CN114477263B - Superfine scandium oxide, preparation method and application thereof - Google Patents

Superfine scandium oxide, preparation method and application thereof Download PDF

Info

Publication number
CN114477263B
CN114477263B CN202210205141.1A CN202210205141A CN114477263B CN 114477263 B CN114477263 B CN 114477263B CN 202210205141 A CN202210205141 A CN 202210205141A CN 114477263 B CN114477263 B CN 114477263B
Authority
CN
China
Prior art keywords
scandium
temperature
oxalate
precipitation reaction
stirring
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
Application number
CN202210205141.1A
Other languages
Chinese (zh)
Other versions
CN114477263A (en
Inventor
付国燕
刘召波
王玮玮
姚心
杜尚超
彭建华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China ENFI Engineering Corp
Original Assignee
China ENFI Engineering Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China ENFI Engineering Corp filed Critical China ENFI Engineering Corp
Priority to CN202210205141.1A priority Critical patent/CN114477263B/en
Publication of CN114477263A publication Critical patent/CN114477263A/en
Application granted granted Critical
Publication of CN114477263B publication Critical patent/CN114477263B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/212—Scandium oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention provides superfine scandium oxide, a preparation method and application thereof. The preparation method comprises the following steps: in the presence of microwaves and an anionic surfactant, carrying out precipitation reaction on scandium-containing soluble salt solution and a precipitant to obtain scandium oxalate precipitate, wherein the precipitant is oxalic acid or oxalate; roasting scandium oxalate precipitate to obtain superfine scandium oxide; anionic surfactants include, but are not limited to, sulfate-based surfactants and/or sulfonate-based surfactants. The microwave can quickly raise the temperature of the reaction system in a short time, and when oxalic acid and oxalate are used as precipitants to carry out precipitation reaction with scandium-containing soluble salt solution, the anionic surfactant has better acid and alkali resistance, larger steric hindrance and rich surface charge, and can enable scandium oxalate to have better dispersibility and stability after being combined to the scandium oxalate precipitation surface. Scandium oxide with small particle size, high specific surface area and uniform particle size can be obtained through roasting.

