium product by carrying out subsequent vanadium precipitation.
In particular embodiments, in step (2), the liquid to solid ratio of the wash liquor to the calcified calcined clinker may be 0.1mL/g, 0.2mL/g, 0.22mL/g, 0.24mL/g, 0.26mL/g, 0.28mL/g, 0.3mL/g, 0.32mL/g, 0.34mL/g, 0.36mL/g, 0.38mL/g, or 0.4mL/g.
In the invention, the first washing filtrate obtained in the step (2) is used for preparing a vanadium product through subsequent vanadium precipitation.
In particular embodiments, in step (3), the liquid-to-solid ratio of the wash liquor to the calcified calcined clinker may be 0.6mL/g, 0.8mL/g, 1mL/g, 1.2mL/g, 1.4mL/g, 1.6mL/g, 1.8mL/g, 2mL/g, 2.2mL/g, 2.4mL/g, 2.6mL/g, 2.8mL/g, or 3mL/g.
Preferably, in step (4), the liquid-to-solid ratio of the secondary leaching agent to the calcified calcined clinker is 0.6-1mL/g. Specifically, the liquid-to-solid ratio of the secondary leaching agent to the calcified calcined clinker may be 0.6mL/g, 0.7mL/g, 0.8mL/g, 0.82mL/g, 0.84mL/g, 0.86mL/g, 0.88mL/g, 0.9mL/g, 0.92mL/g, 0.94mL/g, 0.96mL/g, 0.98mL/g, or 1mL/g.
In particular embodiments, in step (4), the pH of the system during the secondary leaching may be 0.8, 0.82, 0.84, 0.86, 0.88, 0.9, 0.92, 0.94, 0.96, 0.98 or 1.
Preferably, in step (4), the time of the secondary leaching is 5-30min. Specifically, the secondary leaching time may be 5min, 10min, 15min, 20min, 25min or 30min.
Preferably, in step (4), the temperature of the secondary leach is in the range 20-50 ℃.
Preferably, in step (5), the liquid-solid ratio of the washing liquid to the calcified calcined clinker is 0.4-1mL/g. Specifically, the liquid-to-solid ratio of the wash solution to the calcified clinker may be 0.4mL/g, 0.5mL/g, 0.6mL/g, 0.7mL/g, 0.8mL/g, 0.9mL/g, or 1mL/g.
In the invention, the washing liquid in the step (2), the step (3) and the step (5) and the secondary leaching agent in the step (4) are all aqueous solutions with pH value of 2-9 and P content less than or equal to 0.03 g/L.
In the invention, the washing liquid in the step (2), the step (3) and the step (5) and the secondary leaching agent in the step (4) can be obtained by lime neutralization treatment of wastewater generated in the vanadium precipitation process of the vanadium slag calcification roasting-acid leaching vanadium process, and can also be obtained from APV washing filtrate, so long as the pH value is 2-9 and the P content is less than or equal to 0.03 g/L.
In the invention, in the step (6), when P is more than 1g/L and/or Fe is more than 5g/L in the secondary leaching mixed solution, the circulation is stopped, the pH value of the secondary leaching mixed solution is adjusted to 2.2-3.5 for impurity removal, and the impurity removal solution is returned to the step (1) for use as a leaching agent after solid-liquid separation.
In the invention, lime milk and/or ammonia water can be used to adjust the pH of the secondary leaching mixed solution to 2.2-3.5.
Compared with the prior art, the method has the following beneficial effects:
(1) The washing filtrate and the leaching mixed liquor are recycled, the second washing filtrate is used as beating mother liquor to beat the calcified roasting clinker containing vanadium, the second leaching mixed liquor is used as a leaching agent to leach, and the pH value in the leaching process is controlled, on one hand, the solid ratio of the leaching liquor can be improved by adding the second washing filtrate, and the phenomenon of vanadium precipitation caused by difficult diffusion of hydrogen ions in the leaching process due to thick slurry is avoided; on the other hand, the secondary leaching mixed solution has low pH value, low vanadium concentration and high content of iron and phosphorus impurities, and is used as a leaching agent, and the pH value in the leaching process is controlled to be 2.8-3.5, so that the generation and precipitation of the iron and phosphorus impurities are prevented from entering the high-concentration leaching solution, and the recycling of the low-pH and low-vanadium-containing solution is realized.
