CN111304466B - Method for selectively separating vanadium and chromium from vanadium and chromium-containing solution - Google Patents

Method for selectively separating vanadium and chromium from vanadium and chromium-containing solution Download PDF

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CN111304466B
CN111304466B CN202010167445.4A CN202010167445A CN111304466B CN 111304466 B CN111304466 B CN 111304466B CN 202010167445 A CN202010167445 A CN 202010167445A CN 111304466 B CN111304466 B CN 111304466B
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CN111304466A (en
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韩桂洪
刘兵兵
黄艳芳
苏盛鹏
薛毓斌
王益壮
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Zhengzhou University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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
    • C22B3/40—Mixtures
    • C22B3/409—Mixtures at least one compound being an organo-metallic compound
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for selectively separating vanadium and chromium from a vanadium and chromium-containing solution, which comprises the steps of adding a pH regulator into the vanadium and chromium-containing solution to convert vanadium in the solution into poly vanadate radical and chromium in the solution into dichromate radical, adding a selective floating extraction agent into the solution to promote the floating extraction agent and the poly vanadate radical to form a molecular association, adding an association stabilizer and a bubble dispersing agent, introducing air to make bubbles hydrophobic and mineralize to form poly vanadate radical-floating extraction agent-bubble micro-droplets, and finally enriching and separating poly vanadate radical components through floating extraction depth; adding reducing agent into the chromium-enriched flotation residual liquid to obtain Cr6+Reduction to Cr3+Finally, the pH of the solution is regulated to lead the chromium to be Cr (OH)3Precipitating in a precipitation mode, and drying and calcining the vanadium-rich and chromium-rich components to obtain a high-purity vanadium-chromium product. The method has good selective separation effect on vanadium and chromium, simple process flow and low operation cost, and is particularly suitable for deep separation of vanadium and chromium.

Description

Method for selectively separating vanadium and chromium from vanadium and chromium-containing solution
Technical Field
The invention belongs to the field of hydrometallurgy, and particularly relates to a method for selectively separating vanadium and chromium from a solution by using a planktonic extraction method.
Background
Vanadium and chromium are used as important scarce strategic metal resources and are widely applied to the fields of steel, metallurgy, chemical industry, medicine, aerospace and the like. The vanadium and the chromium belong to the fourth-period transition metal, are close to each other in the periodic table of elements, have extremely similar physicochemical properties, and are often associated in vanadium titano-magnetite and chromite in the nature. The vanadium and chromium products have high requirements on the content of associated elements, such as V2O5The chromium content is required to be less than 0.15 wt%, Cr2O3In which the vanadium content is required to be less than 0.1 wt.%. However, the associated presence of vanadium and chromium in minerals and the highly similar physicochemical properties make the separation of vanadium and chromium very difficult.
In order to solve the problem of vanadium-chromium separation, a common idea is to prepare a vanadium-chromium product after a vanadium-chromium-containing raw material is pretreated by roasting and the like and then leached and subjected to vanadium-chromium separation. In the leaching process, vanadium and chromium in the raw materials can simultaneously enter a solution (leachate or acidic wastewater), so that the deep separation of vanadium and chromium is a precondition for obtaining a high-purity vanadium and chromium product. At present, the common methods for separating the dissolved vanadium and chromium mainly comprise chemical precipitation, ion exchange, solvent extraction and the like.
Chemical precipitation method: the separation and recovery of valuable metals in the leaching solution are realized through the selective precipitation of ions, and the separation and recovery mainly comprises ammonium salt precipitation and calcium salt precipitation. If the ammonium salt reacts with vanadate under alkalescent conditions to generate ammonium metavanadate, the solubility of the ammonium metavanadate in water is far lower than that of ammonium dichromate, the ammonium metavanadate is precipitated in a crystallization form, and chromium is remained in the solution, so that the vanadium-chromium separation is realized; under the acidic condition, ammonium salt reacts with vanadate to generate ammonium polyvanadate precipitate. For sodium chromate alkali solutions containing a small amount of vanadium, a calcium precipitation method based on the formation of calcium vanadate precipitates from calcium ions and vanadate radicals is a common method for removing vanadium. Royal jelly and the like (CN 110343866A) adopt an ammonium salt precipitation method to separate vanadium and chromium from the vanadium and chromium reduction slag, and ammonium vanadate and ammonium salt form ammonium polyvanadate precipitate, thereby realizing the separation of vanadium and chromium. The Wangming jade of the university of Zhongnan, etc. (CN 110629047A) adopts an ammonium precipitation method to separate and extract vanadium and chromium from a vanadium and chromium-containing solution, provides a recovery idea of first-stage vanadium precipitation, selective reduction of Cr (VI), second-stage recovery of vanadium and chromium precipitation, and realizes vanadium and chromium separation by combined regulation and control of pH.
