CN108946790B - Preparation method of submicron scandium fluoride - Google Patents
Preparation method of submicron scandium fluoride Download PDFInfo
- Publication number
- CN108946790B CN108946790B CN201811141894.0A CN201811141894A CN108946790B CN 108946790 B CN108946790 B CN 108946790B CN 201811141894 A CN201811141894 A CN 201811141894A CN 108946790 B CN108946790 B CN 108946790B
- Authority
- CN
- China
- Prior art keywords
- scandium
- carboxylic acid
- extractant
- organic
- solution
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/265—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention provides a preparation method of submicron scandium fluoride. The preparation method comprises the following steps: performing saponification reaction on the alkali liquor and the organic carboxylic acid extractant to obtain a saponified extractant; extracting the partially saponified extractant and the scandium-containing solution to obtain a scandium-containing organic phase; mixing the residual saponification extracting agent with a fluorine-containing compound to obtain a fluorine-containing mixed solution, wherein the fluorine-containing compound is one or more of NaF, KF and hydrofluoric acid; carrying out precipitation reaction on the scandium-containing organic phase and the mixed solution to obtain submicron scandium fluoride. The method for preparing the submicron scandium fluoride powder has the characteristics of simplicity and high efficiency, scandium is extracted and enriched from the solution and is separated from impurity ions, and the extracting agent also plays a role in forming a micro-reactor and stabilizing the powder form. The method can regulate and control the size, the shape and the property of the product, and is more beneficial to being applied to industrial production.
Description
Technical Field
The invention relates to the field of material chemistry, in particular to a preparation method of submicron scandium fluoride.
Background
Scandium fluoride (ScF)3) Can be used as optical material and also as important raw material for preparing scandium metal and alloy thereof by molten salt electrolysis and metallothermic reduction. When the aluminum-scandium master alloy is prepared by the molten salt electrolysis method, anhydrous scandium fluoride is needed. Due to the characteristics of small particle size, large specific surface area and the like of the ultrafine powder, the performance of the material prepared into the ultrafine powder is obviously improved. If scandium fluoride fine particle material is used as the raw material, the temperature for molten salt electrolysis can be lowered, and the loss of molten salt can be reduced. The submicron material refers to fine particles having a particle size diameter of 0.1 μm to 1.0. mu.m.
At present, scandium fluoride is mainly prepared from scandium oxide serving as a raw material by a dry method or a wet method. The main problems of dry preparation are high corrosion to equipment and environmental pollution. During the wet preparation, scandium oxide is dissolved with hydrochloric acid, and then a fluorinating agent is added to precipitate hydrated fluoride from an aqueous solution, and then hydrated scandium fluoride is dehydrated in a dry hydrogen fluoride flow to prepare anhydrous scandium fluoride. The method also has the problems of environmental pollution, difficult avoidance of the generation of scandium oxyfluoride ScOF by hydrolysis and further influence on the high scandium yield obtained by molten salt electrolysis.
Disclosure of Invention
The invention mainly aims to provide a preparation method of submicron scandium fluoride, which is used for solving the problems in the prior art.
In order to achieve the above object, the present invention provides a method for producing submicron scandium fluoride, including: performing saponification reaction on the alkali liquor and the organic carboxylic acid extractant to obtain a saponified extractant; extracting the partially saponified extractant and the scandium-containing solution to obtain a scandium-containing organic phase; mixing the residual saponification extracting agent with a fluorine-containing compound to obtain a fluorine-containing mixed solution, wherein the fluorine-containing compound is one or more of NaF, KF and hydrofluoric acid; carrying out precipitation reaction on the scandium-containing organic phase and the mixed solution to obtain submicron scandium fluoride.
Further, before the saponification reaction, the preparation method further comprises: mixing alkali liquor, an organic carboxylic acid extracting agent and a phase regulator to obtain a reactant to be reacted; and carrying out saponification reaction on the reactant to obtain the saponification extracting agent.
Further, the reactant is prepared by the following method: mixing an organic carboxylic acid extractant, a phase regulator and an organic solvent to obtain an extractant organic solution; mixing an organic solution of an extracting agent with alkali liquor to obtain a reactant to be reacted; preferably, the organic solvent is an alkane, more preferably one or more of n-octane, n-heptane, n-hexane, cyclohexane and kerosene.