(2) The primary residue was washed twice: firstly, adopting a low liquid-solid ratio of 0.1-0.4mL/g to carry out first washing, and replacing high-concentration vanadium liquid remained in residues into first washing filtrate to obtain high-concentration vanadium-containing washing filtrate which can be directly used for subsequent precipitation and vanadium recovery; then adopting a liquid-solid ratio of 0.6-3mL/g to carry out secondary washing to obtain a low-concentration vanadium-containing secondary washing filtrate which is used as pulping mother liquor for pulping the vanadium-containing calcified roasting clinker; the vanadium entrained in the residue is simply and effectively distributed to the high-concentration filtrate in the washing process, so that the vanadium in the residue is prevented from circulating in the leaching system.
The method has the advantages of simple and easy use process, wide application range, low cost, good vanadium extraction effect and high social and economic benefits.
The present invention will be described in detail by examples. The method of the present invention is not limited thereto.
The yield calculations of vanadium in the examples and comparative examples are:
yield of vanadium = (1-vanadium content in residue weight/(vanadium content in clinker weight) clinker) 100%
Example 1
(1) Mixing 500g of calcified roasting clinker (the content of vanadium is 9.15 wt%, the content of P is 0.04 wt%) with pulping mother liquor (the pulping mother liquor is an acidic aqueous solution with the pH value of 3 and the content of P is 0.03 g/L), controlling the liquid-solid ratio of the pulping mother liquor and the calcified roasting clinker to be 0.8mL/g, pulping, slowly adding a leaching agent (the leaching agent is an acidic aqueous solution with the pH value of 3, the content of P is 0.07g/L and the content of Fe is 0.05 g/L) under stirring, controlling the liquid-solid ratio of the leaching agent and the calcified roasting clinker to be 1.6mL/g, performing primary leaching, controlling the pH value of a system in the primary leaching process to be 3 by sulfuric acid, controlling the primary leaching time to be 60min, and filtering after the primary leaching is finished to obtain a leaching solution containing vanadium (the concentration of 31.7g/L, P content of 0.02g/L, pH value of 3.14) and primary residues, wherein the leaching solution containing vanadium can be used for preparing a product containing vanadium by subsequent vanadium precipitation;
(2) Washing the primary residue obtained in the step (1) by adopting an aqueous solution with a pH value of 3.0 and a P content of 0.03g/L, wherein the liquid-solid ratio of the aqueous solution to calcified roasting clinker is 0.4mL/g, and obtaining a first washing filtrate (the vanadium concentration is 22.4g/L, P and the P content is 0.02g/L, pH and 3.2) and a first washing residue, wherein the first washing filtrate can be used for preparing vanadium products by subsequent vanadium precipitation;
(3) Washing the first washing residue obtained in the step (2) by adopting an aqueous solution with the pH value of 3.0 and the P content of 0.03g/L, wherein the liquid-solid ratio of the aqueous solution to calcified roasting clinker is 0.8mL/g, obtaining a second washing filtrate (the vanadium concentration is 4.8g/L, P, the content is more than 0.01g/L, pH, and the value is 3.3) and the second washing residue, and returning the second washing filtrate as pulping mother liquor to the step (1) for recycling;
(4) Adding the second washing residue obtained in the step (3) into an aqueous solution with the pH value of 3.0 and the P content of 0.03g/L, wherein the liquid-solid ratio of the aqueous solution to calcified roasting clinker is 1mL/g, performing secondary leaching, controlling the pH value of a system in the secondary leaching process to be 0.8 by adopting sulfuric acid, the secondary leaching time to be 10min, and filtering after the secondary leaching is finished to obtain a secondary leaching solution and a secondary residue, wherein the temperature of the secondary leaching solution is 25-35 ℃;
(5) Washing the secondary residue obtained in the step (4) by adopting an aqueous solution with a pH value of 3.0 and a P content of 0.03g/L, wherein the liquid-solid ratio of the aqueous solution to calcified roasting clinker is 0.6mL/g, and obtaining a third washing filtrate and vanadium extraction tailings (dry weight 468.3g, TV 0.85 wt%, P0.02 wt%), and the yield of vanadium is 91.3%;
(6) Mixing the secondary leaching solution obtained in the step (4) with the third washing filtrate obtained in the step (5) to obtain a secondary leaching mixed solution (the concentration of vanadium is 2.3g/L, the concentration of P is 0.12g/L, the concentration of Fe is 0.38g/L, and the pH value is 0.82), and returning the secondary leaching mixed solution as a leaching agent to the step (1) for recycling;
after 14 times of circulation in the embodiment, the content of P in the secondary leaching mixed liquor is 1.58g/L, fe and 3.53g/L, and the circulation is stopped; adding lime milk into the secondary leaching mixed solution under the condition of stirring, regulating the pH value to 2.5, stirring and reacting for 30min to remove impurities, and then carrying out solid-liquid separation to obtain an impurity-removing solution (the V content is 2.2g/L, P content is 0.048g/L, fe content is 0.084g/L, pH value is 2.55), wherein the impurity-removing solution can be continuously returned to the step (1) for recycling.