Description

Superfine scandium oxide, preparation method and application thereof
Technical Field
The invention relates to the field of material chemistry, in particular to superfine scandium oxide, a preparation method and application thereof.
Background
Scandium oxide (Sc) 2 O 3 ) Is one of the more important products in scandium products. Sc (Sc) 2 O 3 Is white powder, is stable in normal temperature air, has a melting point of 920 ℃ and a density of 3.864g/cm 3 Belongs to the cubic crystal form. Under certain external conditions, sc 2 O 3 Can be made into metal scandium, salts (scandium chloride, scandium fluoride, scandium iodide, scandium oxalate, etc.) and various scandium alloysThe product is obtained. Sc (Sc) 2 O 3 The alloy has some characteristics, so that the alloy has good application in the aspects of aluminum alloy, electric light source, laser, catalyst, activator, ceramic, aerospace and the like, and has very broad development prospect. The superfine scandium oxide powder has a particle size of 10-100 nanometers and can be used for preparing high-efficiency lasers, superconducting materials, electrolyte materials of solid fuel cells and the like. The material structure and the particle size have important influence on the surface performance of the powder material, the superfine powder material and the powder material with the spherical structure have larger specific surface area and larger chemical activity, and have important influence on the performance of the material prepared subsequently, and the superfine spherical scandium oxide powder material can remarkably improve the performance of the metal scandium, scandium salt and scandium-containing alloy prepared subsequently, so that the application field and the prospect of the scandium-containing material are further widened.
CN 110498439A provides a method for preparing scandium oxide powder having a porous structure, the method comprising: a solution forming step of preparing a scandium ion-containing solution; a precipitation step, adding oxalic acid or oxalate serving as a precipitator into the solution under the microwave radiation condition to carry out precipitation reaction; and a roasting step, namely washing and drying the prepared precipitate and roasting the precipitate. Although scandium oxide powder with a porous structure is prepared by the method, the scandium oxide powder has larger granularity, smaller specific surface area and lower uniformity of particle size.
CN109133142 provides a method for preparing ultrafine scandium oxide. The method comprises the following steps: extracting the scandium-containing ion solution by using a carboxylic acid extractant-organic solvent mixed solution to obtain a scandium-loaded organic phase, wherein the carboxylic acid extractant in the carboxylic acid extractant-organic solvent mixed solution is excessively added relative to scandium ions in the scandium-containing ion solution; mixing scandium loaded organic phase with ammonia water and performing saponification reaction to form water-oil emulsion; heating and drying the water-oil emulsion and performing thermal hydrolysis reaction to obtain scandium precipitation; calcining scandium precipitate to obtain superfine scandium oxide. In the preparation method, scandium oxide products with the size of an ultrafine level are effectively prepared, but the process is complex.
In view of the above problems, it is necessary to provide a method for producing scandium oxide having a short process flow and a large specific surface area.
Disclosure of Invention
The invention mainly aims to provide superfine scandium oxide, a preparation method and application thereof, so as to solve the problems of long process flow and small specific surface area of scandium oxide in the existing method for preparing scandium oxide.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing ultrafine scandium oxide, comprising: in the presence of microwaves and an anionic surfactant, carrying out precipitation reaction on scandium-containing soluble salt solution and a precipitant to obtain scandium oxalate precipitate, wherein the precipitant is oxalic acid or oxalate; roasting scandium oxalate precipitate to obtain superfine scandium oxide, wherein the anionic surfactant is selected from sulfate surfactant and/or sulfonate surfactant.
Further, the sulfate surfactant is selected from one or more of the group consisting of sodium dodecyl sulfate, sodium dodecyl benzene sulfate and condensed alkyl phenyl ether sulfate; sulfonate surfactants are selected from one or more of the group consisting of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and lignin sulfonate; preferably, the weight ratio of the sulfate surfactant to the sulfonate surfactant is 1 (2-5).
Further, the scandium ion content in the scandium-containing soluble salt solution is 0.1-2.0 mol/L, and the anionic surfactant content is 0.01-2 g/L; preferably, the scandium ion content in the scandium-containing soluble salt solution is 0.5-1.5 mol/L.
Further, the precipitation reaction step includes: mixing scandium-containing soluble salt solution with an anionic surfactant, and regulating the pH value of a reactant system of the precipitation reaction to 1-5 by adopting a pH regulator to obtain a mixed solution; adding a precipitant into the mixed solution to react to obtain scandium oxalate precipitate; preferably, the precipitant is added to the mixed liquor at a first stirring rate of 150 to 500r/min, preferably 200 to 450r/min.
Further, in the precipitation reaction, the frequency of the microwave is 300 to 700W, preferably 450 to 600W; the reaction temperature is 60 to 100℃and preferably 80 to 90 ℃.