Ion exchange method: the separation is carried out according to the difference of the adsorption performance of the ion exchange resin to the metal ions. The ions in the solution can be exchanged with active groups with the same charge in the resin, so as to achieve the purpose of selectively removing certain ions. For example, the pH value of the solution is regulated to make hexavalent chromium in the solution be CrO4 2-Form exists according to VO3 -Has ion exchange selectivity far greater than CrO4 2-The vanadium and chromium can be separated through an ion exchange process. Yankuliang et al (CN 101538652A) adopt an ion exchange method to separate and recover vanadium and chromium from vanadium and chromium waste, and exchange vanadium through D201 resin, thereby realizing vanadium and chromium separation.
Solvent extraction method: the selective separation of metal ions is achieved according to the difference in the partition coefficient of the metal ions between the aqueous and organic phases. By utilizing the difference of the affinity of the organic extractant to vanadium and chromium, vanadium enters an organic phase and chromium remains in a water phase in the extraction process, thereby achieving the purpose of separating vanadium and chromium. Such as primary amine N1923 vs HVO4 2-The extraction capacity of the catalyst is far greater than that of CrO4 2-Therefore, the extraction separation of vanadium and chromium can be realized by adopting the primary amine extractant. The method comprises the steps of extracting and separating vanadium and chromium from a vanadium-chromium slag acid leaching solution by a solvent extraction method in Li Yong et al (CN 107312942A) of northeast university, extracting pentavalent vanadium and hexavalent chromium in the vanadium-chromium slag acid leaching solution to an organic phase, and separating the vanadium by back extraction to realize the separation of the vanadium and the chromium.
The vanadium-chromium separation method is particularly suitable for high-concentration vanadium-chromium separation systems, and most methods can only be used for alkaline systems. The method for separating and extracting vanadium and chromium from the solution containing vanadium and chromium can only meet the general requirements of the market, the separation degree of vanadium and chromium is low, and high-purity vanadium and chromium products are difficult to obtain. Therefore, on the basis of the existing research on the vanadium-chromium separation method, the difference between the properties of vanadium and chromium is further and deeply researched, and the feasible vanadium-chromium deep separation method has important application value.
Disclosure of Invention
Aiming at the problems that the prior vanadium-chromium separation technology is difficult to realize selective deep separation and the like, the invention aims to provide a method for selectively separating vanadium and chromium from a vanadium-chromium-containing solution, the method adopts a selective floating extraction agent to regulate and control the selectivity of vanadate ions, so that the floating extraction agent and poly-vanadate form a molecular association complex, chromate still exists in the solution, and then the vanadate components are selectively enriched and separated by a floating extraction technology; adding reducing agent into the chromium-enriched flotation residual liquid to obtain Cr6+Reduction to Cr3+Then the pH of the solution is controlled to lead the chromium to be Cr (OH)3Precipitating in a precipitation form, and finally realizing the selective and efficient separation of vanadium and chromium.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a process for selectively separating V and Cr from the solution containing V and Cr includes such steps as dissolving V in water, separating by centrifugal separation, and removing impuritiesAdding a pH regulator into a solution containing vanadium and chromium to convert vanadium in the solution into a polyvanadate radical and chromium into dichromate, adding a selective extraction agent into the solution to promote the extraction agent and the polyvanadate radical to form a molecular association, adding an association stabilizer and a bubble dispersing agent, introducing air to form microbubbles with the diameter of 100 nm-10 mu m to make bubbles hydrophobic and mineralize to form polyvanadate radical-extraction agent-bubble micro-droplets, and finally separating polyvanadate components through floating extraction and enrichment; adding reducing agent into the chromium-enriched flotation residual liquid to obtain Cr6+Reduction to Cr3+Finally, the pH of the solution is regulated to lead the chromium to be Cr (OH)3Precipitate of the above-mentioned polyvanadate, Cr (OH)3And drying and calcining the precipitate at high temperature to obtain a high-purity vanadium pentoxide product and a high-purity chromium trioxide product.
