CN113233493A - Method for synthesizing rare earth nano oxide particle material in batch - Google Patents
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002245 particle Substances 0.000 title claims abstract description 43
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 36
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 39
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract 2
- -1 rare earth chloride Chemical class 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 17
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 16
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 13
- 238000005498 polishing Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 238000011161 development Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- GJFXIYGDVYZDRX-UHFFFAOYSA-N cerium;oxozirconium Chemical compound [Ce].[Zr]=O GJFXIYGDVYZDRX-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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- 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
-
- 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
- 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
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Analytical Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for synthesizing rare earth nano oxide particle materials in batch, which comprises the following steps: the chlorinated rare earth precursor and carbonate/bicarbonate are uniformly mixed, and high-temperature treatment is carried out in air/oxygen atmosphere to obtain the rare earth oxide nano-scale, micron-scale or submicron-scale powder. The method realizes the controllable batch preparation of the nano rare earth oxide powder material, effectively prevents the particles from agglomerating, effectively solves the problems of uncontrollable particles and agglomeration in the high-temperature roasting process caused by conventional salt, and simultaneously effectively keeps the nano rare earth oxide powder material in the similar spherical distribution.
Description
Technical Field
The invention relates to the technical field of nano rare earth oxide powder metallurgy and materials, in particular to a method for synthesizing rare earth nano oxide particle materials in batch.
Background
The development of high technology has increasingly demanded rare earth materials, and rare earth compound materials with high purity and special physical properties are required for developing new properties of rare earth elements, particularly optical, electrical, magnetic and other properties. Conventional purification method of rare earth compoundThere are several methods to do this: solvent extraction, ion exchange chromatography, extractive chromatography, redox and separation of rare earth elements from non-rare earth impurities. The solvent extraction method can generally obtain products with the purity of 2N-4N, and partial elements such as La and Y can reach the purity of 5N-6N. The ion exchange method is less in use at present, the extraction chromatography technology is the organic combination and improvement of the ion exchange technology and the liquid-liquid extraction technology, has the characteristics of small reagent loss, closed environment, easy temperature control and the like, is suitable for the separation and purification of rare earth elements in small batch, multiple varieties and high purity and analysis technology required by modern materials, most rare earth compounds can achieve the purity of 5N-6N at present, and reaches the international advanced level through scientific and technological clearance in the field in the last 90 th century in China. The oxidation-reduction method is mainly used for preparing variable valence elements Ce and Eu, the oxidation method of Ce comprises an electrolytic oxidation method and a strong oxidant oxidation method, and a cerium compound product with the purity of more than 5N can be prepared by combining a cerium oxidation method with an extraction method or a ceric ammonium nitrate crystallization method; the Eu purification method comprises a zinc powder reduction-alkalinity method (extraction method) and an electrolytic reduction-alkalinity method (extraction method), and can prepare 5N-6N Eu2O3And (5) producing the product. The separation method of rare earth elements and non-rare earth impurities includes neutralization method, oxalate precipitation method, sulfide precipitation method and solvent extraction method, etc., and the main separated impurity elements include Fe, Al, Ca, Mg, Zn, Cu and Pb, etc. At present, the research and development investment in the aspects of rare earth extraction separation and purification in foreign countries is basically stopped, China is mainly relied on to provide high-purity rare earth compound products, but the method still has advantages in the aspects of deep removal of non-rare earth impurities and rare earth halide crystallization water in foreign countries.
The cerium oxide-based rare earth polishing powder has been used for polishing glass for more than 40 years, gradually replaces ferric oxide by virtue of good polishing performance, and becomes a main material for polishing. Currently, liquid crystal display panels have a dominant position in the display field, and the requirements for polishing the panels with glass are extremely high: the average particle size of the powder is about 1 mu m, and the particle size distribution is required to be very uniform. The foreign countries have formed unique brand products and larger industrial scale in the field of high-end rare earth polishing powder, and the rare earth polishing powder products in Japan, America and Britain have strong competitiveness in the international market.