In this example, 7000g of calcified-calcined clinker (9.15 wt% of vanadium and 0.04 wt% of P) having a particle size of < 0.125mm was used in total for 14 cycles, and 6566g of vanadium extraction tailings (0.89 wt% of TV and 0.02 wt% of P) were obtained in total, and the total yield of vanadium was 90.9%.
Example 2
(1) Mixing 500g of calcified roasting clinker (the content of vanadium is 9.15 wt%, the content of P is 0.04 wt%) with pulping mother liquor (the pulping mother liquor is an acidic aqueous solution with the pH value of 3 and the content of P is 0.05 g/L), controlling the liquid-solid ratio of the pulping mother liquor and the calcified roasting clinker to be 0.8mL/g, pulping, slowly adding a leaching agent (the leaching agent is an acidic aqueous solution with the pH value of 3, the content of P is 0.05g/L and the content of Fe is 0.03 g/L) under stirring, controlling the liquid-solid ratio of the leaching agent and the calcified roasting clinker to be 1.6mL/g, performing primary leaching, controlling the pH value of a system in the primary leaching process to be 2.8 by sulfuric acid, controlling the primary leaching time to be 40min, and filtering after the primary leaching is finished to obtain a leaching solution containing vanadium (the concentration of 32.6g/L, P content of 0.03g/L, pH value of 2.92) and primary residues, wherein the leaching solution containing vanadium can be used for preparing a product containing vanadium after the subsequent vanadium precipitation;
(2) Washing the primary residue obtained in the step (1) by adopting an acidic aqueous solution with a pH value of 4 and a P content of 0.01g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 0.4mL/g, and obtaining a first washing filtrate (the vanadium concentration is 26.2g/L, P and the P content is 0.02g/L, pH and the value is 2.97) and a first washing residue, wherein the first washing filtrate can be used for preparing vanadium products by subsequent vanadium precipitation;
(3) Washing the first washing residue obtained in the step (2) by adopting an acidic aqueous solution with a pH value of 4 and a P content of 0.01g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 0.8mL/g, obtaining a second washing filtrate (vanadium concentration is 3.2g/L, P, the content is 0.01g/L, pH, and the value is 3.05) and the second washing residue, and returning the second washing filtrate as pulping mother liquor to the step (1) for recycling;
(4) Adding the second washing residue obtained in the step (3) into an acidic aqueous solution with the pH value of 4 and the P content of 0.01g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 1mL/g, performing secondary leaching, controlling the pH value of a system in the secondary leaching process to be 0.8 by adopting sulfuric acid, the secondary leaching time to be 5min, and filtering after the secondary leaching is finished to obtain a secondary leaching solution and a secondary residue, wherein the temperature of the secondary leaching solution is 25-35 ℃;
(5) Washing the secondary residue obtained in the step (4) by adopting an aqueous solution with a pH value of 8 and a P content of 0.01g/L, wherein the liquid-solid ratio of the aqueous solution to calcified roasting clinker is 0.6mL/g, and obtaining a third washing filtrate and vanadium extraction tailings (dry weight of 469.5g, TV of 0.84 wt%, P of 0.02 wt%), and the yield of vanadium of 91.4%;
(6) Mixing the secondary leaching solution obtained in the step (4) with the third washing filtrate obtained in the step (5) to obtain a secondary leaching mixed solution (the concentration of vanadium is 2.4g/L, the concentration of P is 0.11g/L, the concentration of Fe is 0.40g/L, and the pH value is 0.83), and returning the secondary leaching mixed solution as a leaching agent to the step (1) for recycling;
after 16 times of circulation in the embodiment, the content of P in the secondary leaching mixed liquor is 1.64g/L, fe and 5.21g/L, and the circulation is stopped; adding lime milk into the secondary leaching mixed solution under the condition of stirring, regulating the pH value to 2.5, stirring and reacting for 30min to remove impurities, and then carrying out solid-liquid separation to obtain an impurity-removing solution (V content is 2.1g/L, P content is 0.04g/L, fe content is 0.067g/L, pH value is 2.58), wherein the impurity-removing solution can be continuously returned to the step (1) for recycling.
