CN110066929A - A kind of preparation method of oxygen vanadium sulphate solution - Google Patents
A kind of preparation method of oxygen vanadium sulphate solution Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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Abstract
The present invention relates to the preparation technical fields of vanadic sulfate, disclose a kind of preparation method of oxygen vanadium sulphate solution.The preparation method is included under acidic environment, to being restored containing vanadium solution, extract, be stripped latter section of richness vanadium liquid of reduction is made；The pH value for restoring latter section of rich vanadium liquid is adjusted to 1.5~2.5 using carbonate, is separated by solid-liquid separation, obtains two sections of extraction stostes；Two sections of extraction stostes are extracted, are stripped obtained two sections rich vanadium liquids；Two sections of rich vanadium liquids are mixed with active carbon, are stirred, obtain oxygen vanadium sulphate solution through being separated by solid-liquid separation.The preparation method had both been adapted to the raw material of a variety of vanadium contents, such as vanadium slag calcification baking leachate or vanadium wastewater, and can effectively reduce Solvent quantity, reduces the discharge of high-salt wastewater, is conducive to environmental protection；High-purity sulphuric acid vanadyl is prepared with leachate by " extracting-back extraction " twice, realizes and high-purity sulphuric acid vanadyl is prepared by short route containing vanadium leachate, improve the production efficiency of high-purity sulphuric acid vanadyl solution.
Description
Technical field
The present invention relates to vanadic sulfate preparation technical fields, are related to a kind of preparation method of oxygen vanadium sulphate solution.
Background technique
It is significant for all-vanadium flow battery development efficiently to prepare high-purity sulfuric acid vanadyl, and current high-purity sulphuric acid oxygen
Vanadium mainly prepares high-purity sulfuric acid vanadyl solution by high-purity vanadium pentoxide reduction.The process requirement is with the oxidation of high-purity five two
Vanadium is raw material, in purification process, needs to consume a large amount of acid-conditioning solution pH, reagent consumption is big.Precipitation process can generate greatly
High-salt wastewater, the ammonia nitrogen waste water of amount cause larger pressure to environmental protection.In addition, lacking can be contained in the prior art using vanadium
Measure the lower means that high-purity sulfuric acid vanadyl solution is prepared containing vanadium solution (such as vanadium wastewater).
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of oxygen vanadium sulphate solution, currently prepare vanadic sulfate to improve
Technology in, it is high to ingredient requirement, reagent consumption amount is big, can generate the problems such as a large amount of waste water.
The present invention solves its technical problem and adopts the following technical solutions to realize.
A kind of preparation method of oxygen vanadium sulphate solution comprising:
Under acidic environment, to being restored containing vanadium solution, extracted, be stripped latter section of richness vanadium liquid of reduction is made；
The pH value for restoring latter section of rich vanadium liquid is adjusted to 1.5~2.5 using carbonate, is separated by solid-liquid separation, obtains two sections of extractions
Stoste；
Two sections of extraction stostes are extracted, are stripped obtained two sections rich vanadium liquids；
Two sections of rich vanadium liquids are mixed with active carbon, are stirred, obtain oxygen vanadium sulphate solution through being separated by solid-liquid separation.
It in an embodiment of the present invention, is vanadium slag calcification baking leachate containing vanadium solution, under acidic environment, to containing
Vanadium solution is restored, is extracted, being stripped the step of latter section of rich vanadium liquid of reduction is made, and is specifically included:
PH value containing vanadium solution is adjusted to 1.2~2.5, obtains one section of extraction stoste；
One section of extraction stoste is extracted using organic phase, obtains one section of load organic phases；
One section of load organic phases is mixed with sulfuric acid, obtains one section of rich vanadium liquid through back extraction；
One section of rich vanadium liquid is mixed with reducing agent, obtains restoring latter section of rich vanadium liquid.
Further, the step of pH value containing vanadium solution being adjusted to 1.2~2.5, specifically includes:
The pH value containing vanadium solution is adjusted to 1.2~2.5 using sulfuric acid.
Further, the step of one section of load organic phases being mixed with sulfuric acid, obtaining one section of rich vanadium liquid through back extraction, it is specific to wrap
It includes:
The sulfuric acid that one section of load organic phases and molar concentration are 0.5~1.5mol/L is mixed, 2~5 grades of countercurrent reextraction, is obtained
To one section of rich vanadium liquid.
