CN113929139B - Extracting agent and method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel - Google Patents
Extracting agent and method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel Download PDFInfo
- Publication number
- CN113929139B CN113929139B CN202111332041.7A CN202111332041A CN113929139B CN 113929139 B CN113929139 B CN 113929139B CN 202111332041 A CN202111332041 A CN 202111332041A CN 113929139 B CN113929139 B CN 113929139B
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- vanadium
- solution
- nickel
- extracting agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides an extractant and a method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel, wherein the extractant comprises the following components: an extractant P204, an extractant TBP, isooctanol, an extractant Cyanex272 and sulfonated kerosene, the method comprising the steps of: (1) mixing the acidic solution containing vanadium, molybdenum and nickel with the pretreated extractant and extracting to obtain a nickel-containing aqueous solution and a vanadium-molybdenum-containing organic solution; (2) carrying out primary back extraction on the vanadium-molybdenum-containing organic solution to obtain an aqueous solution containing vanadyl sulfate; the process method is simple and easy to implement, and not only can achieve the purposes of separating vanadium, molybdenum and nickel and enriching vanadium through the extraction-back extraction process, but also can directly prepare a vanadyl sulfate solution product from the acidic vanadium-containing mineral leaching solution, obtain a nickel sulfate solution and a sodium molybdate solution byproduct, avoid the discharge of waste water and achieve the purposes of clean production and cyclic utilization.
Description
Technical Field
The invention belongs to the field of vanadium product preparation, and particularly relates to an extracting agent and a method for preparing vanadyl sulfate from an acidic vanadium-containing molybdenum-nickel solution.
Background
Vanadyl sulfate is blue crystalline powder and is mainly used for electrolyte of all-vanadium redox flow energy storage batteries, mordant of fabrics, catalyst, reducing agent and the like. In industrial production, vanadyl sulfate is mainly prepared by dissolving vanadium pentoxide in sulfuric acid and adding a reducing agent to reduce pentavalent vanadium into tetravalent vanadium, thereby preparing vanadyl sulfate solution. The production process of vanadium pentoxide comprises roasting of vanadium-containing minerals, leaching, impurity removal, vanadium precipitation and calcination, so that the process is complex and the product is expensive, thus causing high production cost of vanadyl sulfate.
CN102683733A discloses a preparation method of vanadyl sulfate electrolyte of an all-vanadium redox flow battery. The method is characterized in that vanadyl sulfate solution obtained by leaching, back-extracting and resin analysis of vanadium slag and stone coal is adjusted in pH by using alkali metal or alkaline earth metal oxide or hydroxide, and an inorganic reducing agent is added. P204 or P507, TBP and sulfonated kerosene are used as extracting agents, multistage countercurrent extraction is carried out, and after two phases are separated, a vanadium-loaded organic phase is washed. And (3) carrying out multistage countercurrent back extraction on the vanadium-loaded organic phase by using a sulfuric acid solution at 2-5 stages to prepare vanadyl sulfate back extraction liquid. And adjusting the vanadyl sulfate stripping liquid. Adding an organic reducing agent to adjust the potential value of the solution, extracting by using the extracting agent, separating two phases, washing the vanadium-loaded organic phase by using a sulfuric acid solution, and carrying out multi-stage counter-current back extraction by using the sulfuric acid solution to obtain the vanadyl sulfate solution. Distilling to the concentration required by the all-vanadium redox flow battery. The method adopts a reduction-extraction-back extraction method to obtain the vanadyl sulfate solution, but because the accuracy of the primary product is not high, a subsequent purification step is required, and the process is complicated.
CN104064799A discloses a method for preparing vanadyl sulfate electrolyte by reducing ferrous sulfate/oxalic acid. The method for preparing the vanadyl sulfate electrolyte by reducing the ferrous sulfate/oxalic acid comprises the steps of extracting vanadyl sulfate solution, inorganic reducing vanadyl sulfate solution, preparing mixed extractant, carrying out vanadyl sulfate back extraction, carrying out organic reducing vanadyl sulfate back extraction, concentrating vanadyl sulfate electrolyte precursor and the like to prepare the high-purity vanadyl sulfate electrolyte. Although vanadyl sulfate can be obtained by extraction, the method comprises the steps of leaching vanadium by calcium oxide, reducing and the like, and has a complex process.
CN101580278A discloses a preparation method of vanadyl sulfate, belonging to the technical field of wet metallurgy. The method comprises the steps of using stone coal resources as raw materials, carrying out acid leaching to obtain a leaching solution of tetravalent vanadium, reducing and neutralizing the leaching solution, carrying out two-stage extraction and back extraction to obtain vanadyl sulfate enriched solution, and carrying out evaporation dehydration to obtain a vanadyl sulfate product. The method adopts an acid leaching-solvent extraction technology to directly prepare vanadyl sulfate, but needs reduction and neutralization steps, and has a complex process flow.
Therefore, there is a need to develop a new, more simplified and convenient vanadyl sulfate production process.
Disclosure of Invention
Aiming at the problems of complicated working procedures, high production cost and the like in the prior art, the invention provides an extracting agent and a method for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel, wherein the extracting agent has high selectivity to vanadium, molybdenum and nickel, the extracting agent is used for realizing the selective separation of vanadium, molybdenum and nickel in the solution to obtain an organic phase containing vanadium and molybdenum and a solution containing nickel, then the back extraction separation of vanadium and molybdenum is realized by utilizing the selectivity difference of sulfuric acid to vanadium and molybdenum to obtain a vanadyl sulfate solution and an organic phase containing molybdenum, and finally the regeneration of the extracting agent and the by-product of a sodium molybdate solution are realized by back extraction under an alkaline condition.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an extractant for extracting and separating vanadium, molybdenum and nickel, wherein the extractant comprises: extractant P204, extractant TBP, isooctyl alcohol, extractant Cyanex272 and sulfonated kerosene.