In this example, 8000g of calcified-calcined clinker (9.15 wt% of vanadium, 0.04 wt% of P) having a particle size of < 0.125mm was used 16 times in total, and a total yield of 91.0% of vanadium was obtained, which was 7510g of vanadium extraction tailings (0.88 wt% of TV, 0.02 wt% of P) having a dry weight.
Example 3
(1) Mixing 500g of calcified roasting clinker (the content of vanadium is 8.48 wt%, the content of P is 0.08 wt%) with pulping mother liquor (the pulping mother liquor is an acidic aqueous solution with the pH value of 3 and the content of P is 0.06 g/L), controlling the liquid-solid ratio of the pulping mother liquor and the calcified roasting clinker to be 0.6mL/g, pulping, slowly adding a leaching agent (the leaching agent is an acidic aqueous solution with the pH value of 3, the content of P is 0.06g/L and the content of Fe is 0.02 g/L) under stirring, controlling the liquid-solid ratio of the leaching agent and the calcified roasting clinker to be 2mL/g, performing primary leaching, controlling the pH value of a system in the primary leaching process to be 3.2 by sulfuric acid, controlling the primary leaching time to be 70min, filtering after the primary leaching is finished to obtain a leaching solution containing vanadium (the concentration of 27.8g/L, P content of 0.02g/L, pH value of 3.26) and primary residues, wherein the leaching solution containing vanadium can be used for preparing a product containing vanadium by subsequent vanadium precipitation;
(2) Washing the primary residue obtained in the step (1) by adopting an acidic aqueous solution with a pH value of 3 and a P content of 0.02g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 0.3mL/g, and obtaining a first washing filtrate (the vanadium concentration is 25.6g/L, P and the P content is 0.02g/L, pH and 3.15) and a first washing residue, wherein the first washing filtrate can be used for preparing vanadium products by subsequent vanadium precipitation;
(3) Washing the first washing residue obtained in the step (2) by adopting an acidic aqueous solution with a pH value of 3 and a P content of 0.02g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 0.6mL/g, obtaining a second washing filtrate (vanadium concentration is 5.2g/L, P, the content is 0.02g/L, pH, and the value is 3.05) and the second washing residue, and returning the second washing filtrate as pulping mother liquor to the step (1) for recycling;
(4) Adding the second washing residue obtained in the step (3) into an acidic aqueous solution with the pH value of 3 and the P content of 0.02g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 1mL/g, performing secondary leaching, controlling the pH value of a system in the secondary leaching process to be 0.9 by adopting sulfuric acid, controlling the secondary leaching time to be 15min, and filtering after the secondary leaching is finished at the temperature of 25-35 ℃ to obtain secondary leaching liquid and secondary residue;
(5) Washing the secondary residue obtained in the step (4) by adopting an acidic aqueous solution with a pH value of 6 and a P content of 0.02g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 1mL/g, and obtaining a third washing filtrate and vanadium extraction tailings (dry weight 449g, TV of 0.65 wt%, and P of 0.03 wt%), and the yield of vanadium of 93.1%;
(6) Mixing the secondary leaching solution obtained in the step (4) with the third washing filtrate obtained in the step (5) to obtain a secondary leaching mixed solution (the concentration of vanadium is 2.2g/L, the concentration of P is 0.19g/L, the concentration of Fe is 0.54g/L, and the pH value is 0.95), and returning the secondary leaching mixed solution as a leaching agent to the step (1) for recycling;
after 9 times of circulation in the embodiment, the content of P in the secondary leaching mixed liquor is 1.71g/L, fe and 4.84g/L, and the circulation is stopped; adding lime milk into the secondary leaching mixed solution under the condition of stirring, regulating the pH value to 3, stirring and reacting for 30min to remove impurities, and then carrying out solid-liquid separation to obtain an impurity-removing solution (V content is 2.1g/L, P content is 0.03g/L, fe content is 0.031g/L, pH value is 3.05), wherein the impurity-removing solution can be continuously returned to the step (1) for recycling.