The nanometer cerium oxide powder materials with different particle sizes and different morphologies are prepared by different liquid phase methods including a precipitation method, a microemulsion method, a sol-gel method, a hydrothermal method and the like, but the powder prepared by the methods has the defects of wide particle size distribution, serious agglomeration, non-uniform particle morphology, poor processing performance and the like, and has the problems of complicated preparation process, serious environmental pollution, serious material waste and the like. Meanwhile, because industrial rare earth raw material liquid usually has trace non-cerium impurity ions and residual organic phase, the components and particle size distribution of product powder are difficult to control, and many methods cannot be applied to the industry and cannot meet the product requirement of producing nano cerium oxide powder for high-end application. The method further improves the technology and equipment, develops the nano rare earth oxide powder with simple production process, low production cost, high purity, controllable particle size, less agglomeration and good powder processing performance, and has important significance for promoting the industrialized application of the rare earth oxide powder production technology and the development of the rare earth high-end material industry in China.
Necessity, urgency:
china is a world large rare earth country, the rare earth reserves and the rare earth output are at the top of the world, but the development and utilization of rare earth resources in China are not ideal. In recent years, the rare earth industry is gradually improved, the situation of 'small, scattered and disorderly' in the past is gradually changed into a good situation of large-scale, centralized and ordered development, but the problems of illegal mining, illegal production, insufficient technological innovation capability and the like still exist, so that the rare earth industry is still in a disadvantage in international competition, the resource advantages cannot be fully exerted, and the quality and the benefit need to be further improved. The development of the rare earth nano material is the embodiment of comprehensive national strength in China, the development and application of the nano rare earth material can greatly improve the value of rare earth resources, open up a new way for efficiently utilizing the rare earth resources, expand the application range of the rare earth resources and finally convert the resource advantages into economic advantages. The nanometer rare earth oxide material is an indispensable raw material for developing high and new technologies and national defense industry, but is limited by the development of preparation technology at present, and the application requirements of the nanometer rare earth oxide on the performance and the high and new technologies are still in a large gap. How to realize the deep purification of the cerium chloride raw material liquid and join the rare earth separation process and break through the technical bottleneck of the essentially stable and controllable preparation of the high-performance nano-cerium oxide, and the realization of economically and environmentally producing the nano-rare earth oxide with stable performance, uniform granularity and controllable appearance is the main research direction in the field of future nano-rare earth oxide and has important significance for the further development of the integration of the nano-rare earth oxide and rare earth metallurgy materials.
Market demand: the nano cerium oxide is an important raw material for preparing glass polishing powder, a catalyst, a luminescent material and electronic ceramics, and in recent years, researchers report that the nano cerium oxide has great potential value in the medical field. The application of the nano cerium oxide in luminescent materials is more and more extensive, and the nano cerium oxide is considered to be capable of overcoming the defects of quantum dots and organic fluorescent dyes in the biomedical field, such as the problems of harm to organisms, low detection sensitivity and the like; in the field of automobile exhaust purification catalysts, a cerium-zirconium oxygen storage material taking cerium oxide as a raw material is used as an important catalytic assistant in a three-way catalyst, so that the emission of CO, HC, PM and NOx in exhaust can be remarkably reduced; as a polishing material, the nano cerium oxide polishing powder has the advantages of high polishing speed, high smoothness and long service life, does not pollute the environment and is easy to remove from a stained object compared with the traditional polishing powder (iron red powder); in the aspect of electronic ceramics, because the unique oxygen storage and release function and the high-position rapid vacancy diffusion capacity of the nano cerium oxide powder are used for preparing the nano cerium oxide powder into porous ceramics, on one hand, the high specific surface area of the powder is partially reserved, and on the other hand, the cerium oxide powder can be prepared into any shape for practical application; in the field of fuel cells, the use of the cerium oxide-based electrolyte effectively improves the electrocatalytic performance of a cathode on oxygen and an anode on fuel gas and the conductive performance of a cerium oxide-based electrolyte film, reduces electrode polarization resistance and ohmic polarization resistance, and effectively improves the medium-temperature and low-temperature performances of the cell. With the continuous advancement of the strategy of sustainable development, the demand of various industries on nano cerium oxide is steadily increased, the requirements on the performance of powder are also continuously improved, and the demand on large-scale efficient preparation technology of high-performance nano cerium oxide powder materials is increasingly strong.
Disclosure of Invention
The invention aims to provide a novel method for efficiently and easily industrially preparing nano rare earth oxide powder metallurgy and materials in a controllable manner, and the short-process controllable batch preparation of the nano rare earth oxide powder is realized.
In order to achieve the above object, the present invention provides a method for batch synthesis of rare earth nano oxide particle materials, comprising the following steps:
the chlorinated rare earth precursor and carbonate/bicarbonate are uniformly mixed, and high-temperature treatment is carried out in air/oxygen atmosphere to obtain the rare earth oxide nano-scale, micron-scale or submicron-scale powder.