In an embodiment of the present invention, it is vanadium wastewater containing vanadium solution, under acidic environment, is carried out to containing vanadium solution
The step of latter section of rich vanadium liquid of reduction is made in reduction, extraction, back extraction, specifically includes:
It is restored to containing vanadium solution, adjusting pH value using carbonate is 1.5~3, is separated by solid-liquid separation, obtains a Duan Cuiyuan
Liquid；
One section of extraction stoste is extracted using organic phase, obtains one section of load organic phases；
One section of load organic phases is mixed with sulfuric acid, obtains restoring latter section of rich vanadium liquid through back extraction.
Further, the step of one section of extraction stoste being extracted, obtains one section of load organic phases using organic phase, specifically
Include:
By volume be (1~5) with organic phase by one section of extraction stoste: 1 mixes, and 2~5 grades of counter-current extraction, obtains one section and bears
Carry organic phase.
Further, one section of load organic phases is mixed with sulfuric acid, obtains the step of restoring latter section of rich vanadium liquid through back extraction,
It specifically includes:
The sulfuric acid that one section of load organic phases and molar concentration are 0.5~1.5mol/L is mixed, 2~5 grades of countercurrent reextraction, is obtained
To one section of rich vanadium liquid and one section of lean organic phase.
In an embodiment of the present invention, two sections of extraction stostes extracted, be stripped the step of obtained two sections rich vanadium liquids,
It specifically includes:
By volume (1~5) by two sections of extraction stostes and organic phase: 1 mixes, and 2~5 grades of counter-current extraction, obtains two sections of loads
Organic phase；
The sulfuric acid that two sections of load organic phases and molar concentration are 3~5mol/L is mixed, 2~5 grades of countercurrent reextraction, obtains two
The rich vanadium liquid of section.
In an embodiment of the present invention, two sections of rich vanadium liquids mixed with active carbon, stirred, obtain sulphur through being separated by solid-liquid separation
It the step of sour vanadyl solution, specifically includes:
By two sections of rich vanadium liquids with active carbon (8~15) in mass ratio: 1 mixes, and is separated by solid-liquid separation after stirring, obtains vanadic sulfate
Solution.
In an embodiment of the present invention, organic phase includes di-(2-ethylhexyl)phosphoric acid ester, and surplus is sulfonated kerosene.
The beneficial effect of the preparation method of the oxygen vanadium sulphate solution of the embodiment of the present invention is:
The preparation method of the oxygen vanadium sulphate solution of the embodiment of the present invention is included under acidic environment, goes back to containing vanadium solution
Latter section of reduction rich vanadium liquid is made in former, extraction, back extraction；The pH value for restoring latter section of rich vanadium liquid is adjusted to 1.5 using carbonate
~2.5, it is separated by solid-liquid separation, obtains two sections of extraction stostes；Two sections of extraction stostes are extracted, are stripped obtained two sections rich vanadium liquids；By two sections
Rich vanadium liquid is mixed with active carbon, is stirred, and obtains oxygen vanadium sulphate solution through being separated by solid-liquid separation.The preparation method both can be with vanadium slag calcification
Roasting And Leaching liquid can also recycle the vanadium in vanadium wastewater as raw material using vanadium wastewater as raw material, therefore also mention
A kind of new approaches for handling vanadium wastewater are supplied.Using vanadium slag calcification baking leachate as when raw material, can effectively reduce
Solvent quantity reduces the discharge of high-salt wastewater, is conducive to environmental protection；By " extracting-back extraction " twice with vanadium slag calcification roasting
It burns leachate and prepares high-purity sulphuric acid vanadyl, realize and high-purity sulphuric acid vanadyl is prepared by short route containing vanadium leachate, greatly improve
The production efficiency of high-purity sulphuric acid vanadyl electrolyte.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The preparation method of the oxygen vanadium sulphate solution of the embodiment of the present invention is specifically described below.Oxygen vanadium sulphate solution
Preparation method includes the following steps:
One, one section of rich vanadium liquid is prepared
Under acidic environment, to being restored containing vanadium solution, extracted, be stripped latter section of richness vanadium liquid of reduction is made.Preparation one
The rich vanadium liquid of section be chosen as vanadium slag calcification baking leachate either vanadium wastewater containing vanadium solution can basis when raw material difference
The different mode of following two is handled:
It 1, is vanadium slag calcification baking leachate containing vanadium solution
Firstly, adjusting the pH value containing vanadium solution to 1.2~2.5 using sulfuric acid, one section of extraction stoste is obtained.