Further, the organic carboxylic acid extracting agent is an organic matter containing carboxyl, preferably one or more of chain alkyl carboxylic acid, aromatic alkyl carboxylic acid and cyclic alkyl carboxylic acid; preferably, the alkyl carboxylic acid is selected from one or more of n-hexanoic acid, n-decanoic acid, dodecyl carboxylic acid and isooctanoic acid; preferably, the aromatic hydrocarbyl carboxylic acid is selected from sec-octylphenoxyacetic acid and/or sec-nonylphenoxyphenoxyacetic acid; preferably, the cyclic alkyl carboxylic acid is selected from carboxylic acids containing cyclopentyl or cyclohexyl groups.
Furthermore, in the organic solution of the extracting agent, the concentration of the phase regulator is 5-25 vol%; preferably, the phase modifier is an alkyl alcohol, preferably one or more of n-butanol, n-hexanol, n-octanol, and isooctanol.
Furthermore, the concentration of the organic carboxylic acid extracting agent in the extracting agent organic solution is 0.5-3.5 mol/L.
Furthermore, the ratio of the mole number of the organic carboxylic acid extractant to the mole number of scandium ions in the scandium-containing solution is recorded as A, and A is more than or equal to 3 and less than or equal to 20.
Furthermore, in the precipitation reaction process, the quantity ratio of the fluorine ions to the scandium element in the scandium-containing organic phase is represented as B, wherein B is more than or equal to 4 and less than or equal to 6, and the volume ratio of the scandium-containing organic phase to the fluorine-containing mixed liquid is 1: 10-10: 1.
Further, the extraction process is carried out under the condition that the pH value is 2-4.
Further, the precipitation reaction further comprises: carrying out heat preservation aging, solid-liquid separation, washing and drying treatment on a product system of the precipitation reaction in sequence to obtain submicron scandium fluoride; preferably, the temperature of the heat preservation and aging process is 90-150 ℃, and the time is 1-8 h; preferably, the temperature in the drying process is 90-105 ℃; preferably, the washing process is carried out by washing the product system of the precipitation reaction with ethanol and/or water.
By applying the technical scheme of the invention, the organic carboxylic acid extracting agent has surface activity due to the self hydrophilic and lipophilic special structure, and the unreacted organic carboxylic acid extracting agent in the organic phase and alkali liquor are subjected to saponification reaction to form a saponified extracting agent (saponification product). Compared with organic carboxylic acid extractant, the saponification extractant has stronger surface activity and can form stable water/oil micro emulsion type organic phase. Meanwhile, the alkali liquor can play a role in adjusting the pH value in the microreactor. And extracting the scandium-containing solution by using a partially saponified extractant to obtain a scandium-containing organic phase. Mixing the residual saponification extracting agent with fluorine-containing solution to form water/oil microemulsion type organic phase. And carrying out precipitation reaction on the scandium-containing organic phase and the fluorine-containing mixed solution to obtain submicron scandium fluoride. The method for preparing the submicron scandium fluoride powder has the characteristics of simplicity and high efficiency, scandium is extracted and enriched from the solution and is separated from impurity ions, and the extracting agent also plays a role in forming a micro-reactor and stabilizing the powder form. The method can regulate and control the size, the shape and the property of the product, and is more beneficial to being applied to industrial production.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing preparation method of submicron scandium fluoride has the problems of complex process and low yield of submicron scandium fluoride. In order to solve the above technical problem, the present application provides a method for preparing submicron scandium fluoride, including: performing saponification reaction on the alkali liquor and the organic carboxylic acid extractant to obtain a saponified extractant; extracting the partially saponified extractant and the scandium-containing solution to obtain a scandium-containing organic phase; mixing the residual saponification extracting agent with a fluorine-containing compound to obtain a fluorine-containing mixed solution, wherein the fluorine-containing solution is one or more of NaF, KF and hydrofluoric acid; carrying out precipitation reaction on the scandium-containing organic phase and the mixed solution to obtain submicron scandium fluoride.