The key point of the method is to regulate and control the selectivity difference of the flotation reagent to the vanadium chromate radical, and convert vanadium in the solution into the polyvanadate radical and chromium into the dichromate radical by adjusting the pH value of the solution. According to the fact that the affinity of a primary amine type floating extraction agent to vanadate is far larger than that of chromate, on the basis, a floating extraction agent with high selectivity to vanadate is selected, and a vanadate component is enriched and separated on the basis of a floating extraction method; for Cr in solution6+By reduction to Cr3+Then the pH of the solution is controlled to lead the chromium to be Cr (OH)3Precipitating in a precipitation form, and finally realizing the selective and efficient separation of vanadium and chromium.
In a preferred scheme, the selective extraction agent comprises the following components in parts by mass: 30-60 parts of primary ammonium; 20-40 parts of ionic liquid; and 20-40 parts of tributyl phosphate (TBP). The primary amine is at least one of N1923, dodecylamine, hexadecylamine and octadecylamine; the ionic liquid is at least one of 1-octyl-3-methylimidazole tetrafluoroborate and trioctylmethylammonium nitrate; the addition amount of the selective extraction agent is 100 mg/L-10 g/L. The selective floatation agent has high selectivity on vanadate, and can realize deep separation of vanadate in a leaching solution.
In a preferred scheme, the reducing agent comprises the following components in parts by mass: 30-60 parts of alkyl xanthate; 20-40 parts of thiosulfate; 10-20 parts of sodium sulfide; 10-20 parts of sodium sulfite(ii) a The addition amount of the reducing agent is 100 mg/L-8 g/L. The above-mentioned reducing agent for Cr6+Has high reducibility, and can realize Cr in the leaching solution6+To Cr3+Complete conversion of (2).
Preferably, the association stabilizer comprises the following components in parts by mass: 30-60 parts of sodium sulfate; 20-40 parts of sodium humate; 20-40 parts of trisodium citrate; the addition amount of the association stabilizer is 100 mg/L-1 g/L. The stabilizer effectively avoids Cr6+Doping flotation.
In a preferred scheme, the bubble dispersing agent is at least one of water glass, sodium hexametaphosphate and humic acid; the addition amount of the bubble dispersing agent is 50-300 mg/L. The bubble dispersing agent can efficiently disperse bubbles and promote the bubbles to be hydrophobized and mineralized into micro-droplets.
Preferably, the pH adjusting agent for the solution of the present invention is inorganic acid/base, such as HNO, which is conventional in the art3And/or NaNO3HCl and/or NaOH, H2SO4And/or Na2SO4Adding a pH regulator to adjust the pH of the solution to 6.8; chromium is converted into Cr (OH) by regulating the pH of the solution to be 93Precipitating in a precipitation form.
In a preferred scheme, the drying refers to drying at 100-150 ℃ for 30-60 min, and the calcining refers to calcining at 500-600 ℃ for 4-6 h.
In a preferable scheme, the vanadium-chromium solution is derived from leachate or wastewater of waste vanadium/chromium catalysts, waste vanadium batteries, vanadium-chromium slag and the like, and the concentration ranges of vanadium ions and chromium ions in the solution are both 50 mg/L-5 g/L.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention realizes the selective separation of vanadium and chromium by a floating extraction method. By adjusting proper pH value and adding selective extraction agent, and according to the condition that the affinity of primary amine extraction agent to vanadate is far larger than that of chromate, selecting primary amine extraction agent to efficiently enrich and separate vanadate component; for Cr in the flotation raffinate6+By reduction to Cr3+Then the pH of the solution is controlled to lead the chromium to be Cr (OH)3Precipitation ofAnd finally, the selective and efficient separation of vanadium and chromium is realized. The floating extraction overcomes the defects of low separation efficiency, long process and high operation cost of the traditional vanadium-chromium separation method, and can realize deep separation on low-concentration vanadium-chromium ion solution. Thus, this technique has significant advantages over conventional separation methods.