Single-stage extraction is carried out to one section of extraction stoste using organic phase, obtains one section of load organic phases and one section of raffinate,
In, the mixed volume ratio of one section of extraction stoste and organic phase is (1~2): 1.
By volume (1~2) by sulfuric acid that one section of load organic phases and molar concentration are 0.5~1.5mol/L: 1 mixing,
2~5 grades of countercurrent reextraction, obtain one section of rich vanadium liquid and one section of lean organic phase.
One section of rich vanadium liquid is mixed with reducing agent, obtains restoring latter section of rich vanadium liquid, wherein reducing agent and one section of rich vanadium liquid
Molar ratio be (1.2~2): 1.
It in embodiments of the present invention, is 1~4 as the pH of leaching solution of raw material, vanadium concentration is 8~40g/L, and manganese concentration is
5~30g/L, magnesium density be 3~10g/L, calcium concentration be 0~500mg/L, concentration of iron be 0~50mg/L, aluminum concentration be 0~
50mg/L。
It 2, is vanadium wastewater containing vanadium solution
Reducing agent is added in vanadium wastewater, is stirred, reduction, then pH to 1.5~3.0 is adjusted with calcium carbonate, it is separated by solid-liquid separation,
Obtain one section of extraction stoste and one section of neutralization slag；Wherein, the molar ratio of reducing agent and vanadium in vanadium wastewater is 1.2~2.
By volume (3~5) by one section of extraction stoste and organic phase: 1 mixes, and 2~5 grades of counter-current extraction, obtains one section of load
Organic phase and one section of raffinate；
By volume (1~5) by sulfuric acid that one section of load organic phases and molar concentration are 0.5~1.5mol/L: 1 is mixed
It closes, 2~5 grades of countercurrent reextraction, obtains restoring latter section of rich vanadium liquid and one section of lean organic phase.
It in embodiments of the present invention, is 0~2 as the vanadium wastewater pH value of raw material, vanadium concentration is 1~3g/L, manganese concentration
For 5~30g/L, magnesium density is 3~10g/L, and calcium concentration is 0~500mg/L, and concentration of iron is 0~50mg/L, aluminum concentration is 0~
50mg/L。
Two, two sections of extraction stostes are prepared
The pH value for restoring latter section of rich vanadium liquid is adjusted to 1.5~2.5 using calcium carbonate, is separated by solid-liquid separation, obtains two sections of extractions
Stoste and two sections of neutralization slags.
Three, two sections of rich vanadium liquids are prepared
Two sections of extraction stostes are extracted, are stripped obtained two sections rich vanadium liquids.It specifically includes two sections of extraction stostes and organic phase
By volume (1~5): 1 mixing, obtains two sections of load organic phases and two sections of raffinates by 2~5 grades of counter-current extraction.Two sections are loaded
Organic phase and molar concentration be the sulfuric acid of 3~5mol/L by volume (1~10): 1 mixing, obtains two by 2~5 grades of countercurrent reextraction
The rich vanadium liquid of section and two sections of lean organic phases.Optionally, when containing vanadium solution being vanadium slag calcification baking leachate as raw material, two sections
Extract stoste and organic volume ratio mixed can be (1~2): 1.Optionally, when as the useless for precipitation containing vanadium solution of raw material
When water, the volume ratio of two sections of load organic phases and sulfuric acid can be (5~10): 1.
Four, active carbon is handled
By two sections of rich vanadium liquids with active carbon (8~15) in mass ratio: 1 mixes, and stirs 1~6h, is separated by solid-liquid separation, obtains sulfuric acid
Vanadyl solution and waste active carbon.
In above each step, the organic phase as extractant includes di-(2-ethylhexyl)phosphoric acid ester, and surplus is sulfonation
Kerosene.Further, it is sulfonation which, which is by the di-(2-ethylhexyl)phosphoric acid ester and surplus of percent by volume 5~30%,
What kerosene obtained after mixing.In the embodiment of the present invention, reducing agent is calcium sulfite, in sodium sulfite, oxalic acid, sodium thiosulfate
It is a kind of.