Further, the temperature of the roasting step is 600-900 ℃, preferably 700-850 ℃; the time of the roasting step is 120 to 400 minutes, preferably 220 to 300 minutes.
Further, before the roasting step, the preparation method further comprises the following steps: continuously stirring a product system of the precipitation reaction at a second stirring rate, and then aging and drying to obtain scandium oxalate precipitate; wherein the second stirring speed is 30-300 r/min, and the stirring time is 15-90 min; the temperature of the aging step is 60-100 ℃, and the time of the aging step is 30-350 min; the temperature of the drying step is 70-120 ℃, and the time of the drying step is 120-350 min.
Further, the second stirring speed is 80-150 r/min; stirring for 30-60 min; the temperature of the aging step is 80-90 ℃; the aging step is carried out for 60-300 min; the temperature of the drying step is 80-100 ℃, and the time of the drying step is 180-300 min.
The other aspect of the application also provides the superfine scandium oxide, which is prepared by the preparation method, or the granularity of the superfine scandium oxide is 30-80 nm, and the specific surface area is 200-500 m 2 /g。
In yet another aspect, the present application provides the use of ultra-fine scandium oxide in a laser, a superconducting material or an electrolyte material for a solid fuel cell.
By applying the technical scheme of the invention, the temperature of the reaction system can be quickly increased in a short time by introducing microwaves in the preparation process of scandium oxide, and the risk of uneven granularity of scandium oxide particles caused by uneven internal and external heating due to conventional heating is restrained. The anionic surfactant is capable of binding to the surface of the scandium oxalate precipitate, a precipitation product, when the precipitation reaction is carried out with a scandium-containing soluble salt solution in the presence of a specific anionic surfactant with oxalic acid and oxalic acid as precipitants. The anionic surfactant has better acid and alkali resistance, larger steric hindrance and rich surface charge, so scandium oxalate precipitate in the precipitation reaction product system has better dispersibility and stability. This enables scandium oxalate to obtain scandium oxide having a small particle diameter, a high specific surface area and a uniform particle size upon firing. Meanwhile, the process has the advantages of short flow, simple preparation method, low cost and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
fig. 1 shows a scanning electron microscope result diagram of the ultra-fine spherical scandium oxide powder material prepared in the example.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background art, the existing method for preparing scandium oxide has the problems of long process flow and small specific surface area of scandium oxide. In order to solve the technical problems, the application provides a preparation method of superfine scandium oxide, which comprises the following steps: in the presence of microwaves and an anionic surfactant, carrying out precipitation reaction on scandium-containing soluble salt solution and a precipitant to obtain scandium oxalate precipitate, wherein the precipitant is oxalic acid or oxalate; roasting scandium oxalate precipitate to obtain superfine scandium oxide; anionic surfactants include, but are not limited to, sulfate-based surfactants and/or sulfonate-based surfactants.
Taking oxalate as an example, the reaction principle of the preparation method is as follows:
Sc 3+ +C 2 O 4 2- →S C2 (C 2 O 4 ) 3
S C2 (C 2 O 4 ) 3 →S C2 O 3 +CO 2 ↑+CO↑。
the microwave is introduced in the preparation process of scandium oxide, so that the temperature of a reaction system can be quickly increased in a short time, and the risk of uneven granularity of scandium oxide particles caused by uneven internal and external heating due to conventional heating is restrained. The anionic surfactant is capable of binding to the surface of the scandium oxalate precipitate, a precipitation product, when the precipitation reaction is carried out with a scandium-containing soluble salt solution in the presence of a specific anionic surfactant with oxalic acid and oxalic acid as precipitants. The anionic surfactant has better acid and alkali resistance, larger steric hindrance and rich surface charge, so scandium oxalate precipitate in the precipitation reaction product system has better dispersibility and stability. This enables scandium oxalate to obtain scandium oxide having a small particle diameter, a high specific surface area and a uniform particle size upon firing. Meanwhile, the process has the advantages of short flow, simple preparation method, low cost and the like.
The anionic surfactant has good acid and alkali resistance and steric hindrance, and the purpose of regulating and controlling the appearance of scandium oxide can be achieved by adding the anionic surfactant in the scandium oxide preparation process. In a preferred embodiment, the sulfate-type surfactant is selected from one or more of the group consisting of sodium dodecyl sulfate, sodium dodecyl benzene sulfate, and condensed alkyl phenyl ether sulfate; the sulfonate surfactant is one or more selected from the group consisting of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and lignin sulfonate. The above anionic surfactants have better steric hindrance than other kinds of surfactants, and thus the use of the above anionic surfactants is advantageous in further improving the specific surface area and uniformity of scandium oxide and reducing the particle size thereof. In order to further improve the synergistic effect of the anionic surfactant and further improve the uniformity of distribution and integrity of particle size, it is preferable that the weight ratio of the sulfate-type surfactant to the sulfonate-type surfactant is 1 (2 to 5). The weight ratio of the sulfate surfactant to the sulfonate surfactant can be selected from 1:2, 1:3, 1:4 and 1:5.