The invention adopts the floating extraction process, and has the advantages that: can process vanadium-chromium ion solutions with different concentration ranges; even if the concentration of vanadium and chromium ions in the solution is low, the selective deep separation of vanadium and chromium can be realized. In addition, the prior floating extraction technology is rarely reported in the field of vanadium-chromium separation.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be noted that these examples are only for better understanding of the present invention, and do not limit the scope of the present invention.
Example 1
A method for selectively separating vanadium and chromium from a vanadium and chromium-containing solution is shown in figure 1 and comprises the following steps:
(1) adding 1 mol/L hydrochloric acid and/or 1 mol/L sodium hydroxide into 1L of solution with 5 g/L vanadate concentration and 5 g/L chromate concentration, and adjusting the pH value of the solution to be 6.8 to convert vanadium in the solution into poly vanadate and convert chromium into dichromate;
(2) adding a selective floating extractant into the solution, wherein the selective floating extractant comprises the following components: primary amine N192350 parts by mass, 1-octyl-3-methylimidazole tetrafluoroborate 30 parts by mass, tributyl phosphate 20 parts by mass with the concentration of 10 g/L, and an association stabilizer is added, wherein the association stabilizer comprises the following components: 40 parts of sodium sulfate, 30 parts of sodium humate and 30 parts of trisodium citrate, wherein the concentration is 500 mg/L, and then sodium hexametaphosphate dispersant is added, the concentration is 200 mg/L, in the whole flotation process, air is introduced into the solution to form microbubbles with the diameter of 100 nm-10 mu m, the hydrophobic and mineralized bubbles, polyvanadate acid radicals and the micro-droplets of the flotation reagent are selectively floated and enriched for 5 min, and the foam product is a polyvanadate component;
(3) and then adding a reducing agent into the chromium-enriched flotation residual liquid, wherein the reducing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of sodium sulfide and 10 parts by mass of sodium sulfite, wherein the concentration of the sodium alkyl xanthate is 5 g/L, and Cr is added6+Reduction to Cr3+Then, the solution pH =9 was adjusted by 0.5 mol/L NaOH solution to make chromium Cr (OH)3Precipitating in a form, and filtering to obtain Cr (OH)3Precipitating;
(4) the above-mentioned polyvanadate, Cr (OH)3Drying the precipitate at 120 ℃ for 60 min, and calcining at 580 ℃ for 5 h to obtain high-purity vanadium pentoxide and chromium trioxide products.
The mass of the vanadium pentoxide product is 4.835 g, the impurity chromium content in the vanadium pentoxide is 90 mg, and the purity of the vanadium pentoxide product is as high as 98.1%; the mass of the chromium trioxide product is 4.91 g, the content of vanadium in the chromium trioxide is 165 mg, the purity of the chromium trioxide product is up to 96.6%, and the vanadium-chromium separation effect is good.