It is vanadium slag calcification baking that the preparation method of oxygen vanadium sulphate solution provided in an embodiment of the present invention, which can be applied to raw material,
The case where leachate or vanadium wastewater.When being leachate (the higher raw material of content of vanadium) containing vanadium solution, extraction can be effectively reduced
Agent dosage is taken, the discharge of high-salt wastewater is reduced, is conducive to environmental protection.When containing vanadium solution, for vanadium wastewater, (content of vanadium is lower
Raw material) when, it also can recycle vanadium from vanadium wastewater effectively to prepare oxygen vanadium sulphate solution, be in vanadium wastewater
The recycling of valuable metal provides new thinking.High-purity sulphuric acid vanadyl is prepared with leachate by " extracting-back extraction " twice,
It realizes and high-purity sulphuric acid vanadyl is prepared by short route containing vanadium leachate, greatly improve the production of high-purity sulphuric acid vanadyl electrolyte
Efficiency.In addition, being conventional metallurgical reagent since extraction process uses medicament, industrial application is mature, which is applied to practical
Production is relatively easy to.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment is vanadium slag calcification baking leachate containing vanadium solution, in which: vanadium concentration is 28.84g/L；Manganese concentration is
15.6g/L；Magnesium density is 6.5g/L；Calcium concentration is 0.57g/L；PH value is 2.6.The preparation of the oxygen vanadium sulphate solution of the present embodiment
Method includes:
(1) vanadium slag calcification baking leachate pH to 2.0 is adjusted with sulfuric acid, obtains one section of extraction stoste；
(2) according to one section of extraction stoste: the volume ratio of organic phase is 2, and one section of extraction stoste is mixed with organic, single-stage extraction
It takes, obtains one section of load organic phases and one section of raffinate；
(3) press one section of load organic phases: the volume ratio of sulfuric acid is 1, is 1mol/ by one section of load organic phases and molar concentration
The sulfuric acid of L mixes, and 4 grades of countercurrent reextraction, obtains one section of rich vanadium liquid and one section of lean organic phase；
(4) according to reducing agent: the molar ratio of vanadium is 1.3 mixing in one section of rich vanadium liquid, obtains restoring latter section of rich vanadium liquid；
(5) pH value for restoring latter section of rich vanadium liquid is adjusted to 1.5 with calcium carbonate, is separated by solid-liquid separation, obtains two sections of extraction stostes
With two sections of neutralization slags；
(6) according to two sections of extraction stostes: the volume ratio of organic phase is 1, two sections of extraction stostes is mixed with organic, counter-current extraction
4 grades, obtain two sections of load organic phases and two sections of raffinates；
(7) press two sections of load organic phases: the volume ratio of sulfuric acid is 10, is by two sections of load organic phases and molar concentration
The sulfuric acid of 4.5mol/L mixes, and 3 grades of countercurrent reextraction, obtains two sections of rich vanadium liquids and two sections of lean organic phases.
(8) by two sections of rich vanadium liquids: quality of activated carbon ratio is 12, and two sections of rich vanadium liquids are mixed with active carbon, 4h are stirred, through solid
Liquid separation, obtains high-purity sulphuric acid vanadyl solution and waste active carbon.
Vanadium concentration is 110.2g/L in high-purity sulphuric acid vanadyl solution, and major impurity ions of manganese concentration is less than 1ppm, calcium concentration
For 6ppm, magnesium density is less than 2ppm.
Embodiment 2
The present embodiment is vanadium slag calcification baking leachate containing vanadium solution, in which: vanadium concentration is 25.8g/L；Manganese concentration is
15.6g/L；Magnesium density is 6.5g/L；Calcium concentration is 0.57g/L；PH value is 2.6.The preparation of the oxygen vanadium sulphate solution of the present embodiment
Method includes:
(1) vanadium slag calcification baking leachate pH to 1.5 is adjusted with sulfuric acid, obtains one section of extraction stoste；
(2) according to one section of extraction stoste: the volume ratio of organic phase is 2, and one section of extraction stoste is mixed with organic, single-stage extraction
It takes, obtains one section of load organic phases and one section of raffinate；
(3) press one section of load organic phases: the volume ratio of sulfuric acid is 1, is by one section of load organic phases and molar concentration
The sulfuric acid of 0.5mol/L mixes, and 5 grades of countercurrent reextraction, obtains one section of rich vanadium liquid and one section of lean organic phase；
(4) according to reducing agent: the molar ratio of vanadium is 1.5 mixing in one section of rich vanadium liquid, obtains restoring latter section of rich vanadium liquid；
(5) pH value for restoring latter section of rich vanadium liquid is adjusted to 1.5 with calcium carbonate, is separated by solid-liquid separation, obtains two sections of extraction stostes
With two sections of neutralization slags；
(6) according to two sections of extraction stostes: the volume ratio of organic phase is 1, two sections of extraction stostes is mixed with organic, counter-current extraction
5 grades, obtain two sections of load organic phases and two sections of raffinates；
(7) press two sections of load organic phases: the volume ratio of sulfuric acid is 8, is 5mol/ by two sections of load organic phases and molar concentration
The sulfuric acid of L mixes, and 3 grades of countercurrent reextraction, obtains two sections of rich vanadium liquids and two sections of lean organic phases.