Soluble compounds containing scandium are used as raw materials to prepare a solution. Or a solution of scandium ions is formed by the reaction of a poorly soluble compound of scandium with an acid. Scandium ion-containing solution can be prepared by using scandium chloride as a raw material. Scandium oxide, scandium hydroxide, or scandium carbonate may be used as a raw material and reacted with hydrochloric acid to form a solution, which may be a scandium ion-containing solution. In a preferred embodiment, the scandium ion content of the scandium-containing soluble salt solution is 0.1-2.0 mol/L and the anionic surfactant content is 0.01-2 g/L. The ratio of the two is limited to the above range, which is advantageous in further reducing the particle size of scandium oxide particles while improving the uniformity thereof. More preferably, the scandium ion content in the scandium-containing soluble salt solution is 0.5 to 1.5mol/L. Alternatively, the anionic surfactant is used in an amount of 0.01g/L, 0.05g/L, 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1g/L, 1.1g/L, 1.2g/L, 1.3g/L, 1.4g/L, 1.5g/L, 1.6g/L, 1.7g/L, 1.8g/L, 1.9g/L, 2.0g/L.
Scandium oxalate can be precipitated as a precipitate under acidic conditions. In order to increase the precipitation efficiency of scandium oxalate and at the same time increase the yield of scandium oxide, in a preferred embodiment the precipitation reaction step comprises: mixing scandium-containing soluble salt solution with an anionic surfactant, and regulating the pH value of a reactant system of the precipitation reaction to 1-5 by adopting a pH regulator to obtain a mixed solution; and adding a precipitant into the mixed solution to react, so as to obtain scandium oxalate precipitate. The pH is selected from 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 and 5. In order to further improve the reaction rate of the precipitation reaction and the uniformity of the particle size of the target product, it is preferable that the precipitant is added to the mixed solution at a first stirring rate of 150 to 500r/min. Wherein the first stirring rate is selected from 150r/min, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, and 500r/min. More preferably, the first stirring rate is 200 to 450r/min.
In a preferred embodiment, the microwaves have a frequency of 300 to 700W and a reaction temperature of 60 to 100 ℃. Limiting the frequency of the microwaves and the reaction temperature within the above ranges facilitates better control of the temperature during the precipitation reaction than in other ranges, thereby facilitating a reduced risk of aggregation of the particles of scandium oxide. The microwave frequency can be 300W, 350W, 400W, 450W, 500W, 550W, 600W, 650W, 700W, and the reaction temperature can be 60 ℃,70 ℃, 80 ℃, 90 ℃ and 100 ℃. In order to further reduce the particle size of scandium oxide particles and to increase the specific surface area thereof, more preferably, the frequency of microwaves is 450 to 600W and the reaction temperature is 80 to 90 ℃.
After scandium precipitation, scandium oxide powder can be obtained by simply calcining the scandium precipitate. In a preferred embodiment, the temperature of the calcination step is 600 to 900 ℃ and the calcination time is 120 to 400 minutes. The temperature and time of the calcination step include, but are not limited to, the above range, and the scandium hydroxide is decomposed more thoroughly, and the anionic surfactant and the like precipitated with the scandium hydroxide can also be decomposed into CO 2 And water vapor is removed, so that scandium oxide powder is formed more densely. The roasting step is performed at 600deg.C, 650deg.C, 700deg.C, 750deg.C, 800deg.C, 850deg.C, and the roasting time is 120min, 150min, 200min, 250min, 300min, 350min, or 400min. In order to further improve the comprehensive properties of scandium oxide, more preferably, the roasting step is carried out at a temperature of 700-850 ℃ for 220-300 min.
In a preferred embodiment, the method of preparation further comprises, prior to the firing step: continuously stirring a product system of the precipitation reaction at a second stirring rate, and then aging and drying to obtain scandium oxalate precipitate; wherein the second stirring speed is 30-300 r/min, and the stirring time is 15-90 min; the temperature of the aging step is 60-100 ℃, and the time of the aging step is 30-350 min; the temperature of the drying step is 70-120 ℃, and the time of the drying step is 120-350 min. After the precipitation reaction, the product system of the precipitation reaction is stirred at a slower speed and aged at a specific temperature and time, which is favorable for further improving the precipitation efficiency of scandium oxalate and further improving the yield of scandium oxide. The drying step is favorable for removing the moisture in scandium oxalate, and the drying process is favorable for further improving the removal efficiency of the moisture in scandium oxalate in the drying temperature and time, and simultaneously, the risk of scandium oxalate agglomeration is reduced. The second stirring speed is selected from 30r/min, 50r/min, 100r/min, 150r/min, 200r/min, 250r/min and 300r/min, and the stirring time is selected from 15min, 30min, 45min, 60min, 75min and 90min. The aging step is carried out at 60deg.C, 70deg.C, 80deg.C, 90deg.C, 100deg.C, and the aging step is carried out for 30min, 60min, 120min, 180min, 240min, 300min, 350min; the temperature of the drying step is selected from 70deg.C, 80deg.C, 90deg.C, 100deg.C, 110deg.C, 120deg.C, and the time of the drying step is selected from 120min, 150min, 180min, 210min, 240min, 270min, 300min, 350min.