The extracting agent for extracting and separating vanadium, molybdenum and nickel provided by the invention is prepared by compounding an extracting agent P204, an extracting agent TBP, isooctanol, an extracting agent Cyanex272 and sulfonated kerosene, wherein the P204 is a main extracting agent and has the function of realizing extraction of vanadium and molybdenum, the TBP is a synergistic extracting agent and can improve the extraction rate of vanadium, and the addition of the Cyanex272 and isooctanol can improve the extraction selectivity of the extracting agent on vanadium, molybdenum and nickel and better realize the separation of vanadium, molybdenum and nickel.
Preferably, the volume ratio of the extractant P204 to the extractant TBP to the isooctanol to the extractant Cyanex272 to the sulfonated kerosene is (10-15) to (1-5) to (70-87), and the extractant may be, for example, 10:5:3:5:77, 12:4:2:4:78, 13:2:5:2:78, 10:2:3:4:77, 15:2:4:4:75 or 14:3:4:4:75, but is not limited to the enumerated values, and other unrecited values within the range of values are equally applicable. The vanadium extraction rate is in direct proportion to the volume fraction of P204 in the solution, when the volume fraction of P204 is less than 10%, the vanadium extraction rate is too low, when the volume fraction of P204 is higher than 15%, the vanadium extraction rate is improved extremely little, and when the volume fraction of P204 is higher than 15%, the viscosity of the solution is too high, the adverse effect is caused on the extraction process, so that the concentration range of the main extractant P204 is 10-15%. The addition amount of the synergist TBP depends on the volume fraction of the main extractant, and the ratio of the synergist to the main extractant is not more than 1: 2. The addition amounts of isooctanol and Cyanex272 in the extraction process are in positive correlation with the selectivity of vanadium molybdenum/nickel, and the volume fractions of isooctanol and Cyanex272 are adjusted between 1-5% according to different concentration ratios of vanadium nickel in the solution, so that the vanadium molybdenum/nickel in the solution is separated to the maximum extent.
In a second aspect, the invention provides a method for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel, wherein the method adopts the extractant for extracting and separating vanadium, molybdenum and nickel to perform extraction.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) mixing the acidic solution containing vanadium, molybdenum and nickel with the pretreated extractant and extracting to obtain a nickel-containing aqueous solution and a vanadium-molybdenum-containing organic solution;
(2) and carrying out back extraction on the vanadium-molybdenum-containing organic solution for one time to obtain the aqueous solution containing vanadyl sulfate.
The vanadium molybdenum/nickel extracting agent with high separation factor is used, the steps of reduction, subsequent impurity removal and the like are reduced on the basis of the traditional process, the vanadyl sulfate solution product is obtained by the efficient and rapid extraction and separation process of one-step extraction and two-step back extraction, the byproducts of the nickel sulfate solution and the sodium molybdate solution are separated, and the extracting agent is recycled, so that the vanadium molybdenum/nickel extracting agent has high efficiency and environmental protection.
Preferably, the pretreatment in step (1) is a saponification reaction.
Preferably, the saponifying agent used in the saponification reaction comprises sodium hydroxide.
Preferably, the concentration of sodium hydroxide in the saponification reaction is 0.1-1.0mol/L, and may be, for example, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.5mol/L, 0.7mol/L or 1.0mol/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the saponification reaction is carried out for a period of 5-15min, for example 5min, 7min, 8min, 10min, 11min, 12min or 15min, but is not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the acidic solution containing vanadium, molybdenum and nickel includes any one or a combination of at least two of vanadium-containing shale, vanadium slag or an acidic solution obtained after roasting vanadium titano-magnetite and sulfuric acid leaching, wherein typical but non-limiting combinations are a combination of vanadium-containing shale and vanadium slag, a combination of vanadium-containing shale and vanadium titano-magnetite, a combination of vanadium titano-magnetite and vanadium slag, and the like, but is not limited to the listed combinations, and other combinations not listed in the scope are also applicable.
Preferably, the acidic solution containing vanadium, molybdenum and nickel has a pH of 0.5 to 4, and may be, for example, 0.5, 0.8, 1.0, 1.2, 1.5, 1.8, 2.0, 2.2, 2.5, 2.8, 3.0, 3.2, 3.5, 3.8 or 4.0, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the concentration of vanadium in the acidic solution containing molybdenum and nickel is 1.0-2.5g/L, such as 1.0g/L, 1.2g/L, 1.5g/L, 1.8g/L, 2.0g/L, 2.2g/L or 2.5g/L, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the concentration of the molybdenum element in the acidic solution containing vanadium, molybdenum and nickel is 0.1-1.0g/L, such as 0.1g/L, 0.2g/L, 0.3g/L, 0.5g/L, 0.8g/L or 1.0g/L, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the concentration of nickel element in the acidic solution containing vanadium, molybdenum and nickel is 0.5-1.0g/L, such as 0.5g/L, 0.55g/L, 0.6g/L, 0.7g/L, 0.8g/L or 1.0g/L, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the manner of extraction comprises shaking extraction.
Preferably, the extraction phase ratio O/W is (1:1) - (6:1), and may be, for example, 1:1, 2:1, 3:1, 4:1, 5:1, or 6:1, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the extraction temperature is 25-65 ℃, for example 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or 65 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the extraction time is 5-30min, for example, 5min, 8min, 10min, 12min, 13min, 15min, 18min, 20min, 22min, 23min, 25min, 28min or 30min, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the number of stages of extraction is from 6 to 10, for example 6, 7, 8, 9 or 10, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the primary stripping agent added in the primary stripping in step (2) comprises a sulfuric acid solution.
Preferably, the first back extraction also produces a molybdenum-containing organic solvent.
Preferably, the concentration of vanadium in the molybdenum-containing organic solution is from 5.0 to 20.0g/L, and may be, for example, 5.0g/L, 5.5g/L, 6.0g/L, 7.0g/L, 10.0g/L, 15.0g/L, or 20.0g/L, although not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the concentration of the molybdenum element in the molybdenum-containing organic solution is from 0.5 to 10.0g/L, and may be, for example, 0.5g/L, 1.0g/L, 3.0g/L, 5.0g/L, 6.0g/L, 7.0g/L, 8.0g/L, 9.0g/L, or 10.0g/L, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the concentration of sulfuric acid in the vanadyl sulfate-containing aqueous solution is 1.0-5.0mol/L, and may be, for example, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 4.0mol/L, or 5.0mol/L, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the way of the primary back extraction comprises shaking back extraction.