(8) by two sections of rich vanadium liquids: quality of activated carbon ratio is 10, and two sections of rich vanadium liquids are mixed with active carbon, 5h are stirred, through solid
Liquid separation, obtains high-purity sulphuric acid vanadyl solution and waste active carbon.
Vanadium concentration is 102.2g/L in high-purity sulphuric acid vanadyl solution, and major impurity ions of manganese concentration is less than 1ppm, calcium concentration
For 6ppm, magnesium density is less than 3ppm.
Embodiment 3
The present embodiment is vanadium slag calcification baking leachate containing vanadium solution, in which: vanadium concentration is 23.6g/L；Manganese concentration is
5.6g/L；Magnesium density is 2.5g/L；Calcium concentration is 0.27g/L；PH value is 2.8.The preparation of the oxygen vanadium sulphate solution of the present embodiment
Method includes:
(1) vanadium slag calcification baking leachate pH to 1.5 is adjusted with sulfuric acid, obtains one section of extraction stoste；
(2) press one section of extraction stoste: the volume ratio of organic phase is 1, one section of extraction stoste is mixed with organic, single-stage extraction,
Obtain one section of load organic phases and one section of raffinate；
(3) press one section of load organic phases: the volume ratio of sulfuric acid is 2, is by one section of load organic phases and molar concentration
The sulfuric acid of 1.5mol/L mixes, and 2 grades of countercurrent reextraction, obtains one section of rich vanadium liquid and one section of lean organic phase；
(4) press reducing agent: the molar ratio of vanadium is 1.2 mixing in one section of rich vanadium liquid, obtains restoring latter section of rich vanadium liquid；
(5) pH value for restoring latter section of rich vanadium liquid is adjusted to 1.6 with calcium carbonate, is separated by solid-liquid separation, obtains two sections of extraction stostes
With two sections of neutralization slags；
(6) press two sections of extraction stostes: the volume ratio of organic phase is 1, two sections of extraction stostes is mixed with organic, counter-current extraction 2
Grade, obtains two sections of load organic phases and two sections of raffinates；
(7) press two sections of load organic phases: the volume ratio of sulfuric acid is 10, is by two sections of load organic phases and molar concentration
The sulfuric acid of 5mol/L mixes, and 4 grades of countercurrent reextraction, obtains two sections of rich vanadium liquids and two sections of lean organic phases.
(8) by two sections of rich vanadium liquids: quality of activated carbon ratio is 15, and two sections of rich vanadium liquids are mixed with active carbon, 6h are stirred, through solid
Liquid separation, obtains high-purity sulphuric acid vanadyl solution and waste active carbon.
Vanadium concentration is 95.2g/L in high-purity sulphuric acid vanadyl solution, and major impurity ions of manganese concentration is less than 1ppm, calcium concentration is
6ppm, magnesium density are less than 2ppm.