Through research on the second stirring rate and stirring time, the aging temperature and aging time, and the drying temperature and drying time, the inventor found that the three parameters have a certain correlation, because the particle size of scandium oxide can be further reduced by optimizing the three parameters. In a preferred embodiment, the second stirring rate is 80 to 150r/min; stirring for 30-60 min; the temperature of the aging step is 80-90 ℃; the time of the aging step is 60-300 min; the temperature of the drying step is 80-100 ℃, and the time of the drying step is 180-300 min.
The other aspect of the application also provides the superfine scandium oxide, which is prepared by the preparation method, or the granularity of the superfine scandium oxide is 30-80 nm, and the specific surface area is 200-500 m 2 /g。
The microwave is introduced in the preparation process of scandium oxide, so that the temperature of a reaction system can be quickly increased in a short time, and the probability of heated agglomeration of scandium oxide particles is reduced. The anionic surfactant is capable of binding to the surface of the scandium oxalate precipitate, a precipitation product, when the precipitation reaction is carried out with a scandium-containing soluble salt solution in the presence of a specific anionic surfactant with oxalic acid and oxalic acid as precipitants. The anionic surfactant has better acid and alkali resistance, larger steric hindrance and rich surface charge, so that scandium oxalate precipitate in a precipitation reaction product system has better dispersibility and stability. Thus scandium oxalate can obtain scandium oxide with small particle size, high specific surface area and uniform particle size after roasting. Meanwhile, the process has the advantages of short flow, simple preparation method, low cost and the like.
In yet another aspect, the present application further provides an application of the superfine scandium oxide prepared in the present application in a laser, a superconducting material or an electrolyte material of a solid fuel cell.
Because the scandium oxide has the advantages of small particle size, high specific surface area, uniform particle size and the like, the scandium oxide can be applied to the fields of lasers, superconducting materials or electrolyte materials of solid fuel cells and the like, and the related performance of the scandium oxide can be greatly improved.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
Under the microwave radiation condition of the reaction temperature of 90 ℃ and 600W, 1.0mol/L scandium chloride solution is mixed with an anionic surface area active agent (the weight ratio of sodium dodecyl sulfate to sodium dodecyl sulfonate is 1:2), and the dosage of the anionic surface area active agent is 0.2g/L, so as to obtain a mixed solution; then, a precipitant (oxalic acid) is added dropwise to the mixed solution at a first stirring rate of 450r/min according to a molar ratio of scandium ions to precipitant of 1:2. After the addition of the precipitant is completed, continuously stirring the product system of the precipitation reaction for 30min at a second stirring rate of 200r/min, and ending the reaction.
After aging the product system of the precipitation reaction at 90 ℃ for 60min, centrifuging the obtained product system, washing 3 times by using ethanol and pure water respectively, and placing the obtained precipitate in a vacuum drying oven. Drying at 100deg.C for 180min; placing the dried sample in a corundum crucible, roasting for 250min at 850 ℃ by utilizing a microwave muffle furnace, and cooling the sample to normal temperature along with the furnace; the sample is tested and analyzed to obtain the scandium oxide powder material with the nano-scale spherical structure, the grain diameter is 30-40 nm, and the specific surface area is 450-500 m 2 And/g, the particle size distribution is narrower.
Example 2
Under the microwave radiation condition of the reaction temperature of 70 ℃ and 500W, 0.5mol/L scandium chloride solution is mixed with an anionic surface area active agent (the weight ratio of sodium dodecyl sulfate to sodium dodecyl sulfate is 1:2), and the dosage of the anionic surface area active agent is 0.2g/L, so as to obtain a mixed solution; then slowly adding the precipitant (ammonium oxalate) into the mixed solution at a first stirring rate of 300r/min according to the molar ratio of scandium ions to the precipitant of 1:3. After the addition of the precipitant is completed, continuously stirring the product system of the precipitation reaction for 60min at a second stirring rate of 100r/min, and ending the reaction.