Preferably, the ratio O/W of the first stripping is (1:1) - (6:1), and may be, for example, 1:1, 2:1, 3:1, 4:1, 5:1 or 6:1, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the first stripping is 25-65 ℃, for example 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or 65 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the time of the first stripping is 5-30min, such as 5min, 8min, 10min, 12min, 13min, 15min, 18min, 20min, 22min, 23min, 25min, 28min or 30min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the number of stages of the first stripping is 6 to 10, for example 6, 7, 8, 9 or 10, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the method further comprises the following steps after step (2):
(3) and mixing the molybdenum-containing organic solution with a sodium hydroxide solution, and performing secondary back extraction to obtain a molybdenum-containing aqueous solution and complete the regeneration and recovery of the extractant.
Preferably, the concentration of the molybdenum element in the molybdenum-containing organic solution is 0.5-10.0g/L, and may be, for example, 0.5g/L, 1.0g/L, 3.0g/L, 5.0g/L, 5.5g/L, 6.0g/L, 7.0g/L, or 10.0g/L, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the concentration of sodium hydroxide in the aqueous molybdenum-containing solution is 0.5 to 5.0mol/L, and may be, for example, 0.5mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 4.0mol/L, or 5.0mol/L, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the secondary stripping mode comprises oscillating stripping.
Preferably, the ratio O/W of the second stripping is (1:1) - (5:1), and may be, for example, 1:1, 2:1, 3:1, 4:1 or 5:1, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the temperature of the second stripping is 25-65 ℃, for example 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or 65 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the time of the second stripping is 5-30min, such as 5min, 8min, 10min, 12min, 13min, 15min, 18min, 20min, 22min, 23min, 25min, 28min or 30min, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the number of stages of the secondary stripping is 1 to 3, and may be, for example, 1, 2 or 3, but is not limited to the recited values, and other unrecited values within the range of values are also applicable.
Preferably, the regenerated and recovered extractant in step (3) is returned to the extraction process in step (1).
Preferably, the composition of the organic phase and the proportions of the components in the extractant returned to the circuit remain unchanged.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) mixing an acidic solution containing vanadium, molybdenum and nickel with the concentration of 1.0-2.5g/L, the concentration of molybdenum of 0.1-1.0g/L and the concentration of nickel of 0.5-1.0g/L with an extracting agent subjected to saponification reaction of sodium hydroxide, and performing oscillation extraction with the ratio of O/W to O/W of (1:1) - (6:1), the temperature of 25-65 ℃, the time of 5-30min and the number of stages of 6-10 to obtain a nickel-containing aqueous solution and a vanadium-molybdenum-containing organic solution with the concentration of vanadium of 5.0-20.0g/L and the concentration of molybdenum of 0.5-10.0 g/L;
(2) Mixing the vanadium-molybdenum-containing organic solution with 1.0-5.0mol/L sulfuric acid solution, and performing oscillation once back extraction with the comparison ratio of O/W (1:1) - (6:1), 25-65 ℃, 5-30min and 6-10 stages to obtain vanadyl sulfate-containing aqueous solution and molybdenum-containing organic solution with the molybdenum element concentration of 0.5-10.0 g/L;
(3) mixing the molybdenum-containing organic solution with 0.5-5.0mol/L sodium hydroxide solution, performing oscillation secondary back extraction with the comparison ratio of O/W (1:1) - (5:1), 25-65 ℃, 5-30min and the stage number of 1-3 to obtain a molybdenum-containing aqueous solution, completing the regeneration and recovery of an extractant, and returning the regenerated and recovered extractant to the extraction process in the step (1);
wherein, the extracting agents in the step (1) and the step (3) respectively and independently contain the following components in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene (10-15) = (1-5): (70-87).
Compared with the prior art, the invention has the beneficial effects that:
(1) the extracting agent for extracting and separating vanadium, molybdenum and nickel provided by the invention can be used for directly enriching and separating vanadium from vanadium-containing mineral leaching liquor through extraction to obtain a vanadyl sulfate solution product, wherein when the extracting agent and process parameters are in the optimal range, the purity of the vanadyl sulfate solution is more than or equal to 99.11%, and the yield is more than or equal to 92.71%;
(2) The method for preparing vanadyl sulfate from acidic vanadium-containing molybdenum-nickel solution provided by the invention can realize enrichment and separation of vanadium by extraction from vanadium-containing mineral leachate directly, the obtained vanadyl sulfate solution has high purity, and byproducts such as nickel sulfate solution and sodium molybdate solution are obtained at the same time, when an extractant and process parameters are in a preferred range, the purity of the nickel sulfate solution is not less than 92.15%, the purity of the sodium molybdate solution is not less than 99.03%, the yield of the nickel sulfate solution is =100%, the yield of the sodium molybdate solution is not less than 89.78%, and the economy is good;
(3) the method for preparing vanadyl sulfate from the acidic solution containing vanadium, molybdenum and nickel provided by the invention has the advantages that the process can be carried out circularly, no waste water or other solid wastes are generated, the flow is simple, and the operation is convenient.
Drawings
FIG. 1 is a flow chart of a method for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In one embodiment, the invention provides an extractant for extracting and separating vanadium, molybdenum and nickel, which comprises the following components in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene (10-15) = (1-5): (70-87).