Example 2
A method for selectively separating vanadium and chromium from a vanadium and chromium-containing solution is shown in figure 1 and comprises the following steps:
(1) adding 1 mol/L hydrochloric acid and/or 1 mol/L sodium hydroxide into 1L of solution with the vanadate concentration of 2 g/L and the chromate concentration of 500 mg/L, and adjusting the pH value of the solution to be 6.8 to convert vanadium in the solution into poly vanadate and convert chromium in the solution into dichromate;
(2) adding a selective floating extractant into the solution, wherein the selective floating extractant comprises the following components: primary amine N192360 parts by mass, 1-octyl-3-methylimidazole tetrafluoroborate 20 parts by mass, tributyl phosphate 20 parts by mass with the concentration of 4 g/L, and an association stabilizer is added, wherein the association stabilizer comprises the following components: 40 parts of sodium sulfate, 30 parts of sodium humate and 30 parts of trisodium citrate, wherein the concentration is 200 mg/L, then adding a sodium hexametaphosphate dispersant with the concentration of 100 mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, selectively floating and enriching hydrophobic and mineralized bubbles, polyvanadate acid radical and floating extraction agent droplets for 5 min, and obtaining a foam product, namely a polyvanadate component;
(3) and then adding a reducing agent into the chromium-enriched flotation residual liquid, wherein the reducing agent comprises the following components: 60 parts by mass of sodium hydrocarbyl xanthate20 parts of sodium thiosulfate, 10 parts of sodium sulfide and 10 parts of sodium sulfite, wherein the concentration is 2 g/L, and Cr is6+Reduction to Cr3+Then, the solution pH =9 was adjusted by 0.5 mol/L NaOH solution to make chromium Cr (OH)3Precipitating in a form, and filtering to obtain Cr (OH)3Precipitating;
(4) the above-mentioned polyvanadate, Cr (OH)3Drying the precipitate at 120 ℃ for 60 min, and calcining at 580 ℃ for 5 h to obtain vanadium pentoxide and chromium trioxide products.
The mass of the vanadium pentoxide product is 1.948 g, the impurity chromium content in the vanadium pentoxide is 19.5 mg, and the purity of the vanadium pentoxide product is as high as 97.4%; the mass of the chromium trioxide product is 480.5 mg, the content of vanadium in the chromium trioxide is 52 mg, the purity of the chromium trioxide product is 89.2%, and the vanadium-chromium separation effect is good.
Example 3
A method for selectively separating vanadium and chromium from a vanadium and chromium-containing solution is shown in figure 1 and comprises the following steps:
(1) adding 1 mol/L hydrochloric acid and/or 1 mol/L sodium hydroxide into 1L of solution with 100 mg/L vanadate concentration and 100 mg/L chromate concentration, and adjusting the pH value of the solution to be 6.8 to convert vanadium in the solution into poly vanadate and convert chromium into dichromate;
(2) adding a selective floating extractant into the solution, wherein the selective floating extractant comprises the following components: primary amine N192350 parts by mass, 1-octyl-3-methylimidazole tetrafluoroborate 30 parts by mass, tributyl phosphate 20 parts by mass with the concentration of 200 mg/L, and an association stabilizer is added, wherein the association stabilizer comprises the following components: 40 parts of sodium sulfate, 30 parts of sodium humate and 30 parts of trisodium citrate, wherein the concentration is 100 mg/L, then adding a sodium hexametaphosphate dispersant with the concentration of 80 mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, selectively floating and enriching hydrophobic and mineralized bubbles, polyvanadate acid radical and floating extraction agent droplets for 5 min, and obtaining a foam product, namely a polyvanadate component;
(3) and then adding a reducing agent into the chromium-enriched flotation residual liquid, wherein the reducing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of sodium sulfide and 10 parts by mass of sodium sulfite, wherein the concentration of the sodium alkyl xanthate is 200 mg/L, and Cr is added6+Reduction to Cr3+Then, the solution pH =9 was adjusted by 0.5 mol/L NaOH to make chromium Cr (OH)3Precipitating in a form, and filtering to obtain Cr (OH)3Precipitating;
(4) the above-mentioned polyvanadate, Cr (OH)3Drying the precipitate at 120 ℃ for 60 min, and calcining at 580 ℃ for 5 h to obtain high-purity vanadium pentoxide and chromium trioxide products.
The mass of the vanadium pentoxide product is 97.8 mg, the impurity chromium content in the vanadium pentoxide is 1.4 mg, and the purity of the vanadium pentoxide product is as high as 98.6%; the mass of the chromium trioxide product is 98.6 mg, the content of vanadium in the chromium trioxide is 2.2 mg, the purity of the chromium trioxide product is as high as 97.8%, and the vanadium and chromium separation effect is good.
Comparative example 1
The pH in this comparative example is not within the preferred range.
(1) Adding 1 mol/L hydrochloric acid and/or 1 mol/L sodium hydroxide into 1L of solution with 5 g/L vanadate concentration and 5 g/L chromate concentration, and adjusting the pH value of the solution to be 9.2 to convert vanadium in the solution into poly vanadate and convert chromium into dichromate;
(2) adding a selective floating extractant into the solution, wherein the selective floating extractant comprises the following components: primary amine N192350 parts by mass, 1-octyl-3-methylimidazole tetrafluoroborate 30 parts by mass, tributyl phosphate 20 parts by mass with the concentration of 10 g/L, and an association stabilizer is added, wherein the association stabilizer comprises the following components: 40 parts of sodium sulfate, 30 parts of sodium humate and 30 parts of trisodium citrate, wherein the concentration is 500 mg/L, then adding a sodium hexametaphosphate dispersant with the concentration of 200 mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, selectively floating and enriching hydrophobic and mineralized bubbles, polyvanadate acid radical and floating extraction agent droplets for 5 min, and obtaining a foam product, namely a polyvanadate component;
(3) and then adding a reducing agent into the chromium-enriched flotation residual liquid, wherein the reducing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of sodium sulfide and 10 parts by mass of sodium sulfite, wherein the concentration of the sodium alkyl xanthate is 5 g/L, and Cr is added6+Reduction to Cr3+Then, the solution pH =9 was adjusted by 0.5 mol/L NaOH solution to make chromium Cr (OH)3Precipitating in a form, and filtering to obtain Cr (OH)3Precipitation of；
(4) The above-mentioned polyvanadate, Cr (OH)3Drying the precipitate at 120 ℃ for 60 min, and calcining at 580 ℃ for 5 h to obtain vanadium pentoxide and chromium trioxide products.
The mass of the vanadium pentoxide product is 3.735 g, the impurity chromium content in the vanadium pentoxide is 1.585 g, and the purity of the vanadium pentoxide product is only 57.6%; the mass of the chromium trioxide product is 3.415 g, the content of vanadium as an impurity in the chromium trioxide is 1.265 g, the purity of the chromium trioxide product is only 63.0%, and the vanadium-chromium separation effect is poor.
Comparative example 2
The first stripping agent ratio in this comparative example is not within the preferred range.
(1) 1 mol/L hydrochloric acid and/or 1 mol/L sodium hydroxide are added into 1L of solution with 100 mg/L vanadate concentration and 100 mg/L chromate concentration, the pH value of the solution is adjusted to 6.8, and vanadium in the solution is converted into poly vanadate and chromium is converted into dichromate.
(2) Adding a selective floating extractant into the solution, wherein the selective floating extractant comprises the following components: primary amine N192320 parts by mass, 1-octyl-3-methylimidazole tetrafluoroborate 30 parts by mass, tributyl phosphate 50 parts by mass with the concentration of 100 mg/L, and an association stabilizer is added, wherein the association stabilizer comprises the following components: 40 parts of sodium sulfate, 30 parts of sodium humate and 30 parts of trisodium citrate, wherein the concentration is 100 mg/L, then adding a sodium hexametaphosphate dispersant with the concentration of 80 mg/L, introducing air into the solution to form microbubbles with the diameter of 100 nm-10 mu m, selectively floating and enriching hydrophobic and mineralized bubbles, polyvanadate acid radical and floating extraction agent droplets for 5 min, and obtaining a foam product, namely a polyvanadate component;
(3) and then adding a reducing agent into the chromium-enriched flotation residual liquid, wherein the reducing agent comprises the following components: 50 parts by mass of sodium alkyl xanthate, 30 parts by mass of sodium thiosulfate, 10 parts by mass of sodium sulfide and 10 parts by mass of sodium sulfite, wherein the concentration of the sodium alkyl xanthate is 200 mg/L, and Cr is added6+Reduction to Cr3+Then, the solution pH =9 was adjusted by 0.5 mol/L NaOH solution to make chromium Cr (OH)3Precipitating in a form, and filtering to obtain Cr (OH)3Precipitating;
(4) the above-mentioned polyvanadate, Cr (OH)3Drying the precipitate at 120 deg.C for 60 min, calcining at 580 deg.C for 5 hr to obtain pentoxideVanadium oxide and chromium trioxide.
The mass of the vanadium pentoxide product is 73.8 mg, the impurity chromium content in the vanadium pentoxide is 28.4 mg, and the purity of the vanadium pentoxide product is only 61.5%; the mass of the chromium trioxide product is 71.6 mg, the content of vanadium as an impurity in the chromium trioxide is 26.2 mg, the purity of the chromium trioxide product is only 63.4%, and the vanadium-chromium separation effect is poor.
In conclusion, through comparative example analysis, the vanadium-chromium separation efficiency can be remarkably improved by the floating extraction technology for vanadium-chromium solutions with different concentration ranges. And the technology has the advantages of less medicament consumption, simple operation and lower equipment requirement, and is suitable for industrial scale-up production.

Claims (8)

1. A method for selectively separating vanadium and chromium from a vanadium and chromium-containing solution is characterized by comprising the following steps: adding a pH regulator into a solution containing vanadium and chromium, regulating the pH of the solution to be 6.8 after adding the pH regulator to convert vanadium in the solution into a polyvanadate radical and convert chromium into dichromate, adding a selective floating extraction agent into the solution to promote the floating extraction agent and the polyvanadate radical to form a molecular association, adding an association stabilizer and a bubble dispersing agent, and introducing air to perform flotation separation, wherein a foam product is a polyvanadate component; adding reducing agent into the flotation residual liquid to add Cr6+Reduction to Cr3+Finally, the pH of the solution is regulated to lead the chromium to be Cr (OH)3Precipitate of the above-mentioned polyvanadate, Cr (OH)3Drying and calcining the precipitate to obtain a vanadium product and a chromium product respectively; the selective extraction agent comprises the following components in parts by mass: 30-60 parts of primary amine, 20-40 parts of ionic liquid and 20-40 parts of tributyl phosphate; the primary amine is at least one of N1923, dodecylamine, hexadecylamine and octadecylamine; the ionic liquid is at least one of 1-octyl-3-methylimidazole tetrafluoroborate and trioctylmethylammonium nitrate; the association stabilizer comprises the following components in parts by mass: 30-60 parts of sodium sulfate, 20-40 parts of sodium humate and 20-40 parts of trisodium citrate.
2. The method for selectively separating vanadium and chromium from a vanadium and chromium containing solution according to claim 1, wherein the addition amount of the selective stripping agent is 100 mg/L-10 g/L.
3. The method for selectively separating vanadium and chromium from a vanadium and chromium containing solution according to claim 1, characterized in that the reducing agent consists of the following components in parts by mass: 30-60 parts of alkyl sodium xanthate, 20-40 parts of sodium thiosulfate, 10-20 parts of sodium sulfide and 10-20 parts of sodium sulfite; the addition amount of the reducing agent is 100 mg/L-8 g/L.
4. The method for selectively separating vanadium and chromium from a vanadium and chromium containing solution according to claim 1, wherein the addition amount of the association stabilizer is 100 mg/L-1 g/L.
5. The method for selectively separating vanadium and chromium from a vanadium and chromium containing solution according to claim 1, wherein the bubble dispersing agent is at least one of water glass, sodium hexametaphosphate and humic acid; the addition amount of the bubble dispersing agent is 50-300 mg/L.
6. The method for selectively separating vanadium and chromium from a vanadium and chromium containing solution according to claim 1, characterized in that the solution pH regulator is one of the following: (1) HNO3And/or NaNO3(2) HCl and/or NaOH, (3) H2SO4And/or Na2SO4(ii) a Chromium is converted into Cr (OH) by regulating the pH of the solution to be 93Precipitating in a precipitation form.
7. The method for selectively separating vanadium and chromium from a vanadium and chromium containing solution according to claim 1, wherein the drying is drying at 100-150 ℃ for 30-60 min, and the calcining is calcining at 500-600 ℃ for 4-6 h.
8. The method for selectively separating vanadium and chromium from a vanadium and chromium containing solution according to claim 1, wherein vanadium and chromium in the vanadium and chromium containing solution exist in the form of vanadate and chromate, and the concentrations of the vanadate and the chromate are both 50 mg/L-5 g/L.
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