The organic carboxylic acid extractant has surface activity due to its own hydrophilic-lipophilic special structure, and the unreacted organic carboxylic acid extractant in the organic phase undergoes saponification with alkali liquor to form saponified extractant (saponified product, first water/oil microemulsion type organic phase). Compared with organic carboxylic acid extractant, the saponification extractant has stronger surface activity and can form stable water/oil micro-emulsion type organic phase (micro-reactor). Meanwhile, the alkali liquor can play a role in adjusting the pH value in the microreactor. And extracting the scandium-containing solution by using a partially saponified extractant to obtain a scandium-containing organic phase (a second water/oil microemulsion type organic phase). The remaining saponified extractant is mixed with a fluorochemical to form a fluorochemical mixed liquor (third aqueous/oil microemulsion-type organic phase). And carrying out precipitation reaction on a scandium-containing organic phase and the fluorine-containing mixed liquid to obtain submicron scandium fluoride.
The reaction principle of the reaction is as follows:
the saponification reaction comprises the following steps: HA(o)+NaOH→NaA(o)+H2O，HA(o)Being an organic carboxylic acid, NaA(o)To saponify the organic carboxylic acid extractant.
The extraction reaction is as follows: sc (Sc)3++3NaA(o)→ScA3(o)+3Na+ (o)
The scandium fluoride precipitation reaction is as follows: ScA3(o)+3NaF→ScF3↓+3NaA(o)。
In the preparation process, the micro-reactor of the water/oil micro-emulsion has the size of micron and nanometer, the middle part is a 'small water pool', and the shape is spherical, nearly spherical or ellipsoidal. In the saponification reaction process, the oleophilic end (i.e. alkane chain) of the organic carboxylic acid extracting agent extends to the oil phase, the hydrophilic end (i.e. carboxyl) extends to the water pool and is gathered on the surface of the small water pool, and the organic carboxylic acid has stronger surface activity after reacting with alkali, so that the formed microreactor is more stable. The purpose of adjusting the particle size of scandium fluoride can be achieved through the capacity inside the microreactor.
The method for preparing the submicron scandium fluoride powder has the characteristics of simplicity and high efficiency, scandium is extracted and enriched from the solution and is separated from impurity ions, and the extracting agent also plays a role in forming a micro-reactor and stabilizing the powder form. The method can regulate and control the size, the shape and the property of the product, and is more beneficial to being applied to industrial production.
Preferably, the concentration of the organic carboxylic acid extracting agent is 0.5-3.5 mol/L. In the saponification reaction, the ammonium saponification degree of the organic carboxylic acid extractant is 50 to 90%.
Preferably, in the extraction process, the concentration of scandium ions in the scandium-containing solution is 0.001-1.0 mol/L.
Preferably, when scandium ions are extracted using a carboxylic acid, the ratio of the number of moles of the organic carboxylic acid extractant to the number of moles of scandium ions in the solution is 3 or more and 20 or less.
In a preferred embodiment, the preparation method further comprises, before the saponification reaction is carried out: mixing alkali liquor, an organic carboxylic acid extracting agent and a phase regulator to obtain a reactant to be reacted; and carrying out saponification reaction on the reactant to obtain a saponification extracting agent (saponification product, a first water/oil microemulsion type organic phase).
As used herein, "lye" refers to an aqueous solution of a base including, but not limited to, sodium hydroxide, potassium hydroxide, and the like.
The organic phase of the water/oil microemulsion can be formed after saponification reaction, and the addition of the phase regulator is beneficial to ensuring that the formed water/oil microemulsion is more stable. In the saponification reaction process, a micro-reactor capable of adsorbing the extracting agent and the phase regulator simultaneously can be formed, and the shape, the granularity and the property of the micro-reactor can play a role in regulating and controlling the size, the shape and the property of a product.
In a preferred embodiment, the reactants are prepared by the following method: mixing an organic carboxylic acid extractant, a phase regulator and an organic solvent to obtain an extractant organic solution; and mixing the organic solution of the extracting agent with alkali liquor to obtain a reactant to be reacted.
The organic solution of the extracting agent is prepared firstly and then undergoes saponification reaction with the alkali liquor, which is beneficial to adjusting the concentration of the organic carboxylic acid extracting agent in the saponification reaction process, and further can adjust the extraction efficiency.
Preferably, the organic solvent is an alkane. More preferably, the organic solvent includes, but is not limited to, one or more of n-octane, n-heptane, n-hexane, cyclohexane, and kerosene.