In another embodiment, the invention provides a method for preparing vanadyl sulfate from an acidic molybdenum-nickel-containing solution containing vanadium by using the extracting agent, which specifically comprises the following steps:
(1) mixing an acidic vanadium-containing molybdenum-nickel solution with the vanadium element concentration of 1.00-5.00g/L, the molybdenum element concentration of 0.10-2.00g/L, the nickel element concentration of 0.50-3.00g/L and the pH value of 0.5-4 with an extracting agent subjected to sodium hydroxide saponification reaction, and performing oscillation extraction with the O/W ratio of (1:1) - (3:1), the temperature of 25-65 ℃, the temperature of 15min and the stage number of 1-10 to obtain a nickel-containing aqueous solution and a vanadium-molybdenum-containing organic solution with the vanadium element concentration of 1.0-5.0g/L and the molybdenum element concentration of 0.1-1.0 g/L;
(2) mixing the vanadium-molybdenum-containing organic solution with 1.0-5.0mol/L sulfuric acid solution, and performing oscillation once back extraction with the comparison ratio of O/W (1:1) - (6:1), 25-65 ℃, 15min and the stage number of 1-10 to obtain vanadyl sulfate aqueous solution and molybdenum-containing organic solution;
(3) Mixing the molybdenum-containing organic solution with 0.5-5.0mol/L sodium hydroxide solution, performing oscillation secondary back extraction with the ratio of O/W (1:1) - (6:1), 25-65 ℃, 15min and the stage number of 1-10 to obtain a molybdenum-containing aqueous solution and an extractant, and returning the extractant in the step (3) to the extraction process in the step (1).
FIG. 1 is a schematic diagram of the steps of a process for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel, wherein the acidic solution containing vanadium, molybdenum and nickel is mixed with an extractant and extracted to obtain a nickel-containing aqueous solution, i.e., a nickel sulfate solution byproduct, and simultaneously obtain a vanadium-molybdenum-containing organic solution; mixing the vanadium-molybdenum-containing organic solution with a sulfuric acid solution, and performing one-time back extraction to obtain an aqueous solution containing vanadyl sulfate, namely a vanadyl sulfate solution product, and simultaneously obtain a molybdenum-containing organic solution, wherein the preparation process is finished; and mixing the molybdenum-containing organic solution with a sodium hydroxide solution, and performing secondary back extraction to obtain a molybdenum-containing aqueous solution, namely a sodium molybdate solution byproduct, and simultaneously obtain a regenerated extracting agent, so that the regenerated extracting agent is reused in a production line, and the process added value is improved.
It is understood that processes provided by embodiments of the present invention or substitutions or variations of conventional data are within the scope and disclosure of the present invention.
Example 1
The embodiment provides an extractant for extracting and separating vanadium, molybdenum and nickel, which comprises the following components in percentage by volume: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:5:3:5: 77.
The embodiment also provides a method for preparing vanadyl sulfate from the acidic solution containing vanadium, molybdenum and nickel by using the extracting agent, which specifically comprises the following steps:
(1) mixing an acidic vanadium-molybdenum-nickel-containing solution with the vanadium element concentration of 1.05g/L, the molybdenum element concentration of 0.71g/L, the nickel element concentration of 0.68g/L and the pH =1.14 with an extracting agent treated by a sodium hydroxide saponification reaction, and performing four-stage oscillation extraction at 25 ℃ in comparison with the O/W of 1:1 to obtain a nickel-containing aqueous solution and a vanadium-molybdenum-containing organic solution with the vanadium element concentration of 0.98g/L and the molybdenum element concentration of 0.62 g/L;
(2) mixing the vanadium-molybdenum-containing organic solution with 1.5mol/L sulfuric acid solution, and performing four-stage oscillation once back extraction at 25 ℃ with the O/W ratio of 3:1 to obtain vanadyl sulfate-containing aqueous solution and molybdenum-containing organic solution with the vanadium element concentration of 3.09 g/L;
(3) and (3) mixing the molybdenum-containing organic solution with 0.5mol/L sodium hydroxide solution, performing secondary oscillation back extraction at 25 ℃ with the O/W ratio of 5:1 to obtain a molybdenum-containing aqueous solution with the molybdenum element concentration of 3.21g/L and an extracting agent, and returning the extracting agent in the step (3) to the extraction process in the step (1).
Example 2
The embodiment provides an extractant for extracting and separating vanadium, molybdenum and nickel, which comprises the following components in percentage by volume: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =12:4:2:4: 78.
The embodiment also provides a method for preparing vanadyl sulfate from the acidic solution containing vanadium, molybdenum and nickel by using the extracting agent, which specifically comprises the following steps:
(1) mixing an acidic vanadium-containing molybdenum-nickel solution with the vanadium element concentration of 1.88g/L, the molybdenum element concentration of 1.73g/L, the nickel element concentration of 2.55g/L and the pH =1.43 with an extracting agent treated by a sodium hydroxide saponification reaction, and performing three-stage oscillation extraction at 25 ℃ with the O/W ratio of 2:1 to obtain a nickel-containing aqueous solution and a vanadium-containing molybdenum organic solution with the vanadium element concentration of 1.79g/L and the molybdenum element concentration of 1.59 g/L;
(2) mixing the vanadium-molybdenum-containing organic solution and 2.0mol/L sulfuric acid solution, and performing five-stage oscillation primary back extraction at 35 ℃ compared with the O/W of 6:1 to obtain vanadyl sulfate-containing aqueous solution and molybdenum-containing organic solution with vanadium element concentration of 11.03 g/L;
(3) and (3) mixing the molybdenum-containing organic solution with 0.2mol/L sodium hydroxide solution, performing six-stage oscillation secondary back extraction at 35 ℃ with the O/W ratio of 4:1 to obtain a molybdenum-containing aqueous solution with the molybdenum element concentration of 6.61g/L and an extracting agent, and returning the extracting agent in the step (3) to the extraction process in the step (1).
Example 3
The embodiment provides an extractant for extracting and separating vanadium, molybdenum and nickel, which comprises the following components in percentage by volume: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =13:2:5:2: 78.