Embodiment 4
The present embodiment is vanadium wastewater containing vanadium solution, in which: vanadium concentration is 1.5g/L, and manganese concentration is 15.4g/L, and magnesium is dense
Degree is 6.1g/L, calcium concentration 0.6g/L, pH value 1.1.The preparation method of the oxygen vanadium sulphate solution of the present embodiment includes:
(1) according to reducing agent: the molar ratio of vanadium is 1.2 in vanadium wastewater, and reducing agent is added in vanadium wastewater, stirring,
Reduction, then pH to 1.5 is adjusted with calcium carbonate, it is separated by solid-liquid separation, obtains one section of extraction stoste and one section of neutralization slag；
(2) press one section of extraction stoste: the volume ratio of organic phase is 3, one section of extraction stoste is mixed with organic, counter-current extraction 3
Grade, obtains one section of load organic phases and one section of raffinate；
(3) press one section of load organic phases: the volume ratio of sulfuric acid is 4, is by one section of load organic phases and molar concentration
The sulfuric acid of 1.0mol/L mixes, and 3 grades of countercurrent reextraction, obtains restoring latter section of rich vanadium liquid and one section of lean organic phase；
(4) one section of rich vanadium liquid calcium carbonate is adjusted pH value is 1.5, is separated by solid-liquid separation, obtains in two sections of extractions stostes and two sections
And slag；
(5) press two sections of extraction stostes: the volume ratio of organic phase is 1, two sections of extraction stostes is mixed with organic, counter-current extraction 4
Grade, obtains two sections of load organic phases and two sections of raffinates；
(6) press two sections of load organic phases: the volume ratio of sulfuric acid is 10, is by two sections of load organic phases and molar concentration
The sulfuric acid of 5mol/L mixes, and 3 grades of countercurrent reextraction, obtains two sections of rich vanadium liquids and two sections of lean organic phases.
(7) by two sections of rich vanadium liquids: quality of activated carbon ratio is 10, and two sections of rich vanadium liquids are mixed with active carbon, 6h are stirred, through solid
Liquid separation, obtains high-purity sulphuric acid vanadyl solution and waste active carbon.
Vanadium concentration is 110.3g/L in high-purity sulphuric acid vanadyl, and major impurity ions of manganese concentration is less than 1ppm, calcium concentration is
3ppm, magnesium density are less than 1ppm.
Embodiment 5
The present embodiment is vanadium wastewater containing vanadium solution, in which: vanadium concentration is 1.2g/L, and manganese concentration is 15.4g/L, and magnesium is dense
Degree is 6.1g/L, calcium concentration 0.6g/L, pH value 1.2.The preparation method of the oxygen vanadium sulphate solution of the present embodiment includes:
(1) according to reducing agent: the molar ratio of vanadium is 1.5 in vanadium wastewater, and reducing agent is added in vanadium wastewater, stirring,
Reduction, then pH to 2.0 is adjusted with calcium carbonate, it is separated by solid-liquid separation, obtains one section of extraction stoste and one section of neutralization slag；
(2) press one section of extraction stoste: the volume ratio of organic phase is 3, one section of extraction stoste is mixed with organic, counter-current extraction 3
Grade, obtains one section of load organic phases and one section of raffinate；
(3) press one section of load organic phases: the volume ratio of sulfuric acid is 4, is by one section of load organic phases and molar concentration
The sulfuric acid of 1.0mol/L mixes, and 3 grades of countercurrent reextraction, obtains restoring latter section of rich vanadium liquid and one section of lean organic phase；
(4) will restore latter section of rich vanadium liquid calcium carbonate and adjust pH value is 2.0, is separated by solid-liquid separation, obtain two sections of extraction stostes with
Two sections of neutralization slags；
(5) press two sections of extraction stostes: the volume ratio of organic phase is 1, two sections of extraction stostes is mixed with organic, counter-current extraction 4
Grade, obtains two sections of load organic phases and two sections of raffinates；
(6) press two sections of load organic phases: the volume ratio of sulfuric acid is 9, is 5mol/ by two sections of load organic phases and molar concentration
The sulfuric acid of L mixes, and 3 grades of countercurrent reextraction, obtains two sections of rich vanadium liquids and two sections of lean organic phases.
(7) by two sections of rich vanadium liquids: quality of activated carbon ratio is 12, and two sections of rich vanadium liquids are mixed with active carbon, 5h are stirred, through solid
Liquid separation, obtains high-purity sulphuric acid vanadyl solution and waste active carbon.
Vanadium concentration is 95.1g/L in high-purity sulphuric acid vanadyl solution, and major impurity ions of manganese concentration is less than 1ppm, calcium concentration is
3ppm, magnesium density are less than 1ppm.