In this example, 4500g of calcified-calcined clinker with a particle size of < 0.125mm (vanadium content 8.48 wt%, P content 0.08 wt%) was used in total 9 cycles, yielding a total yield of 92.5% of vanadium with a dry weight of 4050g of vanadium extraction tailings (0.71 wt% TV, 0.03 wt% P).
Example 4
(1) Mixing 500g of calcified roasting clinker (the content of vanadium is 10.68 wt%, the content of P is 0.04 wt%) with pulping mother liquor (the pulping mother liquor is an acidic aqueous solution with the pH value of 3 and the content of P is 0.05 g/L), controlling the liquid-solid ratio of the pulping mother liquor and the calcified roasting clinker to be 1.6mL/g, pulping, slowly adding a leaching agent (the leaching agent is an acidic aqueous solution with the pH value of 3, the content of P is 0.05g/L and the content of Fe is 0.02 g/L) under stirring, controlling the liquid-solid ratio of the leaching agent and the calcified roasting clinker to be 1.6mL/g, performing primary leaching, controlling the pH value of a system in the primary leaching process to be 3.5 by sulfuric acid, controlling the primary leaching time to be 90min, and filtering after the primary leaching is finished to obtain a leaching solution containing vanadium (the concentration of 28.5g/L, P content of 0.01g/L, pH value to be 3.62) and primary residues, wherein the leaching solution containing vanadium can be used for preparing a product containing vanadium after the subsequent vanadium precipitation;
(2) Washing the primary residue obtained in the step (1) by adopting an acidic aqueous solution with a pH value of 2 and a P content of 0.01g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 0.3mL/g, and obtaining a first washing filtrate (the vanadium concentration is 26.9g/L, P and the P content is 0.01g/L, pH and 3.38) and a first washing residue, wherein the first washing filtrate can be used for preparing vanadium products by subsequent vanadium precipitation;
(3) Washing the first washing residue obtained in the step (2) by adopting an acidic aqueous solution with a pH value of 2 and a P content of 0.01g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 1.6mL/g, obtaining a second washing filtrate (vanadium concentration is 3.2g/L, P, the content is 0.01g/L, pH, and the value is 2.81) and the second washing residue, and returning the second washing filtrate as pulping mother liquor to the step (1) for recycling;
(4) Adding the second washing residue obtained in the step (2) into an acidic aqueous solution with the pH value of 2 and the P content of 0.01g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 1mL/g, performing secondary leaching, controlling the pH value of a system in the secondary leaching process to be 1 by adopting sulfuric acid, the secondary leaching time to be 20min, and filtering after the secondary leaching is finished to obtain a secondary leaching solution and a secondary residue, wherein the temperature of the secondary leaching solution is 25-30 ℃;
(5) Washing the secondary residue obtained in the step (4) by adopting an acidic aqueous solution with a pH value of 6 and a P content of 0.01g/L, wherein the liquid-solid ratio of the acidic aqueous solution to calcified roasting clinker is 0.6mL/g, and obtaining a third washing filtrate and vanadium extraction tailings (dry weight 449g, TV of 0.90 wt%, P of 0.02 wt%), and the yield of vanadium of 92.1%;
(6) Mixing the secondary leaching solution obtained in the step (4) with the third washing filtrate obtained in the step (5) to obtain a secondary leaching mixed solution (the concentration of vanadium is 3.1g/L, the concentration of P is 0.09g/L, the concentration of Fe is 0.41g/L, and the pH value is 1.1), and returning the secondary leaching mixed solution as a leaching agent to the step (1) for recycling;
after 18 times of circulation in the embodiment, the content of P in the secondary leaching mixed liquor is 1.62g/L, fe and 5.34g/L, and the circulation is stopped; adding lime milk into the secondary leaching mixed solution under the condition of stirring, regulating the pH value to 3, stirring and reacting for 30min to remove impurities, and then carrying out solid-liquid separation to obtain an impurity-removing solution (V content is 2.8g/L, P content is 0.04g/L, fe content is 0.039g/L, pH value is 3.03), wherein the impurity-removing solution can be continuously returned to the step (1) for recycling.