The embodiment also provides a method for preparing vanadyl sulfate from the acidic solution containing vanadium, molybdenum and nickel by using the extracting agent, which specifically comprises the following steps:
(1) mixing an acidic vanadium-containing molybdenum-nickel solution with the vanadium element concentration of 0.81g/L, the molybdenum element concentration of 0.92g/L, the nickel element concentration of 1.80g/L and the pH =0.95 with an extracting agent treated by sodium hydroxide saponification reaction, and performing five-stage oscillation extraction at 45 ℃ compared with the O/W of 1:1 to obtain a nickel-containing aqueous solution and a vanadium-containing molybdenum organic solution with the vanadium element concentration of 0.80g/L and the molybdenum element concentration of 0.88 g/L;
(2) mixing the vanadium-molybdenum-containing organic solution with 2.0mol/L sulfuric acid solution, and performing two-stage oscillation and one-time back extraction at 45 ℃ with the O/W ratio of 5:1 to obtain vanadyl sulfate-containing aqueous solution and molybdenum-containing organic solution with the vanadium element concentration of 3.88 g/L;
(3) and (3) mixing the molybdenum-containing organic solution with 0.8mol/L sodium hydroxide solution, performing secondary oscillation back extraction at 45 ℃ with the O/W ratio of 4:1 to obtain a molybdenum-containing aqueous solution with the molybdenum element concentration of 3.42g/L and an extracting agent, and returning the extracting agent in the step (3) to the extraction process in the step (1).
Example 4
The embodiment provides an extractant for extracting and separating vanadium, molybdenum and nickel, which comprises the following components in percentage by volume: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:2:3:4: 77.
The embodiment also provides a method for preparing vanadyl sulfate from the acidic solution containing vanadium, molybdenum and nickel by using the extracting agent, which specifically comprises the following steps:
(1) mixing an acidic vanadium-containing molybdenum-nickel solution with the vanadium element concentration of 2.08g/L, the molybdenum element concentration of 1.37g/L, the nickel element concentration of 2.91g/L and the pH =2.24 with an extracting agent treated by a sodium hydroxide saponification reaction, and performing secondary oscillation extraction at the temperature of 45 ℃ compared with the O/W of 3:1 to obtain a nickel-containing aqueous solution and a vanadium-containing molybdenum organic solution with the vanadium element concentration of 1.72g/L and the molybdenum element concentration of 1.24 g/L;
(2) mixing the vanadium-molybdenum-containing organic solution with 2.3mol/L sulfuric acid solution, and performing seven-stage oscillation once back extraction at 25 ℃ with the O/W ratio of 6:1 to obtain vanadyl sulfate-containing aqueous solution and molybdenum-containing organic solution with the vanadium element concentration of 11.57 g/L;
(3) and (2) mixing the molybdenum-containing organic solution with 1.0mol/L sodium hydroxide solution, performing five-stage oscillation secondary back extraction at 35 ℃ with the O/W ratio of 3:1 to obtain a molybdenum-containing aqueous solution with the molybdenum element concentration of 3.69g/L and an extracting agent, and returning the extracting agent in the step (3) to the extraction process in the step (1).
Example 5
The embodiment provides an extractant for extracting and separating vanadium, molybdenum and nickel, which comprises the following components in percentage by volume: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =15:2:4:4: 75.
The embodiment also provides a method for preparing vanadyl sulfate from the acidic solution containing vanadium, molybdenum and nickel by using the extracting agent, which specifically comprises the following steps:
(1) mixing an acidic vanadium-containing molybdenum-nickel solution with the vanadium element concentration of 1.78g/L, the molybdenum element concentration of 0.62g/L, the nickel element concentration of 1.21g/L and the pH =2.77 with an extracting agent treated by a sodium hydroxide saponification reaction, and performing nine-stage oscillation extraction at 55 ℃ in comparison with the O/W of 1:1 to obtain a nickel-containing aqueous solution and a vanadium-containing molybdenum organic solution with the vanadium element concentration of 1.76g/L and the molybdenum element concentration of 0.62 g/L;
(2) mixing the vanadium-molybdenum-containing organic solution with 3.2mol/L sulfuric acid solution, and performing secondary oscillation and primary back extraction at 45 ℃ with the O/W ratio of 5:1 to obtain vanadyl sulfate-containing aqueous solution and molybdenum-containing organic solution with vanadium element concentration of 8.56 g/L;
(3) and (3) mixing the molybdenum-containing organic solution with 1.2mol/L sodium hydroxide solution, carrying out four-stage oscillation secondary back extraction at 65 ℃ with the O/W ratio of 3:1 to obtain a molybdenum-containing aqueous solution with the molybdenum element concentration of 1.81g/L and an extracting agent, and returning the extracting agent in the step (3) to the extraction process in the step (1).
Example 6
The embodiment provides an extractant for extracting and separating vanadium, molybdenum and nickel, which comprises the following components in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =14:3:4:4: 75.
The embodiment also provides a method for preparing vanadyl sulfate from the acidic solution containing vanadium, molybdenum and nickel by using the extracting agent, which specifically comprises the following steps:
(1) mixing an acidic vanadium-molybdenum-nickel-containing solution with the vanadium element concentration of 2.73g/L, the molybdenum element concentration of 0.65g/L, the nickel element concentration of 1.49g/L and the pH =3.13 with an extracting agent treated by a sodium hydroxide saponification reaction, and performing seven-stage oscillation extraction at 35 ℃ in comparison with the O/W of 1:1 to obtain a nickel-containing aqueous solution and a vanadium-molybdenum-containing organic solution with the vanadium element concentration of 2.70g/L and the molybdenum element concentration of 0.61 g/L;
(2) mixing the vanadium-molybdenum-containing organic solution with 1.5mol/L sulfuric acid solution, and performing secondary oscillation and primary back extraction at 25 ℃ with the O/W ratio of 4:1 to obtain vanadyl sulfate-containing aqueous solution and molybdenum-containing organic solution with the vanadium element concentration of 10.62 g/L;
(3) and (3) mixing the molybdenum-containing organic solution with 1.2mol/L sodium hydroxide solution, carrying out four-stage oscillation secondary back extraction at 65 ℃ with the O/W ratio of 3:1 to obtain a molybdenum-containing aqueous solution with the molybdenum element concentration of 1.78g/L and an extracting agent, and returning the extracting agent in the step (3) to the extraction process in the step (1).