Embodiment 6
The present embodiment is vanadium wastewater containing vanadium solution, in which: vanadium concentration is 1.02g/L；Manganese concentration is 15.4g/L；Magnesium
Concentration is 6.1g/L；Calcium concentration is 0.6g/L；PH value is 1.2.The preparation method of the oxygen vanadium sulphate solution of the present embodiment includes:
(1) according to reducing agent: the molar ratio of vanadium is 1.2 in vanadium wastewater, and reducing agent is added in vanadium wastewater, stirring,
Reduction, then pH to 1.8 is adjusted with calcium carbonate, it is separated by solid-liquid separation, obtains one section of extraction stoste and one section of neutralization slag；
(2) press one section of extraction stoste: the volume ratio of organic phase is 4, one section of extraction stoste is mixed with organic, counter-current extraction 3
Grade, obtains one section of load organic phases and one section of raffinate；
(3) press one section of load organic phases: the volume ratio of sulfuric acid is 3, is by one section of load organic phases and molar concentration
The sulfuric acid of 0.5mol/L mixes, and 4 grades of countercurrent reextraction, obtains restoring latter section of rich vanadium liquid and one section of lean organic phase；
(4) will restore latter section of rich vanadium liquid calcium carbonate and adjust pH value is 1.5, is separated by solid-liquid separation, obtain two sections of extraction stostes with
Two sections of neutralization slags；
(5) press two sections of extraction stostes: the volume ratio of organic phase is 1, two sections of extraction stostes is mixed with organic, counter-current extraction 4
Grade, obtains two sections of load organic phases and two sections of raffinates；
(6) press two sections of load organic phases: the volume ratio of sulfuric acid is 10, is by two sections of load organic phases and molar concentration
The sulfuric acid of 4.5mol/L mixes, and 3 grades of countercurrent reextraction, obtains two sections of rich vanadium liquids and two sections of lean organic phases.
(7) by two sections of rich vanadium liquids: quality of activated carbon ratio is 15, and two sections of rich vanadium liquids are mixed with active carbon, 4h are stirred, through solid
Liquid separation, obtains high-purity sulphuric acid vanadyl solution and waste active carbon.
Vanadium concentration is 110.2g/L in high-purity sulphuric acid vanadyl solution, and major impurity ions of manganese concentration is less than 1ppm, calcium concentration
For 3ppm, magnesium density is less than 1ppm.
To sum up, the preparation method of the oxygen vanadium sulphate solution of the embodiment of the present invention is included under acidic environment, to containing vanadium solution
It restored, extracted, being stripped the rich vanadium liquid of latter section of obtained reduction；The pH value for restoring latter section of rich vanadium liquid is adjusted using carbonate
To 1.5~2.5, it is separated by solid-liquid separation, obtains two sections of extraction stostes；Two sections of extraction stostes are extracted, are stripped obtained two sections rich vanadium liquids；It will
Two sections of rich vanadium liquids are mixed with active carbon, are stirred, and obtain oxygen vanadium sulphate solution through being separated by solid-liquid separation.The preparation method both can be with vanadium slag
Calcification baking leachate can also recycle the vanadium in vanadium wastewater, therefore as raw material using vanadium wastewater as raw material
Also provide a kind of new approaches for handling vanadium wastewater.It, can be effective using vanadium slag calcification baking leachate as when raw material
Solvent quantity is reduced, the discharge of high-salt wastewater is reduced, is conducive to environmental protection；By " extracting-back extraction " twice with leachate
High-purity sulphuric acid vanadyl is prepared, realizes and high-purity sulphuric acid vanadyl is prepared by short route containing vanadium leachate, greatly improve high purity sulphur
The production efficiency of sour vanadyl electrolyte.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of oxygen vanadium sulphate solution, which is characterized in that the preparation method includes:
Under acidic environment, to being restored containing vanadium solution, extracted, be stripped latter section of richness vanadium liquid of reduction is made；
The pH value of latter section of rich vanadium liquid of the reduction is adjusted to 1.5~2.5 using carbonate, is separated by solid-liquid separation, obtains two sections of extractions
Stoste；
Two sections of extractions stoste is extracted, is stripped obtained two sections rich vanadium liquids；
Described two sections rich vanadium liquids are mixed with active carbon, are stirred, obtain oxygen vanadium sulphate solution through being separated by solid-liquid separation.
2. the preparation method of oxygen vanadium sulphate solution according to claim 1, which is characterized in that the vanadium solution that contains is vanadium slag
Calcification baking leachate, it is described under acidic environment, to being restored containing vanadium solution, extracted, be stripped to be made and restore latter section of richness
The step of vanadium liquid, specifically includes:
The pH value containing vanadium solution is adjusted to 1.2~2.5, obtains one section of extraction stoste；
One section of extraction stoste is extracted using organic phase, obtains one section of load organic phases；
One section of load organic phases are mixed with sulfuric acid, obtain one section of rich vanadium liquid through back extraction；
Described one section rich vanadium liquid is mixed with reducing agent, obtains the rich vanadium liquid of latter section of the reduction.