The organic solvent may be any one commonly used in the art. In a preferred embodiment, the organic carboxylic acid extractant is a carboxyl group-containing organic substance, preferably one or more of a linear alkyl carboxylic acid, an aromatic alkyl carboxylic acid, and a cyclic alkyl carboxylic acid.
Preferably, the chain alkyl carboxylic acids include, but are not limited to, one or more of n-hexanoic acid, n-decanoic acid, dodecyl carboxylic acid, and isooctanoic acid; preferably, the aromatic hydrocarbyl carboxylic acids include, but are not limited to, sec-octylphenoxyacetic acid (CA-12) and/or sec-nonylphenoxyphenoxyacetic acid; preferably, the cyclic alkyl carboxylic acid is selected from cyclopentyl or cyclohexyl containing carboxylic acids.
In a preferred embodiment, the concentration of the phase modifier in the organic solution of the extractant is 5 to 25 vol%. In the above preparation method, the concentration of the phase modifier in the organic solution of the extractant includes, but is not limited to, the above range, and is limited to the above range, which is beneficial to further improving the extraction efficiency and further improving the yield of the submicron scandium fluoride.
Preferably, the phase modifier is an alkyl alcohol, more preferably, the phase modifier includes, but is not limited to, one or more of n-butanol, n-hexanol, n-octanol, and isooctanol.
In a preferred embodiment, the concentration of the organic carboxylic acid extractant in the extractant organic solution is 0.5 to 3.5 mol/L. The extraction mechanism is a cation exchange mechanism. The concentration of the organic carboxylic acid extractant includes, but is not limited to, the above range, and is limited to the above range.
In a preferred embodiment, the ratio of the number of moles of organic carboxylic acid extractant to the number of moles of scandium ion in the scandium-containing solution in the organic solution of extractant is denoted as A and 3. ltoreq. A.ltoreq.20. The ratio of the number of moles of the organic carboxylic acid extractant to the number of moles of scandium ions in the scandium-containing solution includes, but is not limited to, the above range, and it is preferable to limit the ratio to the above range in order to further improve the extraction rate of scandium ions.
In a preferred embodiment, the ratio of the amount of fluoride ions to the amount of scandium species in the scandium-containing organic phase during the precipitation reaction is denoted B, and 4. ltoreq. B.ltoreq.6, the volume ratio of scandium-containing organic phase to the fluoride-containing organic phase of the water/oil microemulsion type being from 1:10 to 10: 1. The ratio of the amount of scandium in the scandium-containing organic phase to the amount of the scandium element in the scandium-containing organic phase and the volume ratio of the scandium-containing organic phase to the aqueous/oil microemulsion-type organic phase containing the fluorine ions are not limited to the above ranges, and limiting the ratio to the above ranges is advantageous for further improving the precipitation rate of scandium fluoride, and thus for improving the yield of submicron scandium fluoride.
In a preferred embodiment, the extraction process is carried out at a pH of 2 to 4. The pH of the reaction system during extraction includes, but is not limited to, the above range, and limiting it to the above range is advantageous to further improve the extraction efficiency of scandium ions.
In a preferred embodiment, the precipitation reaction further comprises: carrying out heat preservation aging, solid-liquid separation, washing and drying treatment on a product system of the precipitation reaction in sequence to obtain submicron scandium fluoride;
preferably, the temperature of the heat preservation and aging process is 90-150 ℃ and the time is 1-8 h. Limiting the temperature and time of the incubation process within the above ranges is advantageous for further improving the yield of submicron scandium fluoride. Preferably, the temperature of the drying process is 90-105 ℃.
Preferably, the temperature of the drying process is 90-105 ℃. Limiting the temperature in the drying process within the range is beneficial to improving the moisture removal rate, and further improving the yield of scandium fluoride.
Preferably, in the washing process, the scandium fluoride precipitate is washed by ethanol and/or water, which is beneficial to reducing the loss rate of scandium fluoride double salt in the washing process, and further improving the yield of scandium fluoride.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
In an extraction reactor, 1000mL of kerosene solution containing 1mol/L of CA-12 extractant and 10% of n-butanol (phase regulator) is added with a solution of sodium hydroxide to cause saponification of CA-12, thus obtaining a saponified extractant (first aqueous/oil microemulsion type organic phase) with a saponification degree of 90%.
Mixing 500mL of first water/oil microemulsion type organic phase with 500mL of scandium chloride solution containing 0.25mol/L of scandium to extract scandium in the scandium-containing hydrochloric acid solution, controlling the pH value of an extraction endpoint of the scandium-containing solution to be 2.5 by using a sodium hydroxide solution, and separating and removing raffinate to obtain a second water/oil microemulsion type organic phase (scandium-containing organic phase), wherein the extraction rate of scandium is 99.0 wt%.
Adding 100mL of 4mol/L sodium fluoride solution into 500mL of the first water/oil microemulsion type organic phase to form a mixed solution (a third water/oil microemulsion type organic phase);
and mixing the second water/oil microemulsion type organic phase and the third water/oil microemulsion type organic phase to generate a precipitation reaction, carrying out heat preservation treatment on a product system of the precipitation reaction at 200 ℃ for 4 hours, centrifuging by using a high-speed centrifuge and carrying out solid-liquid separation treatment to obtain submicron scandium fluoride powder with the surface adsorbed by the extractant and the phase regulator. Washing the submicron scandium hydrofluoride powder adsorbed by the extractant and the phase regulator with ethanol at 40 ℃ and water at 60 ℃ for 2 times respectively; drying at 90 ℃ in a drying oven to obtain 37.2g of submicron scandium fluoride powder, wherein the total yield of scandium is 98.1 wt%. The particle size of the powder is 0.2-0.5 μm by transmission electron microscope detection.
Wherein, the 'extracting agent organic solution is a kerosene solution of 1mol/L CA-12 extracting agent-10% n-butyl alcohol' means that the CA-12 extracting agent and the n-butyl alcohol regulator are used as solutes, the kerosene solution is used as a solvent, and the volume percentage content of the n-butyl alcohol in the extracting agent organic solution is 10%.
Example 2
In an extraction reactor, 1000mL of an n-heptane solution containing 3mol/L naphthenic acid extractant-20% isooctyl alcohol (phase modifier) is added with a solution of sodium hydroxide to carry out saponification reaction with the naphthenic acid extractant, so as to obtain an ammonium saponification extractant (a first water/oil microemulsion type organic phase), wherein the saponification degree is 60%.
Mixing 500mL of first water/oil microemulsion type organic phase with 500mL of scandium chloride solution containing 0.1mol/L of scandium to extract scandium in the scandium-containing hydrochloric acid solution, controlling the pH value of an extraction endpoint of the scandium-containing solution to be 3.5 by using a sodium hydroxide solution, and separating and removing raffinate to obtain a second water/oil microemulsion type organic phase (scandium-containing organic phase), wherein the extraction rate of scandium is 99.5 wt%.
50mL of a 6.8mol/L hydrofluoric acid solution was added to 500mL of the first aqueous/oil microemulsion type organic phase to form a mixed solution (third aqueous/oil microemulsion type organic phase).
And mixing the second water/oil microemulsion type organic phase and the third water/oil microemulsion type organic phase to generate a precipitation reaction, carrying out heat preservation treatment on a reaction system of the precipitation reaction at 150 ℃ for 8 hours, centrifuging by using a high-speed centrifuge and carrying out solid-liquid separation treatment to obtain submicron scandium fluoride powder with the surface adsorbed by the extractant and the phase regulator. Washing the submicron scandium hydrofluoride powder adsorbed by the extractant and the phase regulator with ethanol and water alternately for 2 times; drying at 105 ℃ to obtain submicron scandium fluoride powder, wherein the total yield of scandium is 98.1%. The particle size of the powder is 0.5-1 μm by transmission electron microscope detection.
Wherein the 'organic solution of the extractant is a 3mol/L naphthenic acid extractant-20% isooctanol n-heptane solution' means that the naphthenic acid extractant and the isooctanol regulator are used as solutes, the n-heptane solution is used as a solvent, and the volume percentage content of the isooctanol in the organic solution of the extractant is 20%.
Example 3
The differences from example 1 are: the extractant is n-hexanoic acid.
The total yield of scandium was 99.1 wt%. The particle size of the powder is 0.1-0.3 μm by transmission electron microscope detection.
Example 4
The differences from example 1 are: the concentration of the phase modifier in the organic solution of the extractant was 1 vol%.
The total yield of scandium was 88.3 wt%. The particle size of the powder is 0.4-0.6 μm by transmission electron microscope detection.
Example 5
The differences from example 1 are: the concentration of the organic carboxylic acid extractant in the extractant organic solution is 4 mol/L.
The total yield of scandium was 86.9 wt%. The particle size of the powder is 0.5-0.6 μm by transmission electron microscope detection.
Example 6
The differences from example 1 are: the ratio of the number of moles of organic carboxylic acid extractant to the number of moles of scandium ions in the scandium-containing solution was 1: 1.
The total yield of scandium was 90.2 wt%. The particle size of the powder is 0.1-0.2 μm by transmission electron microscope detection.
Example 7
The differences from example 1 are: during the extraction, the pH of the reaction system was adjusted to 5.
The total yield of scandium was 93.5 wt%. The particle size of the powder is 0.3-0.7 μm by transmission electron microscope detection.
Example 8
The differences from example 1 are: the temperature of the heat preservation and aging process is 80 ℃, and the time is 10 hours.
The total yield of scandium was 91.1 wt%. The particle size of the powder is 0.6-1 μm by transmission electron microscope detection.
Comparative example 1
Directly mixing 1000mL of a first water/oil microemulsion type organic phase, 500mL of a scandium chloride solution containing 0.25mol/L scandium and 100mL of a 4mol/L sodium fluoride solution, carrying out precipitation reaction, carrying out heat preservation treatment on a product system of the precipitation reaction at 200 ℃ for 4h, centrifuging by using a high-speed centrifuge and carrying out solid-liquid separation treatment to obtain submicron scandium fluoride powder with the surface adsorbed by an extractant and a phase regulator. Washing the submicron scandium hydrofluoride powder adsorbed by the extractant and the phase regulator with ethanol at 40 ℃ and water at 60 ℃ for 2 times respectively; drying at 90 ℃ in a drying oven, wherein the yield is 62 wt%, and the particle size of the powder is 5-8 μm by detection of a transmission electron microscope.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
comparing examples 1 to 8 and comparative example 1, it can be seen that the preparation method provided by the present application is advantageous for increasing the yield of scandium fluoride and reducing the particle size thereof.
Comparing examples 1 to 3 with comparative example 1, it can be seen that the method for preparing scandium fluoride provided by the present application is advantageous for increasing the yield of submicron scandium fluoride.
Comparing examples 1 and 4, it is found that limiting the concentration of the phase modifier in the extractant organic solution to the range preferred in the present application is advantageous in increasing the yield of submicron scandium fluoride.
Comparing examples 1 and 5, it is found that limiting the concentration of the organic carboxylic acid extractant in the extractant organic solution to the range preferred in the present application is advantageous in increasing the yield of submicron scandium fluoride.
Comparing examples 1 and 6, it is found that limiting the ratio of the number of moles of organic carboxylic acid extractant to the number of moles of scandium ions in the scandium-containing solution to the range preferred in the present application is advantageous in increasing the yield of submicron scandium fluoride.
Comparing examples 1 and 7, it is found that limiting the pH of the reaction system during the extraction to the range preferred in the present application is advantageous in increasing the yield of submicron scandium fluoride.
Comparing examples 1 and 8, it is found that limiting the temperature and time during the soaking and aging process to the preferred ranges in the present application is advantageous for increasing the yield of submicron scandium fluoride.
The method for preparing the submicron scandium fluoride powder has the following advantages: (1) the enrichment, extraction and purification integrated process shortens the process, namely, scandium is extracted and enriched from the solution and separated from impurity ions by utilizing an extraction method, so that the scandium purification effect is achieved. (2) Controlling the particle size of the precipitate: forming a stable water/oil microemulsion type organic phase by using an organic carboxylic acid extractant, and using a microreactor which is adsorbed by the extractant and a phase regulator in the organic carboxylic acid extractant, (3) carrying out back extraction and precipitation to integrally shorten the flow: the back extraction simultaneously generates submicron ammonium fluoride scandium double salt precipitated powder the surface of which is adsorbed by the extractant and the phase regulator, the double salt precipitated crystal is easy to separate, (4) the product has uniform grain diameter and high purity: the extractant and the phase regulator can prevent powder agglomeration, play a role in stabilizing the powder form, and further inhibit the generation of scandium oxyfluoride in the process of dehydration and deammoniation so as to generate high-purity submicron scandium fluoride powder.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for producing submicron scandium fluoride, comprising:
mixing an organic carboxylic acid extractant, a phase regulator and an organic solvent to obtain an extractant organic solution, wherein the concentration of the organic carboxylic acid extractant is 0.5-3.5 mol/L;
mixing alkali liquor and the organic solution of the extracting agent, and performing saponification reaction to obtain a saponified extracting agent;
extracting part of the saponified extractant and a scandium-containing solution to obtain a scandium-containing organic phase, wherein the ratio of the mole number of the organic carboxylic acid extractant to the mole number of scandium ions in the scandium-containing solution is marked as A, A is more than or equal to 3 and less than or equal to 20, and the extraction is carried out at a pH of 2-4;
mixing the rest saponification extracting agent with a fluorine-containing compound to obtain a fluorine-containing mixed solution, wherein the fluorine-containing compound is one or more of NaF, KF and hydrofluoric acid, the quantity ratio of fluorine ions to scandium in the scandium-containing organic phase in the fluorine-containing mixed solution is marked as B, and B is more than or equal to 4 and less than or equal to 6;
and carrying out a precipitation reaction on the scandium-containing organic phase and the mixed solution to obtain the submicron scandium fluoride, wherein the volume ratio of the scandium-containing organic phase to the fluorine-containing mixed solution is 1: 10-10: 1.
2. The method of claim 1, wherein the organic solvent is an alkane.
3. The method according to claim 2, wherein the organic solvent is one or more of n-octane, n-heptane, n-hexane, cyclohexane and kerosene.
4. The preparation method according to claim 1, wherein the organic carboxylic acid extractant is one or more of a chain alkyl carboxylic acid, an aromatic alkyl carboxylic acid and a cyclic alkyl carboxylic acid;
the alkyl carboxylic acid is selected from one or more of n-hexanoic acid, n-decanoic acid, dodecyl carboxylic acid and isooctanoic acid;
the aromatic hydrocarbyl carboxylic acid is selected from sec-octylphenoxyacetic acid and/or sec-nonylphenoxyphenoxyacetic acid;
the cyclic alkyl carboxylic acid is selected from carboxylic acids containing cyclopentyl or cyclohexyl.
5. The method according to claim 2 or 3, wherein the concentration of the phase modifier in the organic solution of the extractant is 5 to 25 vol%.
6. The method according to claim 5, wherein the phase modifier is an alkyl alcohol.
7. The method according to claim 6, wherein the phase modifier is one or more of n-butanol, n-hexanol, n-octanol, and isooctanol.
8. The production method according to any one of claims 1 to 4, characterized in that the precipitation reaction further comprises: and (3) sequentially carrying out heat preservation ageing, solid-liquid separation, washing and drying treatment on a product system of the precipitation reaction to obtain the submicron scandium fluoride.
9. The preparation method according to claim 8, wherein the temperature of the heat preservation and aging process is 90-150 ℃ and the time is 1-8 h; the temperature in the drying process is 90-105 ℃; and in the washing process, the product system of the precipitation reaction is washed by adopting ethanol and/or water.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811141894.0A CN108946790B (en) | 2018-09-28 | 2018-09-28 | Preparation method of submicron scandium fluoride |
| PCT/CN2019/108710 WO2020063913A1 (en) | 2018-09-28 | 2019-09-27 | Preparation method for scandium fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811141894.0A CN108946790B (en) | 2018-09-28 | 2018-09-28 | Preparation method of submicron scandium fluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108946790A CN108946790A (en) | 2018-12-07 |
| CN108946790B true CN108946790B (en) | 2021-05-07 |
Family
ID=64471217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811141894.0A Active CN108946790B (en) | 2018-09-28 | 2018-09-28 | Preparation method of submicron scandium fluoride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108946790B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020063913A1 (en) * | 2018-09-28 | 2020-04-02 | 中国恩菲工程技术有限公司 | Preparation method for scandium fluoride |
| CN111170352B (en) * | 2020-01-21 | 2022-11-29 | 包头稀土研究院 | Method for preparing rare earth fluoride particles by using fluorine-containing waste acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397653A (en) * | 2002-08-01 | 2003-02-19 | 中国科学院长春应用化学研究所 | Process for enriching and preparing high-purity scandium by use of oxyl substituted acetic acid as extractant |
| CN101602519A (en) * | 2008-06-12 | 2009-12-16 | 北京有色金属研究总院 | A kind of technology of directly preparing rare-earth compound from extraction separation load organic phase |
| RU2382735C1 (en) * | 2008-06-23 | 2010-02-27 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Method of processing permanent magnet wastes |
| CN101824555A (en) * | 2010-06-09 | 2010-09-08 | 攀枝花学院 | Method for extracting scandium |
| CN105793447A (en) * | 2014-02-17 | 2016-07-20 | 学校法人关西大学 | Scandium separation method |
-
2018
- 2018-09-28 CN CN201811141894.0A patent/CN108946790B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397653A (en) * | 2002-08-01 | 2003-02-19 | 中国科学院长春应用化学研究所 | Process for enriching and preparing high-purity scandium by use of oxyl substituted acetic acid as extractant |
| CN101602519A (en) * | 2008-06-12 | 2009-12-16 | 北京有色金属研究总院 | A kind of technology of directly preparing rare-earth compound from extraction separation load organic phase |
| RU2382735C1 (en) * | 2008-06-23 | 2010-02-27 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Method of processing permanent magnet wastes |
| CN101824555A (en) * | 2010-06-09 | 2010-09-08 | 攀枝花学院 | Method for extracting scandium |
| CN105793447A (en) * | 2014-02-17 | 2016-07-20 | 学校法人关西大学 | Scandium separation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108946790A (en) | 2018-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022000881A1 (en) | Carboxylic acid compound, and preparation method therefor and application thereof | |
| DE60010702T2 (en) | TREATMENT OF TITANIUM FOR THE MANUFACTURE OF TITANIUM DIOXIDE PIGMENTS | |
| CN108946790B (en) | Preparation method of submicron scandium fluoride | |
| CN108712999B (en) | Method for preparing synthetic hectorite at low temperature and normal pressure | |
| CN113684369A (en) | Method for treating waste industrial lithium-containing aluminum electrolyte | |
| CA1278417C (en) | Process for manufacture of metal oxide | |
| WO2022110821A1 (en) | Carboxylic acid compound, preparation method therefor and use thereof | |
| CN107557598B (en) | The method for preparing V electrolyte | |
| CN105801531A (en) | Method for preparing alpha-ethyl furan methanol | |
| CN108946791B (en) | Preparation method of micron-sized scandium fluoride | |
| CN111116429A (en) | Method for synthesizing alkali metal trifluoromethanesulfonate | |
| CN112479241A (en) | Method for preparing flake aluminum oxide by utilizing flake aluminum hydroxide | |
| US4574074A (en) | Process for the production of aluminum trihydroxide having a medium of less than 4 microns, which can be varied as required | |
| US1515001A (en) | Process for obtaining lithium salts or metallic lithium | |
| JPH0449489B2 (en) | ||
| CN109266871B (en) | Preparation method of submicron scandium oxide | |
| CN112209819A (en) | Preparation method of D-pantoic acid calcium | |
| CN109133142B (en) | Preparation method of ultramicro scandium oxide | |
| JP2007176710A (en) | Method for producing antimony oxide sol and antimony oxide sol | |
| US1951718A (en) | Production of sols and highly dispersed suspensions comprising oxygen-containing metal compounds | |
| CN110857263B (en) | Preparation method of perfluoropolyether alcohol | |
| KR100995401B1 (en) | Hollow magnesium fluoride particle, preparing process thereof and anti-reflection coating solution comprising the same | |
| AU2016232141A1 (en) | Method for manufacturing furan-2,5-dicarboxylic acid (FDCA) from a solid salt | |
| CN111233036B (en) | Is composed of Sb 2 O 3 Direct preparation of Sb with aqueous hydrochloric acid 4 O 5 Cl 2 Method (2) | |
| CN108698840B (en) | Method for producing synthetic hectorite at low temperature and atmospheric pressure |
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 |