In this example, 9000g of calcified-calcined clinker having a particle size of < 0.125mm (vanadium content: 10.68% by weight, P content: 0.04% by weight) was used in total for 18 cycles, and 8370g of vanadium-extracted tailings (TV: 0.94% by weight, P content: 0.01% by weight) were obtained in total, and the total yield of vanadium was 91.8%.
Comparative example 1
The existing method for extracting vanadium by using calcified roasting clinker comprises the following steps:
(1) Taking 500g of calcified clinker (the vanadium content is 9.15 wt% and the P content is 0.04 wt%) and adding 1250mL of leaching mother liquor (water) for mixing and pulping, then adding sulfuric acid to adjust the pH of the system to 3.0, carrying out acid leaching reaction at normal temperature for 60min, and carrying out solid-liquid separation to obtain leaching liquid (containing 31.7g/L of vanadium) and residues to be washed;
(2) The residue to be washed is washed by adopting 1250mL of acid aqueous solution with pH value of 3 and P content of 0.01g/L, so as to obtain washing filtrate (containing 10.1g/L of vanadium and volume of 1250 mL) and 460g of vanadium extraction tailings (TV is 1.21 wt%) and the yield of vanadium is 87.8%, and the washing filtrate is returned to the step (1) to be recycled as leaching mother liquor.
The comparative example was circulated 14 times by using 7000g of calcified-calcined clinker (vanadium content 9.15 wt%, P content 0.04 wt%) having a particle size of < 0.125mm, and a total yield of vanadium was 87.6% by dry weight of 6440g of vanadium-extracted tailings (TV 1.23 wt%, P content 0.03 wt%).
Comparative example 2
The process described in example 2 was carried out, except that in step (1), the pH of the system during the primary leaching was controlled to be 2;
467g of vanadium extraction tailings (TV 0.83 wt%) are obtained in step (5) of this comparative example, and the yield of vanadium is 91.5%;
when the vanadium-containing leaching solution in the step (1) is recycled to the 2 nd time in the comparative example, the P content of the vanadium-containing leaching solution is 0.18g/L, the vanadium-containing leaching solution cannot be directly used for preparing vanadium products (the P content is higher, phosphorus removal is needed) by subsequent vanadium precipitation, and meanwhile, the precipitation phenomenon of vanadium occurs when the vanadium-containing leaching solution is placed for 10 hours due to the lower pH.
At the 3 rd recycle in this comparative example, 470g of vanadium extraction tailings (TV 1.14 wt%) were obtained in step (5), this time with a vanadium yield of 88.3%;
when recycled to the 5 th time in this comparative example, 472g of vanadium extraction tailings (TV 1.34 wt%) were obtained in the step (5), and the vanadium yield was 86.2%.
When the pH value of the vanadium extraction system is low, along with the extension of the leaching time and the standing time of the leaching liquid, the precipitation phenomenon of vanadium possibly exists, so that the vanadium yield is reduced (high-concentration vanadium cannot be stored for a long time under the condition of low pH value, and hydrolysis and precipitation can occur); meanwhile, when the pH value is low, a large amount of P in clinker can enter the solution, and the content of P in the obtained leaching solution is increased, so that the subsequent further recovery of vanadium from the leaching solution is seriously influenced.