After the product system of the precipitation reaction is aged at 70 ℃ for 180min, the obtained product system is subjected to suction filtration, and is respectively washed 3 times by ethanol and water, and the obtained precipitate is placed in a vacuum drying oven. Drying at 80deg.C for 300min; placing the dried sample in a corundum crucible, roasting in a microwave muffle furnace at 700 ℃ for 300min, and cooling the sample to normal temperature along with the furnace; the sample is tested and analyzed to obtain the nano-level spherical scandium oxide powder material with the particle diameter of 50-60 nm and the specific surface area of 380-420 m 2 And/g, the particle size distribution is uniform.
Example 3
Under the microwave radiation condition of 80 ℃ and 500W, 1.5mol/L scandium chloride solution is mixed with an anionic surface area active agent (the weight ratio of sodium dodecyl sulfate to sodium dodecyl sulfonate is 1:2), and the dosage of the anionic surface area active agent is 0.2g/L, so as to obtain a mixed solution; then, a precipitant (oxalic acid) was added dropwise to the above-mentioned mixed solution at a first stirring rate of 200r/min in a molar ratio of scandium ions to precipitant of 1:5. After the addition of the precipitant is completed, continuously stirring the product system of the precipitation reaction for 45min at a second stirring rate of 50r/min, and ending the reaction.
And (3) ageing the product system of the precipitation reaction at 80 ℃ for 300min, filtering the obtained product system, washing 3 times by using ethanol and water respectively, and placing the obtained precipitate in a vacuum drying oven. Drying at 90deg.C for 240min; placing the dried sample in a corundum crucible, roasting in the muffle furnace at 800 ℃ for 200min by utilizing the muffle furnace, and cooling the sample to normal temperature along with the furnace; the sample is tested and analyzed to obtain the nano spherical scandium oxide powder material with uniform particle size and nano spherical scandium oxide powder material with particle size of 40-60 nm and specific surface area of 380-485 m 2 And/g, the particle size distribution span is larger, and the particle size of the nano particles prepared in examples 1 and 2 is not uniform.
Example 4
The differences from example 1 are: the amount of anionic surfactant was 0.005g/L.
When the dosage of the surfactant is small, the grain diameter is 30-70 nm, the grain diameter distribution of the reaction product is large, and the specific surface area is 260-340 m 2 And/g, the nanosphere structure is incomplete, wherein the nanosphere structure is doped with a non-spherical structure.
Example 5
The differences from example 1 are:
in the precipitation reaction process, the second stirring speed is 80r/min, and the stirring time is 60min; the frequency of the microwave is 300W, and the reaction temperature is 80 ℃; the temperature of the aging step is 90 ℃, and the time of the aging step is 120min; the temperature of the drying step is 80 ℃, and the time of the drying step is 240min.
Compared with the example 1, the second stirring speed is slowed, the grain diameter of the product is 30-50 nm, and the specific surface area is 420-500 m 2 And/g, the particle size distribution is wider.
Example 6
The differences from example 1 are:
in the precipitation reaction process, the second stirring speed is 150r/min, and the stirring time is 60min; the frequency of the microwave is 700Hz, and the reaction temperature is 90 ℃; the temperature of the aging step is 80 ℃, and the time of the aging step is 120min; the temperature of the drying step is 100 ℃, and the time of the drying step is 240min.
Compared with the embodiment 1, the second stirring speed is too fast, the grain diameter is 30-40 nm, the specific surface area is 450-500 m 2 /g, but the partial scandia sphere is not structurally complete.
Example 7
The differences from example 1 are:
in the precipitation reaction process, the second stirring speed is 200r/min, and the stirring time is 60min; the frequency of the microwave is 300W, and the reaction temperature is 70 ℃; the temperature of the aging step is 70 ℃, and the time of the aging step is 120min; the temperature of the drying step is 120 ℃, and the time of the drying step is 240min.
Nanosphere scandium oxide powder material and nanosphere scandium oxidePowder with particle diameter of 50-70 nm and specific surface area of 350-420 m 2 And/g, the particle size distribution span is larger.
Comparative example 1
The differences from example 1 are: the surfactant is polyethylene glycol nonionic surfactant (manufacturer is national drug group chemical reagent Co., ltd.).
The nano spherical scandium oxide powder material has a layered structure, the grain size distribution is 3-15 mu m, and the specific surface area is 12-23 m 2 /g。
Comparative example 2
The differences from example 1 are: no surfactant is added in the preparation process.
The scandium oxide is of a long strip structure, the grain size distribution is 3-20 mu m, and the specific surface area is 9-20 m 2 And/g, the particle size distribution is relatively broad.
Comparative example 3
The differences from example 1 are: the preparation process is not carried out under microwave conditions.
Compared with the example 1, the scandium oxide prepared by the reaction under the condition of no microwave radiation has wider particle size distribution, non-uniformity and small specific surface area.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: by adopting the preparation method provided by the application, the spherical scandium oxide with small particle size, high specific surface area and uniform particle size can be obtained. Meanwhile, the process has the advantages of short flow, simple preparation method, low cost and the like.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (14)

1. A method for preparing superfine scandium oxide, which is characterized by comprising the following steps:
in the presence of microwaves and an anionic surfactant, carrying out precipitation reaction on scandium-containing soluble salt solution and a precipitator to obtain scandium oxalate precipitate, wherein the precipitator is oxalic acid or oxalate;
roasting the scandium oxalate precipitate to obtain the superfine scandium oxide; the anionic surfactant is sodium dodecyl sulfate and sodium dodecyl sulfonate with a weight ratio of 1:2.
2. The method according to claim 1, wherein the scandium ion content in the scandium-containing soluble salt solution is 0.1 to 2.0mol/L, and the anionic surfactant content is 0.01 to 2g/L.
3. The method according to claim 1, wherein the scandium ion content in the scandium-containing soluble salt solution is 0.5 to 1.5mol/L.
4. The method of claim 1, wherein the precipitation reaction step comprises:
mixing the scandium-containing soluble salt solution with the anionic surfactant, and then adjusting the pH value of a reactant system of the precipitation reaction to 1-5 by adopting a pH regulator to obtain a mixed solution;
and adding the precipitant into the mixed solution to react, so as to obtain scandium oxalate precipitate.
5. The method of claim 4, wherein the precipitation reaction step comprises: and adding the precipitant into the mixed liquid at a first stirring rate, wherein the first stirring rate is 150-500 r/min.
6. The method according to claim 5, wherein the first stirring rate is 200 to 450r/min.
7. The method according to claim 1, wherein the microwave has a frequency of 300 to 700W in the precipitation reaction; the reaction temperature is 60-100 ℃.
8. The method according to claim 7, wherein the microwave is at a frequency of 450 to 600W and a reaction temperature of 80 to 90 ℃.
9. The method of claim 7, wherein the temperature of the firing step is 600-900 ℃; the roasting step is carried out for 120-400 min.
10. The method according to claim 9, wherein the temperature of the calcination step is 700 to 850 ℃, and the time of the calcination step is 220 to 300 minutes.
11. The method of producing according to claim 4, characterized in that before the firing step, the method of producing further comprises:
continuously stirring the product system of the precipitation reaction at a second stirring rate, and then aging and drying to obtain scandium oxalate precipitate;
wherein the second stirring speed is 30-300 r/min, and the stirring time is 15-90 min; the temperature of the aging step is 60-100 ℃, and the time of the aging step is 30-350 min; the temperature of the drying step is 70-120 ℃, and the time of the drying step is 120-350 min.
12. The method of claim 11, wherein the second stirring rate is 80-150 r/min; stirring for 30-60 min; the temperature of the aging step is 80-90 ℃; the time of the aging step is 60-300 min; the temperature of the drying step is 80-100 ℃, and the time of the drying step is 180-300 min.
13. A process for producing ultrafine scandia according to any one of claims 1 to 12, wherein the ultrafine scandia has a particle size of 30 to 80nm and a specific surface area of 200 to 500m 2 /g。
14. Use of the superfine scandium oxide according to claim 13 in a laser, a superconducting material or an electrolyte material for a solid fuel cell.
CN202210205141.1A 2022-03-02 2022-03-02 Superfine scandium oxide, preparation method and application thereof Active CN114477263B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210205141.1A CN114477263B (en) 2022-03-02 2022-03-02 Superfine scandium oxide, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210205141.1A CN114477263B (en) 2022-03-02 2022-03-02 Superfine scandium oxide, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114477263A CN114477263A (en) 2022-05-13
CN114477263B true CN114477263B (en) 2024-02-13

Family

ID=81483844

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210205141.1A Active CN114477263B (en) 2022-03-02 2022-03-02 Superfine scandium oxide, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114477263B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008127248A (en) * 2006-11-21 2008-06-05 National Institute For Materials Science Method for powdering inorganic oxide or inorganic hydroxide
CN103418316A (en) * 2010-01-29 2013-12-04 张颖 Preparation method of modified micro-granules
JP2019147716A (en) * 2018-02-27 2019-09-05 住友金属鉱山株式会社 Scandium compound
CN110498439A (en) * 2019-09-27 2019-11-26 中国恩菲工程技术有限公司 Prepare the method with the scandium oxide powder of porous structure
KR20200136219A (en) * 2019-05-27 2020-12-07 한국화학연구원 Mesoporous hydrophobic oxide material for adsorbing air and preparing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008127248A (en) * 2006-11-21 2008-06-05 National Institute For Materials Science Method for powdering inorganic oxide or inorganic hydroxide
CN103418316A (en) * 2010-01-29 2013-12-04 张颖 Preparation method of modified micro-granules
JP2019147716A (en) * 2018-02-27 2019-09-05 住友金属鉱山株式会社 Scandium compound
KR20200136219A (en) * 2019-05-27 2020-12-07 한국화학연구원 Mesoporous hydrophobic oxide material for adsorbing air and preparing method thereof
CN110498439A (en) * 2019-09-27 2019-11-26 中国恩菲工程技术有限公司 Prepare the method with the scandium oxide powder of porous structure

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
用微波均相沉淀法合成Sc_2O_3纳米粉;吕滨;孙旭东;孙挺;王毅;;材料研究学报;25(03);255-258 *
稀有元素钪的研究现状;朱敏杰;沈春英;丘泰;;材料导报;20(S1);379-381 *

Also Published As

Publication number Publication date
CN114477263A (en) 2022-05-13

Similar Documents

Publication Publication Date Title
CN102337136B (en) Metal-nanoparticle-doped oxide luminescent material with hollow structure and preparation method thereof
CN105665742A (en) Method for preparing nano sliver wire dispersion liquid controllable in wire diameter and high in length-diameter ratio in batches
CN109019656B (en) Method for producing nano rare earth oxide powder
CN104925867B (en) A kind of nanometer wolframic acid caesium powder body and preparation method and application
CN106082358A (en) The preparation method of Cobalto-cobaltic oxide
CN107565124B (en) Nickel cobalt lithium manganate precursor and preparation method thereof
CN103682301A (en) Preparation method of nanometer lithium titanate covered with double highly-conductive materials
CN108611088A (en) A kind of method that sonochemical method prepares ZnO quantum dot
CN104528799A (en) Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder
CN110642283B (en) Method for preparing spherical scandium oxide
CN106992285B (en) A kind of preparation method of nickel cobalt aluminium ternary precursor
CN109052450A (en) A kind of preparation method of high-purity mangesium oxide gadolinium
CN114477263B (en) Superfine scandium oxide, preparation method and application thereof
CN109133144B (en) Preparation method of monodisperse ultra-small particle size cerium dioxide nanocrystal
CN109678211A (en) A kind of tantalum doping caesium tungsten bronze and the preparation method and application thereof
CN105602566A (en) Rare earth-doped NaGdF4 upconversion nanocrystalline and preparation method thereof
CN105271443A (en) Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating
CN110498439B (en) Method for preparing scandium oxide powder with porous structure
CN103663543B (en) A kind of method preparing nano zinc oxide material
CN113800574B (en) Nickel-manganese-iron-aluminum-lithium positive electrode material and preparation method thereof
CN113363444B (en) Nano lithium titanate-coated modified graphite negative electrode material, and preparation method and application thereof
CN111056564B (en) Microwave preparation method of lanthanum-cerium-terbium oxide fluorescent powder
CN109133161B (en) A kind of preparation method of strontium titanate nanoparticles
CN106365192A (en) Preparation method of ultra-small scale rare-earth oxide nano-powder
CN106816588B (en) A kind of preparation method in nano lithium titanate surface enrichment strontium element

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