3. the preparation method of oxygen vanadium sulphate solution according to claim 2, which is characterized in that described described to contain vanadium solution
PH value the step of being adjusted to 1.2~2.5, specifically include:
The pH value containing vanadium solution is adjusted to 1.2~2.5 using sulfuric acid.
4. the preparation method of oxygen vanadium sulphate solution according to claim 2, which is characterized in that described to load described one section
The step of organic phase is mixed with sulfuric acid, obtains one section of rich vanadium liquid through back extraction, specifically includes:
The sulfuric acid that one section of load organic phases and molar concentration are 0.5~1.5mol/L is mixed, 2~5 grades of countercurrent reextraction, is obtained
To described one section rich vanadium liquid.
5. the preparation method of oxygen vanadium sulphate solution according to claim 1, which is characterized in that the vanadium solution that contains is precipitation
Waste water, it is described under acidic environment, to being restored containing vanadium solution, extracted, be stripped the step of latter section of richness vanadium liquid of reduction is made,
It specifically includes:
It is restored to described containing vanadium solution, adjusting pH value using carbonate is 1.5~3, is separated by solid-liquid separation, obtains a Duan Cuiyuan
Liquid；
One section of extraction stoste is extracted using organic phase, obtains one section of load organic phases；
One section of load organic phases are mixed with sulfuric acid, obtain the rich vanadium liquid of latter section of the reduction through back extraction.
6. the preparation method of oxygen vanadium sulphate solution according to claim 5, which is characterized in that described to utilize organic phase to institute
The step of one section of extraction stoste is extracted, obtains one section of load organic phases is stated, is specifically included:
By volume be (1~5) with organic phase by one section of extraction stoste: 1 mixes, and 2~5 grades of counter-current extraction, obtains described one
Section load organic phases.
7. the preparation method of oxygen vanadium sulphate solution according to claim 5, which is characterized in that described to load described one section
The step of organic phase is mixed with sulfuric acid, obtains the latter section of rich vanadium liquid of reduction through back extraction, specifically includes:
The sulfuric acid that one section of load organic phases and molar concentration are 0.5~1.5mol/L is mixed, 2~5 grades of countercurrent reextraction, is obtained
To one section of rich vanadium liquid and one section of lean organic phase.
8. the preparation method of oxygen vanadium sulphate solution described in any one of -7 according to claim 1, which is characterized in that described to institute
It states two sections of extraction stostes to be extracted, be stripped the step of obtained two sections rich vanadium liquids, specifically include:
By volume (1~5) by two sections of extraction stoste and organic phase: 1 mixes, and 2~5 grades of counter-current extraction, obtains two sections of loads
Organic phase；
The sulfuric acid that two sections of load organic phases and molar concentration are 3~5mol/L is mixed, 2~5 grades of countercurrent reextraction, obtains institute
State two sections of rich vanadium liquids.
9. the preparation method of oxygen vanadium sulphate solution described in any one of -7 according to claim 1, which is characterized in that described by institute
It states two sections of rich vanadium liquids to mix, stir with active carbon, is separated by solid-liquid separation the step of obtaining oxygen vanadium sulphate solution, specifically included:
By described two sections rich vanadium liquids with active carbon (8~15) in mass ratio: 1 mixes, and is separated by solid-liquid separation after stirring, obtains the sulfuric acid
Vanadyl solution.
10. the preparation method of the oxygen vanadium sulphate solution according to any one of claim 2-7, which is characterized in that described to have
Machine mutually includes di-(2-ethylhexyl)phosphoric acid ester, and surplus is sulfonated kerosene.
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| CN115404361A (en) * | 2022-09-02 | 2022-11-29 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadyl sulfate solution from sodium salt roasting water extract of industrial vanadium slag |
| CN115477326A (en) * | 2022-09-02 | 2022-12-16 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadyl sulfate solution from industrial vanadium slag calcification roasting pickle liquor |
| WO2023093046A1 (en) * | 2021-11-25 | 2023-06-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadyl sulfate solution from recovered titanium tetrachloride refining tailings |
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