Example 7
In the same way as in example 1, the process for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel, the extractant is distinguished in that it comprises the following constituents in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:7:3:5: 75.
Example 8
In the same way as in example 1, the process for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel, the extractant is distinguished in that it comprises the following constituents in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:5:3:7: 77.
Example 9
In the same way as in example 1, the process for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel, the extractant is distinguished in that it comprises the following constituents in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:5:7:5: 73.
Comparative example 1
In the same way as in example 1, the process for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel, the extractant is distinguished in that it comprises the following constituents in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:0:3:5:82, the method comprising in particular the steps of:
Comparative example 2
The same procedure as in example 1 for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel was followed, with the difference that the extractant contained the following constituents in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:5:3:0: 80.
Comparative example 3
In the same way as in example 1, the process for preparing vanadyl sulfate from an acidic solution containing vanadium, molybdenum and nickel, the extractant is distinguished in that it comprises the following constituents in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:5:0:5: 80.
The concentration of each element in the solution is quantitatively determined and analyzed by ICP-OES, and the purity is calculated by the following method: target element purity = target element concentration/total concentration of all metal elements in solution. The product yield calculation method comprises the following steps: product yield = target element concentration in strip/target element concentration in feed solution.
The purity and yield were obtained according to the above test methods and calculation formulas, and the yields and purities of the vanadyl sulfate solution, nickel sulfate solution and sodium molybdate solution products prepared in examples 1-9 and comparative examples 1-3 are shown in table 1.
TABLE 1
| Purity of vanadyl sulfate solution (%) | Purity of nickel sulfate solution (%) | Purity of sodium molybdate solution (%) | Yield (%) of vanadyl sulfate solution | Nickel sulfate solution yield (%) | Yield (%) | |
| Example 1 | 99.65 | 92.15 | 99.88 | 98.09 | 100 | 90.45 |
| Example 2 | 99.11 | 93.22 | 99.79 | 97.78 | 100 | 95.52 |
| Example 3 | 99.18 | 94.11 | 99.81 | 95.81 | 100 | 92.93 |
| Example 4 | 99.29 | 94.89 | 99.69 | 92.71 | 100 | 89.78 |
| Example 5 | 99.44 | 93.57 | 99.03 | 96.18 | 100 | 97.31 |
| Example 6 | 99.52 | 92.19 | 99.91 | 97.25 | 100 | 91.28 |
| Example 7 | 99.88 | 92.98 | 99.98 | 87.22 | 100 | 95.73 |
| Example 8 | 93.26 | 96.11 | 99.90 | 90.51 | 98.26 | 82.55 |
| Example 9 | 96.17 | 91.10 | 99.59 | 85.08 | 99.27 | 96.46 |
| Comparative example 1 | 99.92 | 92.27 | 99.26 | 79.81 | 100 | 86.07 |
| Comparative example 2 | 94.17 | 94.69 | 99.80 | 97.99 | 98.72 | 89.41 |
| Comparative example 3 | 96.88 | 98.12 | 99.62 | 94.65 | 99.15 | 98.35 |
From the data in table (1) we can see that:
(1) the purity of the vanadyl sulfate solution obtained by the extractant for extracting and separating the vanadium, molybdenum and nickel provided in the embodiments 1 to 6 is equal to or more than 99.11%, the purity of the nickel sulfate solution is equal to or more than 92.15%, the purity of the sodium molybdate solution is equal to or more than 99.03%, a high-purity vanadyl sulfate solution product and a sodium molybdate solution byproduct are obtained, meanwhile, the yield of the vanadyl sulfate solution in the whole extraction-back extraction process is equal to or more than 92.71%, the yield of the nickel sulfate solution is equal to =100%, and the yield of the sodium molybdate solution is equal to or more than 89.78%, which proves that the purposes of high yield, low waste and low pollution are also realized in the extraction and enrichment process;
(2) by combining example 1, example 7 and comparative example 1, it can be seen that the volume ratio of the components in the extractant of example 1 is: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:5:3:5:77, compared to the extractants of example 7 and comparative example 1, extractant P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: the volume ratio of sulfonated kerosene is 10:7:3:5:75 and 10:0:3:5:82 respectively, the purity of the vanadyl sulfate solution obtained in example 1 is 99.65%, and the yield of the vanadyl sulfate solution is 98.09%, while the purity of the vanadyl sulfate solution obtained in example 7 and comparative example 1 reaches 99.88% and 99.92% respectively, but the yield of the vanadyl sulfate solution is only 87.22% and 79.81% respectively; therefore, the proportion of the extracting agent TBP and other substances in the extracting agent is controlled in a specific range, so that the high concentration of the main product vanadyl sulfate solution can be ensured, and the high yield can be ensured;
(3) By combining example 1, example 8 and comparative example 2, it can be seen that the volume ratio of the components in the extractant of example 1 is: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:5:3:5:77, compared to the extractants of example 7 and comparative example 1, extractant P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: the volume ratio of sulfonated kerosene is 10:5:3:7:77 and 10:5:3:0:80 respectively, the purity of the vanadyl sulfate solution obtained in example 1 is 99.65%, and the yield of the vanadyl sulfate solution is 98.09%, while the yields of the vanadyl sulfate solutions obtained in example 8 and comparative example 2 are only 93.26% and 94.17%, and the yields of the vanadyl sulfate solution are only 90.51% and 97.99%, respectively; therefore, the invention shows that the extraction agent is used for preparing the vanadyl sulfate solution, wherein the proportion of the extraction agent Cyanex272 to other substances in the extraction agent is controlled in a specific range, so that the high yield of the main product vanadyl sulfate solution can be ensured, and the higher concentration can be ensured;
(4) by combining example 1, example 9 and comparative example 3, it can be seen that the volume ratio of the components in the extractant of example 1 is: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene =10:5:3:5:77, as compared to the extractants of example 7 and comparative example 1, extractant P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: the volume ratio of sulfonated kerosene was 10:5:3:7:77 and 10:5:3:0:80, respectively, the purity of the vanadyl sulfate solution obtained in example 1 was 99.65%, and the yield of the vanadyl sulfate solution was 98.09%, while the yields of the vanadyl sulfate solutions obtained in example 8 and comparative example 2 were only 96.17% and 96.88%, and the yields of the vanadyl sulfate solution were only 85.08% and 94.65%, respectively. Therefore, the invention shows that the extraction agent is used for preparing the vanadyl sulfate solution, wherein the proportion of isooctanol and other substances in the extraction agent is controlled in a specific range, and the main product vanadyl sulfate solution with high concentration and high yield can be obtained simultaneously.