From the results, the calcified vanadium extraction clinker can greatly improve the yield of vanadium through secondary low-pH acid leaching, but the secondary leaching solution obtained in the secondary low-pH acid leaching process has the characteristics of low pH, low vanadium and high impurity, and is difficult to directly recycle. The invention returns the secondary leaching mixed liquor which is difficult to be directly recycled as an acidity regulator/leaching agent to the primary leaching of the vanadium-containing clinker, recycles vanadium resources and dilute acid in the secondary leaching liquor, and simultaneously controls the pH value of the leaching process to be 2.8-3.5 so that impurities such as iron and phosphorus in the secondary leaching mixed liquor enter primary residues to obtain the low-phosphorus leaching liquor which can be directly used for subsequent vanadium precipitation. The whole process fully extracts and recovers vanadium in the clinker, has high vanadium yield and low cost, and has high social and economic benefits.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (7)
1. A method for extracting vanadium from calcified roasting clinker and recycling leaching washing liquid, which is characterized by comprising the following steps:
(1) Mixing calcified roasting clinker with pulping mother liquor, pulping, adding a leaching agent for primary leaching, controlling the pH value of a system in the primary leaching process to be 2.8-3.5, and filtering after the primary leaching is finished to obtain vanadium-containing leaching solution and primary residues; wherein the liquid-solid ratio of the beating mother liquor to the calcified roasting clinker is 0.6-3mL/g, and the liquid-solid ratio of the leaching agent to the calcified roasting clinker is 1-2mL/g;
(2) Washing the primary residue obtained in the step (1) by adopting a washing liquid to obtain a primary washing filtrate and a primary washing residue;
(3) Washing the first washing residues obtained in the step (2) by adopting a washing liquid to obtain a second washing filtrate and second washing residues, and returning the second washing filtrate as pulping mother liquor to the step (1) for recycling;
(4) Adding the second washing residue obtained in the step (3) into a second leaching agent for second leaching, controlling the pH value of a system in the second leaching process to be 0.8-1, and filtering after the second leaching is finished to obtain second leaching liquid and second residue;
(5) Washing the secondary residue obtained in the step (4) by adopting a washing liquid to obtain a third washing filtrate and vanadium extraction tailings;
(6) Mixing the secondary leaching solution obtained in the step (4) with the third washing filtrate obtained in the step (5) to obtain a secondary leaching mixed solution, and returning the secondary leaching mixed solution as a leaching agent to the step (1) for recycling;
wherein in step (2), the liquid-solid ratio of the washing liquid to the calcified calcined clinker is 0.1-0.4mL/g;
in the step (3), the liquid-solid ratio of the washing liquid to the calcified roasting clinker is 0.6-3mL/g;
in the step (4), the liquid-solid ratio of the secondary leaching agent to the calcified roasting clinker is 0.6-1mL/g;
in the step (5), the liquid-solid ratio of the washing liquid to the calcified roasting clinker is 0.4-1mL/g;
the washing liquid and the secondary leaching agent are both aqueous solutions with the pH value of 2-9 and the P content less than or equal to 0.03 g/L.
2. The method according to claim 1, wherein in step (1), the calcified calcined clinker has a vanadium content of 5-15 wt% and a phosphorus content of 0.1 wt% or less.
3. A method according to claim 1 or 2, characterized in that in step (1) the calcified clinker has a particle size of < 0.125mm.