Preferably, the rare earth chloride precursor is prepared by adopting a rare earth chloride solution as a raw material and performing evaporative crystallization; the rare earth chloride precursor is a mixture of rare earth chloride crystals and/or other rare earth salts, wherein the other rare earth salts comprise one or more of rare earth oxide, rare earth carbonate and rare earth oxalate.
Preferably, the carbonate/bicarbonate salt comprises one or more of sodium carbonate/bicarbonate, potassium carbonate/bicarbonate, lithium carbonate/bicarbonate, magnesium carbonate/bicarbonate.
Preferably, the rare earth chloride precursor and the carbonate/bicarbonate are uniformly mixed according to the molar ratio of 2:1-1:3 of chloride ions and sodium ions.
Preferably, the rare earth chloride precursor and the carbonate/bicarbonate are uniformly mixed according to the molar ratio of 2:1-1:3 of chloride ions and potassium ions.
Preferably, a modifier or a roasting aid is also added during the high-temperature treatment.
Preferably, the modifier or the roasting aid is an inorganic sodium salt or an organic sodium salt.
Preferably, the parameters of the high-temperature treatment are as follows: raising the temperature to 500 ℃ and 1500 ℃, and naturally cooling after heat preservation treatment for 0-6 h.
Preferably, the parameters of the high-temperature treatment are as follows: heating to 700 ℃ and 1200 ℃, and naturally cooling after heat preservation treatment for 0.3-3 h.
Preferably, the temperature rise rate of the high-temperature treatment is 1-100 ℃/min.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the controllable batch preparation of the nano rare earth oxide powder material is realized, the particle agglomeration is effectively prevented, the difficult problems of uncontrollable particles and agglomeration in the high-temperature roasting process caused by conventional salt are effectively solved, and the nano rare earth oxide powder material is effectively kept to be in the similar spherical distribution.
(2) The rare earth elements of the nano rare earth oxide powder material synthesized by the invention can be one, two or more.
(3) The invention can realize the control of the particle size and the shape of the nano rare earth oxide powder material by adjusting the type and the proportion of carbonate or bicarbonate.
(4) The method has the advantages of simple operation, short process flow, easy industrialization, and cheap and economic chemical agents.
Drawings
FIG. 1 is a SEM image and particle size distribution plot for sample 1;
FIG. 2 is a SEM image and particle size distribution plot for sample 2;
FIG. 3 is a SEM image and particle size distribution plot for sample 3;
FIG. 4 is a SEM image and particle size distribution plot for sample 4;
FIG. 5 is a SEM image and particle size distribution plot for sample 5;
FIG. 6 is a SEM image and particle size distribution plot for sample 6;
FIG. 7 is a SEM image and particle size distribution plot for sample 7;
FIG. 8 is a SEM image and particle size distribution plot for sample 8;
FIG. 9 is an SEM photograph of a sample obtained in a comparative example, wherein (a) is CeCO3KCl is 2:1, and CeCO is shown in figure (b)3:KCl＝1:1。
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
10g of cerium chloride is mixed with sodium carbonate and ground into uniform powder, wherein the ratio of chlorine to sodium is 1:2 and 1: 1. Putting the powder into a muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, carrying out heat treatment for 3 hours, and cooling to room temperature. A white sample was taken.
10g of cerium chloride is mixed with sodium bicarbonate and ground into uniform powder, wherein the ratio of chlorine to sodium is 1:2 and 1: 1. Putting the powder into a muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, carrying out heat treatment for 3 hours, and cooling to room temperature. A white sample was taken.
The specific sample numbers for this experiment are shown in table 1.
TABLE 1
| Sample number | Experimental reagent | Ratio of chlorine to sodium |
| 1 | Cerium chloride and sodium carbonate | 1:2 |
| 2 | Cerium chloride and sodium carbonate | 1:1 |
| 3 | Cerium chloride and sodium bicarbonate | 1:2 |
| 4 | Cerium chloride and sodium bicarbonate | 1:1 |
FIGS. 1-4 show SEM images and particle size distribution plots for samples 1-4, respectively, showing that the sample particles are uniformly distributed and spherical; wherein, when the ratio of sodium chloride to sodium chloride is 1:1, the particle size is uniform and fine. The sample was also analyzed by XRD to be ceria.