In conclusion, according to the extracting agent and the method for preparing vanadyl sulfate from the acidic vanadium-containing molybdenum-nickel solution, provided by the invention, vanadium, molybdenum and nickel are separated and vanadium is enriched through an extraction-back extraction process, a vanadyl sulfate solution product can be directly prepared from the acidic vanadium-containing mineral leaching solution, and a nickel sulfate solution and a sodium molybdate solution byproduct are obtained, so that the purposes of clean production and recycling are achieved, and the extracting agent and the method are suitable for industrial production.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (31)
1. An extractant for extracting and separating vanadium, molybdenum and nickel, which is characterized by comprising: extracting agent P204, extracting agent TBP, isooctyl alcohol, extracting agent Cyanex272 and sulfonated kerosene;
the volume ratio of the extracting agent P204, the extracting agent TBP, the isooctyl alcohol, the extracting agent Cyanex272 and the sulfonated kerosene in the extracting agent is (10-15): 1-5: (1-5): 70-87.
2. A method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel, which is characterized in that the method adopts the extractant for extracting and separating vanadium, molybdenum and nickel in claim 1 for extraction;
the method comprises the following steps:
(1) mixing the acidic solution containing vanadium, molybdenum and nickel with an extractant subjected to saponification reaction, and extracting to obtain a nickel-containing aqueous solution and a vanadium-molybdenum-containing organic solution;
(2) and carrying out primary back extraction on the vanadium-molybdenum-containing organic solution by using a sulfuric acid solution to obtain an aqueous solution containing vanadyl sulfate.
3. The method of claim 2, wherein the saponification reaction uses a saponifying agent comprising sodium hydroxide.
4. The method according to claim 3, wherein the concentration of sodium hydroxide in the saponification reaction is 0.1 to 1.0 mol/L.
5. The method of claim 2, wherein the saponification reaction is carried out for a reaction time of 5-15 min.
6. The method according to claim 2, wherein the acidic solution containing vanadium, molybdenum and nickel comprises any one or a combination of at least two of vanadium-containing shale, vanadium slag or an acidic solution obtained after sulfuric acid leaching of vanadium titano-magnetite after roasting.
7. The method of claim 2, wherein the acidic solution containing vanadium, molybdenum and nickel has a pH of 0.5 to 4.
8. The method according to claim 2, wherein the concentration of vanadium in the acidic vanadium-containing molybdenum-nickel solution is 1.0-2.5 g/L.
9. The method according to claim 2, wherein the concentration of molybdenum element in the acidic solution containing vanadium, molybdenum and nickel is 0.1-1.0 g/L.
10. The method according to claim 2, wherein the concentration of nickel element in the acidic solution containing vanadium, molybdenum and nickel is 0.5-1.0 g/L.
11. The method of claim 2, wherein the extracting comprises shaking.
12. The method of claim 2, wherein the extracted phase ratio O/W is (1:1) - (6: 1).
13. The method of claim 2, wherein the temperature of the extraction is 25-65 ℃.
14. The method according to claim 2, wherein the extraction time is 5-30 min.
15. The method of claim 2, wherein the number of stages of extraction is 6 to 10.
16. The method according to claim 2, wherein the first stripping also yields a molybdenum-containing organic solution.
17. The method according to claim 2, wherein the concentration of sulfuric acid in the aqueous solution containing vanadyl sulfate is 1.0-5.0 mol/L.
18. The method according to claim 2, wherein the first stripping comprises oscillating stripping.
19. The method according to claim 2, wherein the phase ratio O/W of the first stripping is (1:1) - (6: 1).
20. The method according to claim 2, wherein the temperature of the first stripping is 25-65 ℃.
21. The method according to claim 2, wherein the time for the first stripping is 5-30 min.
22. The method according to claim 2, wherein the stage number of the first back extraction is 6-10.
23. The method of claim 16, further comprising the following step after step (2):
(3) and mixing the molybdenum-containing organic solution with a sodium hydroxide solution, and performing secondary back extraction to obtain a molybdenum-containing aqueous solution and finish regeneration and recovery of an extracting agent.
24. The process of claim 23, wherein the concentration of sodium hydroxide in the aqueous molybdenum-containing solution is from 0.5 to 5.0 mol/L.
25. The method according to claim 23, wherein the second stripping comprises oscillating stripping.
26. The method of claim 23, wherein the second stripping has a phase ratio O/W of (1:1) - (5: 1).
27. The process according to claim 23, wherein the temperature of the secondary stripping is 25-65 ℃.
28. The method of claim 23, wherein the time for the second stripping is 5-30 min.
29. The method of claim 23, wherein the secondary stripping is performed in stages of 1 to 3.
30. The process of claim 23, wherein the regenerated and recovered extractant in step (3) is returned to the extraction process in step (1).