4. The method of claim 1, wherein in step (1), the primary leaching time is 40-90min.
5. The method of claim 4, wherein in step (1), the primary leaching is at a temperature of 20-60 ℃.
6. The method of claim 1, wherein in step (4), the secondary leaching is for a period of 5-30 minutes.
7. The method of claim 6, wherein in step (4), the temperature of the secondary leach is 20-50 ℃.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161831A (en) * | 2007-11-09 | 2008-04-16 | 攀钢集团攀枝花钢铁研究院 | Calcification vanadium slag sintering method |
| CN103937978A (en) * | 2014-04-22 | 2014-07-23 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing raw material roasted clinker through ammonia leaching |
| CN104131161A (en) * | 2014-08-13 | 2014-11-05 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting soluble vanadium from calcified clinker through sulfuric acid leaching and method for testing soluble vanadium and roasting conversion rate |
| CN104745828A (en) * | 2015-04-14 | 2015-07-01 | 重庆大学 | Method for improving leaching rate of calcification roasting vanadium slag and improving filtering effect |
| CN105219976A (en) * | 2015-11-19 | 2016-01-06 | 攀钢集团西昌钢钒有限公司 | Improve the method for vanadium slag calcification baking grog leaching yield |
| CN105331832A (en) * | 2015-11-27 | 2016-02-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Acid-leaching washing method for vanadium-containing roasting clinker |
| CN109097567A (en) * | 2018-10-10 | 2018-12-28 | 攀钢集团钒钛资源股份有限公司 | The secondary pickling technique of vanadium slag calcification baking clinker |
| CN109252047A (en) * | 2018-10-31 | 2019-01-22 | 攀钢集团钒钛资源股份有限公司 | Calcification clinker acidleach method |
| CN109338103A (en) * | 2018-11-30 | 2019-02-15 | 攀钢集团研究院有限公司 | The method of calcification baking clinker counter current acid leaching vanadium extraction |
| CN111394576A (en) * | 2020-03-30 | 2020-07-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for deep leaching of acid leaching vanadium tailings and solution circulation |
| RU2743355C1 (en) * | 2018-11-30 | 2021-02-17 | Паньган Груп Рисёч Инститьют Ко., Лтд. | Method of extracting vanadium from vanadium slag with high content of calcium and phosphorus |
| CN112593097A (en) * | 2020-12-02 | 2021-04-02 | 攀钢集团研究院有限公司 | Continuous leaching vanadium extraction method for vanadium slag calcified clinker |
-
2021
- 2021-11-30 CN CN202111444394.6A patent/CN114350982B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161831A (en) * | 2007-11-09 | 2008-04-16 | 攀钢集团攀枝花钢铁研究院 | Calcification vanadium slag sintering method |
| CN103937978A (en) * | 2014-04-22 | 2014-07-23 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing raw material roasted clinker through ammonia leaching |
| CN104131161A (en) * | 2014-08-13 | 2014-11-05 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for extracting soluble vanadium from calcified clinker through sulfuric acid leaching and method for testing soluble vanadium and roasting conversion rate |
| CN104745828A (en) * | 2015-04-14 | 2015-07-01 | 重庆大学 | Method for improving leaching rate of calcification roasting vanadium slag and improving filtering effect |
| CN105219976A (en) * | 2015-11-19 | 2016-01-06 | 攀钢集团西昌钢钒有限公司 | Improve the method for vanadium slag calcification baking grog leaching yield |
| CN105331832A (en) * | 2015-11-27 | 2016-02-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Acid-leaching washing method for vanadium-containing roasting clinker |
| CN109097567A (en) * | 2018-10-10 | 2018-12-28 | 攀钢集团钒钛资源股份有限公司 | The secondary pickling technique of vanadium slag calcification baking clinker |
| CN109252047A (en) * | 2018-10-31 | 2019-01-22 | 攀钢集团钒钛资源股份有限公司 | Calcification clinker acidleach method |
| CN109338103A (en) * | 2018-11-30 | 2019-02-15 | 攀钢集团研究院有限公司 | The method of calcification baking clinker counter current acid leaching vanadium extraction |
| RU2743355C1 (en) * | 2018-11-30 | 2021-02-17 | Паньган Груп Рисёч Инститьют Ко., Лтд. | Method of extracting vanadium from vanadium slag with high content of calcium and phosphorus |
| CN111394576A (en) * | 2020-03-30 | 2020-07-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for deep leaching of acid leaching vanadium tailings and solution circulation |
| CN112593097A (en) * | 2020-12-02 | 2021-04-02 | 攀钢集团研究院有限公司 | Continuous leaching vanadium extraction method for vanadium slag calcified clinker |
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