Example 2
10g of cerium chloride and potassium carbonate are mixed and ground into uniform powder, wherein the ratio of chlorine to potassium is 2:1 and 1: 1. Putting the powder into a muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, carrying out heat treatment for 3 hours, and cooling to room temperature. A white sample was taken.
10g of cerium chloride is mixed with potassium bicarbonate and ground into uniform powder, wherein the ratio of chlorine to potassium is 2:1 and 1: 1. Putting the powder into a muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, carrying out heat treatment for 3 hours, and cooling to room temperature. A white sample was taken.
The specific sample numbers for this experiment are shown in table 2.
TABLE 2
| Sample number | Experimental reagent | Ratio of chlorine to |
| 5 | Cerium chloride and potassium carbonate | 2:1 |
| 6 | Cerium chloride and carbonic acidPotassium salt | 1:1 |
| 7 | Cerium chloride and potassium bicarbonate | 2:1 |
| 8 | Cerium chloride and potassium bicarbonate | 1:1 |
FIGS. 5-8 show SEM images and particle size distribution plots for samples 5-8, respectively, showing that the sample particles are uniformly distributed and spherical; wherein, when the ratio of potassium chloride to potassium chloride is 1:1, the particle size is uniform and fine. The sample was also analyzed by XRD to be ceria.
Comparative example
Grinding and uniformly mixing cerium carbonate and sodium chloride, putting the powder into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, carrying out heat treatment for 3 hours, and cooling to room temperature. A white sample was taken. Fig. 9 shows that a large number of agglomerated ceria particles were present in the sample, the particle size was not controllable, and the particles were not spheroidal and morphology was not controllable.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A method for the batch synthesis of rare earth nano oxide particle materials, which is characterized by comprising the following steps:
the chlorinated rare earth precursor and carbonate/bicarbonate are uniformly mixed, and high-temperature treatment is carried out in air/oxygen atmosphere to obtain the rare earth oxide nano-scale, micron-scale or submicron-scale powder.
2. The method for mass production of rare earth nano oxide particle materials according to claim 1, wherein the rare earth chloride precursor is prepared by evaporative crystallization using a rare earth chloride solution as a raw material; the rare earth chloride precursor is a mixture of rare earth chloride crystals and/or other rare earth salts, wherein the other rare earth salts comprise one or more of rare earth oxide, rare earth carbonate and rare earth oxalate.
3. The method for batch synthesis of rare earth nano-oxide particulate material according to claim 1, wherein the carbonate/bicarbonate salt comprises one or more of sodium carbonate/bicarbonate, potassium carbonate/bicarbonate, lithium carbonate/bicarbonate, magnesium carbonate/bicarbonate.
4. The method for mass production of rare earth nano oxide particle material according to claim 3, wherein the rare earth chloride precursor and the carbonate/bicarbonate are uniformly mixed in a molar ratio of chloride ions to sodium ions of 2:1 to 1: 3.
5. The method for mass production of rare earth nano oxide particle material according to claim 3, wherein the rare earth chloride precursor and the carbonate/bicarbonate are uniformly mixed in a molar ratio of chloride ions to potassium ions of 2:1 to 1: 3.
6. The method for mass production of rare earth nano-oxide particle materials according to claim 1, wherein a modifier or a baking aid is further added during the high temperature treatment.
7. The method for mass production of rare earth nano-oxide particle materials according to claim 6, wherein the modifier or the baking aid is an inorganic sodium salt or an organic sodium salt.
8. The method for mass synthesis of rare earth nano-oxide particle materials according to claim 1, wherein the parameters of the high temperature treatment are: raising the temperature to 500 ℃ and 1500 ℃, and naturally cooling after heat preservation treatment for 0-6 h.
9. The method for batch synthesis of rare earth nano-oxide particle materials according to claim 8, wherein the parameters of the high temperature treatment are: heating to 700 ℃ and 1200 ℃, and naturally cooling after heat preservation treatment for 0.3-3 h.
10. The method for mass production of rare earth nano oxide particle materials according to claim 8, wherein the temperature increase rate of the high-temperature treatment is 1-100 ℃/min.
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| CN113800551A (en) * | 2021-10-27 | 2021-12-17 | 福建省长汀金龙稀土有限公司 | Method for preparing rare earth oxide powder by utilizing steam roasting of rare earth chloride |
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