31. Method according to claim 2, characterized in that it comprises the following steps:
(1) mixing an acidic vanadium-containing molybdenum-nickel solution with the vanadium element concentration of 1.0-2.5g/L, the molybdenum element concentration of 0.1-1.0g/L and the nickel element concentration of 0.5-1.0g/L with an extractant subjected to sodium hydroxide saponification reaction, and performing oscillation extraction with the O/W ratio of (1:1) - (6:1), the temperature of 25-65 ℃, the time of 5-30min and the stage number of 6-10 to obtain a nickel-containing aqueous solution and a vanadium-molybdenum-containing organic solution;
(2) mixing the vanadium-molybdenum-containing organic solution with 1.0-5.0mol/L sulfuric acid solution, and performing oscillation once back extraction with the comparison ratio of O/W (1:1) - (6:1), 25-65 ℃, 5-30min and 6-10 stages to obtain vanadyl sulfate-containing aqueous solution and molybdenum-containing organic solution with the molybdenum element concentration of 0.5-10.0 g/L;
(3) Mixing the molybdenum-containing organic solution with 0.5-5.0mol/L sodium hydroxide solution, performing oscillation secondary back extraction with the comparison of O/W (1:1) - (5:1), 25-65 ℃, 5-30min and 1-3 stages to obtain a molybdenum-containing aqueous solution and complete regeneration and recovery of an extracting agent, and returning the regenerated and recovered extracting agent to the extraction process in the step (1);
wherein, the extracting agents in the step (1) and the step (3) respectively and independently contain the following components in volume ratio: extracting agent P204: extracting agent TBP: isooctyl alcohol: extractant Cyanex 272: sulfonated kerosene (10-15), (1-5) and (70-87).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111332041.7A CN113929139B (en) | 2021-11-11 | 2021-11-11 | Extracting agent and method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111332041.7A CN113929139B (en) | 2021-11-11 | 2021-11-11 | Extracting agent and method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113929139A CN113929139A (en) | 2022-01-14 |
| CN113929139B true CN113929139B (en) | 2022-06-28 |
Family
ID=79286102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111332041.7A Active CN113929139B (en) | 2021-11-11 | 2021-11-11 | Extracting agent and method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113929139B (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06192761A (en) * | 1992-12-24 | 1994-07-12 | Catalysts & Chem Ind Co Ltd | Separation and recovering method for molybdenum |
| CN104319413A (en) * | 2014-09-16 | 2015-01-28 | 青岛乾运高科新材料股份有限公司 | Vanadyl-sulfate electrolyte preparation method applied to full-vanadium flow cell |
| CN106521153B (en) * | 2016-11-17 | 2018-08-03 | 中国科学院长春应用化学研究所 | The phosphine extractant of neutrality containing amino is used for the purposes and method of extraction and separation uranium |
| CN107226484B (en) * | 2017-05-12 | 2019-04-05 | 重庆康普化学工业股份有限公司 | A kind of method that compound extracting prepares vanadic anhydride |
| CN107475540B (en) * | 2017-08-30 | 2019-03-29 | 河南理工大学 | A kind of technique of titanium white devil liquor recovery vanadium and titanium |
| CN107828961B (en) * | 2017-11-02 | 2024-04-05 | 中国科学院过程工程研究所 | Extraction method of rare earth element ions and obtained rare earth enrichment liquid |
| CN110629051B (en) * | 2018-06-25 | 2021-02-26 | 中国科学院过程工程研究所 | Method for extracting and separating chromium from alkaline vanadium-chromium-containing solution |
| CN109097570B (en) * | 2018-09-25 | 2020-06-19 | 中国科学院长春应用化学研究所 | Application and method of amino-containing acidic phosphine extraction agent for extracting and separating cobalt and nickel |
| CN111628202B (en) * | 2020-06-09 | 2021-12-07 | 中国恩菲工程技术有限公司 | VOSO4Preparation method of sulfuric acid solution and VOSO4Electrolyte solution |
-
2021
- 2021-11-11 CN CN202111332041.7A patent/CN113929139B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113929139A (en) | 2022-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107419104B (en) | The comprehensive recovering process of useless SCR denitration | |
| CN114436328B (en) | Method for preparing vanadyl sulfate electrolyte from sodium vanadate-containing solution | |
| CN112538569B (en) | Method for separating nickel, cobalt and manganese from feed liquid containing nickel, cobalt and manganese | |
| CN104263946A (en) | Method for recovering tungsten, vanadium and titanium from waste SCR (selective catalytic reduction) denitration catalyst | |
| CN104046786B (en) | A kind of method reclaiming metal from vanadium slag | |
| CN101955228A (en) | Method for separating tantalum and niobium | |
| CN112520790A (en) | Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant | |
| CN115286019A (en) | Method for producing high-purity lithium carbonate from spodumene | |
| EP4209605A1 (en) | Method for recycling nickel, cobalt and manganese from feed liquid containing nickel, cobalt and manganese | |
| CN113929139B (en) | Extracting agent and method for preparing vanadyl sulfate from acidic solution containing vanadium, molybdenum and nickel | |
| CN111304451B (en) | Method for recycling waste vanadium catalyst by using phosphoric acid solution | |
| CN110229964B (en) | Method for extracting rubidium from fly ash | |
| CN116404220A (en) | Method for preparing high-concentration vanadium electrolyte by vanadate crystallization purification-chemical reduction | |
| CN112320847B (en) | Method for extracting vanadium from high-phosphate vanadium solution and recycling wastewater | |
| CN111732123B (en) | Method for preparing magnesium metavanadate from waste SCR denitration catalyst | |
| CN108975402A (en) | A method of preparing bulky grain high purity vanadic anhydride | |
| CN114349047B (en) | Method for preparing vanadyl sulfate by reduction back extraction method | |
| CN115094250A (en) | Method for recovering hafnium and other metals from hafnium-containing waste residues | |
| CN115181867A (en) | Hafnium-zirconium separation method | |
| CN115215368A (en) | Method for regenerating raw materials of waste cadmium-nickel battery based on solvent extraction | |
| CN114250362A (en) | Method for separating, purifying and recycling waste lithium ion battery anode material and obtained anode material | |
| CN112569736B (en) | Tail gas recycling method in uranium oxide preparation process by ammonium uranyl tricarbonate | |
| CN114772642B (en) | Preparation method of high-purity vanadyl sulfate solution | |
| CN114525405B (en) | Method for preparing nickel powder and cobalt powder by utilizing nickel-cobalt-containing waste liquid | |
| CN117303330B (en) | Method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |