CN116814990B - Method for extracting and separating vanadium in vanadium-arsenic solution by utilizing hydrophobic eutectic solvent - Google Patents
Method for extracting and separating vanadium in vanadium-arsenic solution by utilizing hydrophobic eutectic solvent Download PDFInfo
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- 230000005496 eutectics Effects 0.000 title claims abstract description 80
- 239000002904 solvent Substances 0.000 title claims abstract description 80
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 66
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 59
- WLMKEIPQEQYXIC-UHFFFAOYSA-N [V].[As] Chemical compound [V].[As] WLMKEIPQEQYXIC-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 108
- 239000001257 hydrogen Substances 0.000 claims abstract description 108
- 238000000605 extraction Methods 0.000 claims abstract description 61
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005191 phase separation Methods 0.000 claims abstract description 24
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 20
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 18
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 16
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 21
- -1 arsenic ions Chemical class 0.000 claims description 12
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 abstract description 9
- 239000010937 tungsten Substances 0.000 abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000370 acceptor Substances 0.000 description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 34
- 230000010355 oscillation Effects 0.000 description 22
- 239000011780 sodium chloride Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012071 phase Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009993 causticizing Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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 application discloses a method for extracting and separating vanadium from a vanadium-arsenic solution by utilizing a hydrophobic eutectic solvent, which relates to the technical field of nonferrous metal metallurgy, and comprises the following steps of: s100: preparation of hydrophobic eutectic solvent: mixing a hydrogen bond acceptor with a hydrogen bond donor, wherein the hydrogen bond acceptor comprises tetrabutylammonium chloride or tetrabutylammonium bromide, and the hydrogen bond donor comprises n-octanol, n-nonanol or n-decanol, and reacting to form a hydrogen bond network, and S200: extraction and separation of vanadium: mixing the hydrophobic eutectic solvent with the vanadium-arsenic solution, oscillating, standing for phase separation, and back extraction after phase separation. The method can be applied to the precise separation of vanadium, arsenic, tungsten and other impurities in vanadium crystals, the pH value of the solution does not need to be deliberately adjusted in the extraction and separation process of vanadium and arsenic by adopting the hydrophobic eutectic solvent, the operation is simple, the economy is good, the safety is high, the safety risk in the extraction process can be greatly reduced, and the method has good application prospect in the extraction and separation process of vanadium and arsenic.
Description
Technical Field
The application relates to the technical field of nonferrous metal metallurgy, in particular to a method for extracting and separating vanadium in a vanadium-arsenic solution by utilizing a hydrophobic eutectic solvent.
Background
In a coal-fired power plant, the denitration activity of an SCR catalyst for denitration gradually decreases along with the increase of the operation time due to poisoning, aging and the like of active components, and at present, the waste SCR catalyst mainly adopts an alkaline leaching-step precipitation process to lead elements such as vanadium, arsenic, silicon, phosphorus and the like and TiO 2 And separating the carrier, and then realizing step separation by utilizing the solubility difference of each element under the conditions of different temperatures and alkali concentrations. The application number CN202110213239.7 discloses a method for separating vanadium, tungsten and arsenic from sodium hydroxide waste liquid and application thereof, which comprises the steps of evaporating, concentrating and cooling crystallization treatment of the sodium hydroxide waste liquid to crystallize vanadate ions, tungstate ions and arsenate ions to obtain alkali treatment crystals (namely vanadium crystals), dissolving the vanadium crystals, regulating the concentration of sodium hydroxide in a system and carrying out causticizing reaction twice, forming gradient precipitation of each element according to different solubilities under different alkali concentrations, carrying out causticizing reaction for multiple times after obtaining the vanadium crystals, realizing separation of vanadium, tungsten and arsenic, and having complex operation steps, regulating the alkali concentration in the system for multiple times, and improving production process cost.
The extraction method is a common method for separating similar ions or ionic groups, but the traditional extraction method has the characteristics of high cost, strong volatility and poor safety of the extractant, and has larger difference from the environment-friendly production concept. The development of efficient green novel extractants has received great attention. The ionic liquid is a novel extractant with low vapor pressure and high stability, but has the defects of high preparation cost and poor degradability. The eutectic solvent has similar properties with the ionic liquid, has the advantages of extremely low vapor pressure, good thermal stability and chemical stability, and the eutectic solvent has simple preparation and good biodegradability, and is widely focused by researchers. At present, a specific extraction separation method capable of accurately separating vanadium, arsenic and tungsten in the vanadium crystal purification process after alkali treatment of a waste SCR catalyst is not available.
Disclosure of Invention
In view of the above, the present application provides a method for extracting and separating vanadium from a vanadium-arsenic solution by using a hydrophobic eutectic solvent, wherein the hydrophobic eutectic solvent can be applied to the precise separation of vanadium, arsenic and tungsten in a vanadium crystal, and meanwhile, the pH value of the solution does not need to be adjusted in the extraction and separation process of the present application, and the hydrophobic eutectic solvent and the vanadium-arsenic solution can be mixed to adjust the vanadium-arsenic solution system to be extracted to a suitable range.
In a first aspect, the present application provides a method for extracting and separating vanadium from a vanadium-arsenic solution using a hydrophobic eutectic solvent, the method comprising the steps of: s100: preparation of hydrophobic eutectic solvent: a hydrogen bond acceptor comprising tetrabutylammonium chloride or tetrabutylammonium bromide is mixed with a hydrogen bond donor comprising any one of n-octanol, n-nonanol, or n-decanol and reacted to form a hydrogen bond network. S200: extraction and separation of vanadium: mixing the hydrophobic eutectic solvent with the vanadium-arsenic solution, oscillating, standing for phase separation, and back extraction after phase separation. The application firstly provides a hydrophobic eutectic solvent suitable for accurately separating vanadium, arsenic and tungsten in vanadium crystals, a hydrogen bond network formed by the hydrophobic eutectic solvent can effectively extract vanadium ions in a vanadium-arsenic solution, and the responsiveness to other ions is not high. Preferably, the hydrogen bond acceptor comprises tetrabutylammonium bromide and the hydrogen bond donor comprises n-octanol.
In some embodiments, in step S100, the reaction temperature is 65-85 ℃, the reaction time is 3-5 h, and the stirring speed is 100-200 RPM. Preferably, the reaction temperature of the reaction is 70-80 ℃, the reaction time is 4-5 h, and the stirring speed is 180-200 RPM. When the reaction conditions of the specific hydrogen bond acceptor and the specific hydrogen bond donor are in the above range, the generated hydrogen bond network is more favorable for extracting vanadium ions in the vanadium-arsenic solution, and has low responsiveness to other ions.
In some embodiments, in step S100, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1-1.4. Preferably, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2.
In some embodiments, the viscosity of the hydrophobic eutectic solvent is 110-180 cp. Preferably, the viscosity of the hydrophobic eutectic solvent is 115-130 cp. The viscosity of the hydrophobic eutectic solvent is proper, which is more beneficial to the mass transfer process of droplet dispersion in the oscillating process after mixing with the vanadium-arsenic solution and the phase separation after extraction, thereby further improving the single-stage extraction rate of vanadium.
In some embodiments, mixing the hydrophobic eutectic solvent with the vanadium arsenic solution comprises: and mixing the hydrophobic eutectic solvent with the vanadium-arsenic solution according to the volume ratio of 1:1-2. Preferably, the hydrophobic eutectic solvent is mixed with the vanadium-arsenic solution according to the volume ratio of 1:1.
In some embodiments, the concentration of vanadium ions in the vanadium-arsenic solution is 9-12 g/L, the concentration of arsenic ions is 8-8.5 g/L, and the vanadium-arsenic solution further comprises 0.3-0.4 g/L of tungsten ions, 0.08-1 g/L of silicon ions and 0.4-0.6 g/L of phosphorus ions.
In some embodiments, in step S200, the oscillating includes oscillating at 40-60 ℃ for 8-12 min, and the standing time of the standing phase separation is 30-50 min.
In some embodiments, the oscillation has an oscillation amplitude of 38-42 mm and a rotation frequency of 280-320 RPM.
In some embodiments, in step S200, the stripping after phase separation includes: and after phase separation, obtaining a vanadium-loaded hydrophobic eutectic solvent (loaded organic phase), mixing a stripping agent and the vanadium-loaded hydrophobic eutectic solvent according to a volume ratio of 3-5:1, and oscillating and stripping for 5-10 min, wherein the concentration of the stripping agent NaCl solution is 1.5-2 mol/L.
The technical scheme provided by the embodiments of the application has the beneficial effects that at least: the hydrogen bond network formed by the hydrophobic eutectic solvent can effectively extract vanadium ions in the vanadium-arsenic solution, has lower extraction rate on other ions, can be applied to the accurate separation of vanadium from impurity ions such as arsenic, tungsten and the like in vanadium crystals, does not need to deliberately adjust the pH value of the solution in the extraction and separation process of vanadium and arsenic by adopting the hydrophobic eutectic solvent, has simple operation, good economy and high safety, can greatly reduce the safety risk in the extraction process, and has good application prospect in the extraction and separation process of vanadium and arsenic.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The eutectic solvent is a two-component or three-component eutectic mixture of Hydrogen Bond Donors (HBD) and Hydrogen Bond Acceptors (HBA) in a stoichiometric ratio. Because of the extensive hydrogen bonding network present in the eutectic solvent, the viscosity is tens of times greater than water at room temperature. Increasing the temperature or increasing the hydrogen bond donor content can effectively reduce the viscosity of the eutectic solvent. At present, a eutectic solvent capable of being specifically applied to the precise separation of vanadium and arsenic in the vanadium crystal purification process and a corresponding extraction separation method are not available.
A method for extracting and separating vanadium in a vanadium-arsenic solution by utilizing a hydrophobic eutectic solvent comprises the following steps:
s100: preparation of hydrophobic eutectic solvent: mixing a hydrogen bond acceptor with a hydrogen bond donor, wherein the hydrogen bond acceptor comprises tetrabutylammonium chloride or tetrabutylammonium bromide, and the hydrogen bond donor comprises n-octanol, n-nonanol or n-decanol, and reacting to form a hydrogen bond network, and S200: extraction and separation of vanadium: mixing the hydrophobic eutectic solvent with vanadium-arsenic solution, oscillating for extraction, standing for phase separation, and back extraction after phase separation.
In some embodiments, the hydrogen bond acceptor comprises tetrabutylammonium bromide and the hydrogen bond donor comprises n-octanol.
In some embodiments, in step S100, the reaction temperature is 65-85 ℃, the reaction time is 3-5 h, and the stirring speed of the reaction is 100-200 rpm.
Illustratively, the reaction temperature of the reaction is 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, or a range of any two values recited above.
Illustratively, the reaction time is 3h, 3.5h, 4h, 4.5h, 5h, or a range of any two values recited above.
Illustratively, the stirring speed of the reaction is 100RPM, 120RPM, 140RPM, 150RPM, 160RPM, 180RPM, 200RPM, or a range of any two values noted above.
In some embodiments, in step S100, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1-1.4.
Illustratively, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1, 1:1.2, 1:1.3, 1:1.4, or a range of any two values recited above.
In some embodiments, the viscosity of the hydrophobic eutectic solvent is 110-180 cp.
Illustratively, the viscosity of the hydrophobic eutectic solvent is 110cP, 115cP, 120cP, 125cP, 130cP, 135cP, 150cP, 160cP, 180cP, or a range of any two values described above.
In some embodiments, mixing the hydrophobic eutectic solvent with the vanadium arsenic solution comprises: and mixing the hydrophobic eutectic solvent with the vanadium-arsenic solution according to the volume ratio of 1:1-2.
Illustratively, the volume ratio of the hydrophobic eutectic solvent to the vanadium arsenic solution is 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8, 1:2, or a range of any two values of the foregoing.
In some embodiments, the concentration of vanadium ions in the vanadium-arsenic solution is 9-12 g/L, the concentration of arsenic ions is 8-8.5 g/L, and the vanadium-arsenic solution further comprises 0.3-0.4 g/L of tungsten ions, 0.08-1 g/L of silicon ions and 0.4-0.6 g/L of phosphorus ions.
In some embodiments, in step S200, the oscillating includes oscillating at 40-60 ℃, the oscillating time is 8-12 min, and the standing time of the standing phase separation is 30-50 min.
In some embodiments, the oscillation has a shimmy amplitude of 38-42 mm and a rotational frequency of 280-320 RPM.
In some embodiments, in step S200, the stripping after phase separation includes: mixing a stripping agent and a hydrophobic eutectic solvent loaded with vanadium according to a volume ratio of 3-5:1, and oscillating and stripping for 5-10 min, wherein the concentration of NaCl solution of the stripping agent is 1.5-2 mol/L.
The reagents used in the examples described below, if not specified, can be purchased from conventional biochemical reagent stores, and the methods used in the examples described below, if not specified, are all conventional in the art.
The vanadium crystal is dissolved to obtain a vanadium crystal solution with a pH value of 13, and the following examples and comparative examples take the vanadium crystal solution (i.e. vanadium-arsenic solution) as a research object, and the main element component contents are shown in Table 1:
TABLE 1
Example 1
Tetrabutylammonium chloride is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes after the oscillation for 10 minutes to split phases, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, and is shown in Table 2.
Example 2
Tetrabutylammonium chloride is used as a hydrogen bond acceptor, n-nonanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes for phase separation after oscillating for 10 minutes, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillating back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, see Table 2.
Example 3
Tetrabutylammonium chloride is used as a hydrogen bond acceptor, n-decyl alcohol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes for phase separation after oscillating for 10 minutes, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillating back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, see Table 2.
Example 4
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is oscillated for 10 minutes and then is stood for 30 minutes for phase separation, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, see Table 2.
Example 5
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-nonanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes for phase separation after oscillating for 10 minutes, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillating back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, see Table 2.
Example 6
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-decyl alcohol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes for phase separation after oscillating for 10 minutes, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillating back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, and is shown in Table 2.
Example 7
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the ambient temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes after the oscillation for 10 minutes, the mixture is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, see Table 2.
Example 8
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.1, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes after the oscillation for 10 minutes to split phases, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, and is shown in Table 2.
Example 9
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.3, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes after the oscillation for 10 minutes to split phases, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, and is shown in Table 2.
Example 10
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.4, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes after the oscillation for 10 minutes to split phases, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, and is shown in Table 2.
Example 11
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 65 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes after the oscillation for 10 minutes to split phases, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, and is shown in Table 2.
Example 12
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 85 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes after the oscillation for 10 minutes to split phases, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, and is shown in Table 2.
Example 13
Tetrabutylammonium bromide is used as a hydrogen bond acceptor, n-octanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 5 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 130 RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the ambient temperature of 45 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 45 minutes for phase separation after 8 minutes of oscillation, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.8 mol/L NaCl solution according to the ratio of 5:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, see Table 2.
Comparative example 1
The preparation method comprises the steps of taking tetrapropyl ammonium chloride as a hydrogen bond acceptor, taking n-octanol as a hydrogen bond donor, enabling the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor to be 1:1.2, reacting for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, preparing a hydrophobic eutectic solvent, mixing the prepared hydrophobic eutectic solvent with vanadium-arsenic solution according to the ratio of 1:1, oscillating for 10 minutes at the environment temperature of 50 ℃, the shimmy amplitude of 40 mm and the rotating frequency of 300 RPM, standing for 30 minutes for phase separation to obtain a loaded organic phase, mixing the eutectic solvent loaded with vanadium with 1.5 mol/L NaCl solution according to the ratio of 4:1, oscillating for back extraction for 10 minutes, and calculating the single-stage extraction rate, wherein the table 2 is referred to.
Comparative example 2
Tetrabutylammonium chloride is used as a hydrogen bond acceptor, n-hexanol is used as a hydrogen bond donor, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2, the reaction is carried out for 4 hours under the conditions that the heating temperature is 75 ℃ and the stirring rotating speed is 180RPM, the prepared hydrophobic eutectic solvent is mixed with vanadium-arsenic solution according to the ratio of 1:1, the shimmy amplitude is 40 mm at the environment temperature of 50 ℃, the rotating frequency is 300 RPM, the mixture is kept stand for 30 minutes after the oscillation for 10 minutes for phase separation, the loaded organic phase is obtained, the eutectic solvent loaded with vanadium is mixed with 1.5 mol/L NaCl solution according to the ratio of 4:1, the oscillation back extraction is carried out for 10 minutes, and the single-stage extraction rate is calculated, see Table 2.
TABLE 2
As can be seen from Table 2, example 4 is the best example, namely when the hydrogen bond acceptor is tetrabutylammonium bromide and the hydrogen bond donor is n-octanol, the tetrabutylammonium bromide and the n-octanol are mixed according to the mol ratio of 1:1.2, the reaction is carried out for 4 hours under the conditions of heating temperature of 75 ℃ and stirring speed of 180RPM, the prepared hydrophobic eutectic solvent has the best extraction effect on vanadium, the single-stage vanadium extraction rate is up to 80.21%, when tetrabutylammonium bromide is replaced by tetrabutylammonium chloride, the single-stage vanadium extraction rate can be more than 75%, when tetrabutylammonium bromide is replaced by tetrapropylammonium chloride, the single-stage vanadium extraction rate is only 45.78%, when other fatty alcohols such as n-nonanol and n-decanol are adopted, the single-stage vanadium extraction rate is only 38.54%, and when n-hexanol is adopted, the proper hydrogen bond donor and hydrogen bond acceptor form a hydrogen bond network under specific reaction conditions, the single-stage vanadium extraction rate is more favorable for vanadium extraction in vanadium solution.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (7)
1. A method for extracting and separating vanadium from a vanadium-arsenic solution by using a hydrophobic eutectic solvent, which is characterized by comprising the following steps:
s100: preparation of hydrophobic eutectic solvent: mixing a hydrogen bond acceptor with a hydrogen bond donor, and then reacting to form a hydrogen bond network;
the hydrogen bond acceptor comprises tetrabutylammonium chloride or tetrabutylammonium bromide;
the hydrogen bond donor includes any one of n-octanol, n-nonanol or n-decanol;
s200: extraction and separation of vanadium: mixing the hydrophobic eutectic solvent with vanadium-arsenic solution, oscillating, standing for phase separation, and back extraction after phase separation;
in the step S100, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1-1.4;
in the step S200, the hydrophobic eutectic solvent and the vanadium-arsenic solution are mixed according to the volume ratio of 1:1-2, wherein the concentration of vanadium ions in the vanadium-arsenic solution is 9-12 g/L, and the concentration of arsenic ions is 8-8.5 g/L.
2. The method according to claim 1, wherein in step S100, the reaction temperature is 65-85 ℃, the reaction time is 3-5 h, and the stirring speed is 100-200 rpm.
3. The method of claim 1, wherein in step S100, the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1:1.2.
4. The method of claim 1, wherein the hydrophobic eutectic solvent has a viscosity of 110 to 180cp.
5. The method of claim 4, wherein the hydrophobic eutectic solvent has a viscosity of 115-130 cp.
6. The method according to claim 1, wherein in step S200, the oscillating includes oscillating at 40-60 ℃;
and standing time of standing phase separation is 30-50 min.
7. The method according to claim 1, wherein in step S200, the phase separation back extraction comprises:
and (3) obtaining a vanadium-loaded hydrophobic eutectic solvent, mixing the stripping agent and the vanadium-loaded hydrophobic eutectic solvent according to a volume ratio of 3-5:1, and oscillating and stripping for 5-10 min.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213777A (en) * | 1987-04-01 | 1993-05-25 | Imperial Chemical Industries Plc | Process for the recovery of metals |
| JP2005220282A (en) * | 2004-02-09 | 2005-08-18 | Mitsui Chemicals Inc | Ethylenic copolymer containing vicinally substituted functional group and use of the same |
| JP2006193508A (en) * | 2004-12-13 | 2006-07-27 | Sumitomo Chemical Co Ltd | Method for producing alcohol |
| JP2013159822A (en) * | 2012-02-06 | 2013-08-19 | Sumitomo Metal Mining Co Ltd | Impurity removal method |
| CN103540745A (en) * | 2013-08-26 | 2014-01-29 | 中国科学院过程工程研究所 | Method for preparing high-purity vanadium from heteropolyacid impurity in amine extraction mode |
| CN106048261A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting vanadium from acidic solution by using ionic liquid [OMIM]BF4 |
| WO2018167130A1 (en) * | 2017-03-15 | 2018-09-20 | Fundacion Tecnalia Research & Innovation | Extraction of rare earth elements with deep eutectic solvents |
| CN109022797A (en) * | 2018-08-24 | 2018-12-18 | 肇庆市珈旺环境技术研究院 | A method of separating and recovering molybdenum and vanadium for the mixing amine extractant of molybdenum vanadium separation and from dead catalyst |
| CN112226632A (en) * | 2020-09-11 | 2021-01-15 | 江苏大学 | Method for selectively extracting and precipitating lithium in lithium mother liquor by using hydrophobic eutectic solvent |
| CN112726253A (en) * | 2021-01-21 | 2021-04-30 | 天津科技大学 | Method for efficiently separating plant fibers by acidic eutectic solvent/metal salt multi-component system |
| EP3878534A1 (en) * | 2020-03-12 | 2021-09-15 | Wageningen Universiteit | Extraction and back-extraction of hydrophobic compounds using deep eutectic solvent with tuneable hydrophobicity |
| CN114588660A (en) * | 2022-02-24 | 2022-06-07 | 广东工业大学 | Hydrophobic deep eutectic solvent and preparation method and application thereof |
| CN115198094A (en) * | 2022-07-19 | 2022-10-18 | 安徽格派锂电循环科技有限公司 | Process method for removing cadmium from cobalt sulfate solution through binary solvent synergistic extraction |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016073149A1 (en) * | 2014-11-03 | 2016-05-12 | Exxonmobil Research And Engineering Company | Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof |
| CA2925149C (en) * | 2015-05-25 | 2022-10-04 | Xiamen Institute Of Rare Earth Materials | Extractant and method for extracting and separating yttrium |
| WO2020121220A1 (en) * | 2018-12-11 | 2020-06-18 | Eni S.P.A. | Process for the selective recovery of transition metals from organic residues |
-
2023
- 2023-08-31 CN CN202311114154.9A patent/CN116814990B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213777A (en) * | 1987-04-01 | 1993-05-25 | Imperial Chemical Industries Plc | Process for the recovery of metals |
| JP2005220282A (en) * | 2004-02-09 | 2005-08-18 | Mitsui Chemicals Inc | Ethylenic copolymer containing vicinally substituted functional group and use of the same |
| JP2006193508A (en) * | 2004-12-13 | 2006-07-27 | Sumitomo Chemical Co Ltd | Method for producing alcohol |
| JP2013159822A (en) * | 2012-02-06 | 2013-08-19 | Sumitomo Metal Mining Co Ltd | Impurity removal method |
| CN103540745A (en) * | 2013-08-26 | 2014-01-29 | 中国科学院过程工程研究所 | Method for preparing high-purity vanadium from heteropolyacid impurity in amine extraction mode |
| CN106048261A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting vanadium from acidic solution by using ionic liquid [OMIM]BF4 |
| WO2018167130A1 (en) * | 2017-03-15 | 2018-09-20 | Fundacion Tecnalia Research & Innovation | Extraction of rare earth elements with deep eutectic solvents |
| CN109022797A (en) * | 2018-08-24 | 2018-12-18 | 肇庆市珈旺环境技术研究院 | A method of separating and recovering molybdenum and vanadium for the mixing amine extractant of molybdenum vanadium separation and from dead catalyst |
| EP3878534A1 (en) * | 2020-03-12 | 2021-09-15 | Wageningen Universiteit | Extraction and back-extraction of hydrophobic compounds using deep eutectic solvent with tuneable hydrophobicity |
| CN112226632A (en) * | 2020-09-11 | 2021-01-15 | 江苏大学 | Method for selectively extracting and precipitating lithium in lithium mother liquor by using hydrophobic eutectic solvent |
| CN112726253A (en) * | 2021-01-21 | 2021-04-30 | 天津科技大学 | Method for efficiently separating plant fibers by acidic eutectic solvent/metal salt multi-component system |
| CN114588660A (en) * | 2022-02-24 | 2022-06-07 | 广东工业大学 | Hydrophobic deep eutectic solvent and preparation method and application thereof |
| CN115198094A (en) * | 2022-07-19 | 2022-10-18 | 安徽格派锂电循环科技有限公司 | Process method for removing cadmium from cobalt sulfate solution through binary solvent synergistic extraction |
Non-Patent Citations (2)
| Title |
|---|
| Novel Nonanol-Based deep eutectic solvents:Thermophysical properties and their applications in Liquid-Liquid extraction and amino acid detection;Karzan A.Omar et al.;Journal of Molecular Liquids;1-11 * |
| 燃煤电厂废旧SCR脱硝催化剂中TiO2载体的回收与再利用;戚春萍等;化工学报;第68卷(第11期);4239-4248 * |
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