CN112939052A - Preparation method of small-particle-size cerium oxide - Google Patents
Preparation method of small-particle-size cerium oxide Download PDFInfo
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- CN112939052A CN112939052A CN202110300454.0A CN202110300454A CN112939052A CN 112939052 A CN112939052 A CN 112939052A CN 202110300454 A CN202110300454 A CN 202110300454A CN 112939052 A CN112939052 A CN 112939052A
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 50
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 68
- 239000007787 solid Substances 0.000 claims abstract description 40
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 37
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims abstract description 32
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 29
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 29
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 8
- 238000000875 high-speed ball milling Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 58
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 230000010355 oscillation Effects 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 13
- -1 graphite alkene Chemical class 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 102220042174 rs141655687 Human genes 0.000 description 2
- 102220043159 rs587780996 Human genes 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
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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
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- 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
- C01P2006/14—Pore volume
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- 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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a preparation method of small-granularity cerium oxide, which comprises the following specific steps: (1) preparing graphene by a hummer method and carrying out high-speed ball milling; (2) the concentration of the prepared ammoniated graphene is 2-7 g/L; (3) slowly titrating; (4) adding ammonia water with the concentration of 7-8mol/L into the cerium chloride solution according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.5-2, and continuously stirring; (5) ammonium bicarbonate deposition to prepare grey white solid powder for later use; (6) and (4) delivering the grey white powder into a kiln for high-temperature calcination. The method improves the preparation efficiency of the small-granularity cerium oxide, lays a raw material foundation for large-scale industrial application, and particularly has cerium oxide particles with high specific surface area and uniform particle size.
Description
Technical Field
The invention relates to the technical field of cerium oxide preparation, in particular to a preparation method of small-granularity cerium oxide.
Background
With the improvement of the performance requirements of high and new materials in industry, the interest of preparing cerium oxide powder materials with different physical properties is more and more aroused. Therefore, the preparation of cerium oxide ultrafine powder materials with controllable physical properties becomes a focus of research on inorganic powder materials. The small-granularity rare earth oxide powder serving as a functional material has the advantages of high specific surface area, high surface activity, high chemical reaction speed, quick dissolution, high sintered body strength and remarkable effects on refractory materials, semiconductor materials, sensors, ultra-high temperature heat-resistant alloys and the like due to small granularity, uniform granules and narrow distribution. For many years, the production process technology of cerium oxide mainly comprises methods such as an extraction method, an electrolytic oxidation method, an extraction separation method and the like, but the existing process is complex in operation and high in cost, and the prepared cerium oxide is uneven in particle size, poor in flowability and not beneficial to industrial application.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of small-particle-size cerium oxide, which improves the preparation efficiency of the small-particle-size cerium oxide, lays a raw material foundation for large-scale industrial application, and particularly provides cerium oxide particles with high specific surface area and uniform particle size.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of small-particle-size cerium oxide comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 25-28wt.%, carrying out ultrasonic oscillation of a cell disruption instrument, and raising the temperature of the ammonia water solution to 80-90 ℃ when the ammonia water solution is oscillatedoC, stopping ultrasonic oscillation, and keeping the temperature at 80-90 DEGoC, refluxing for 4-6 h; naturally cooling, filtering once, diluting to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8-8.5, and the concentration of the ammoniated graphene is 2-7 g/L;
(3) and (3) adding water into the cerium chloride stock solution to dilute until the REO is 60-90g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 150-.
(4) Heating the solution to 30-35 ℃, adding 7-8mol/L ammonia water according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.5-2, and continuously stirring;
(5) heating the solution obtained in the step (4) to 45-55 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of REO mass (g) of the solution obtained in the step (4) to solid ammonium bicarbonate mass (g) of 1:0.7-1, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6-7, and then carrying out centrifugal drying on the precipitate to obtain off-white solid powder for later use;
(6) and (4) delivering the grey white powder into a kiln for high-temperature calcination, and performing temperature programmed calcination.
In some embodiments, after the ball milling and cell disruption ultrasonication, the longest dimension of the graphene sheet layer is controlled to be not greater than 2 μm and the thickness is controlled to be not greater than 10 nm.
In some embodiments, the temperature-programmed calcination is 2-3oC/min, up to 300-oC, keeping the temperature for 1-2h, and then 10-15oC/min heating to 900-oAnd C, keeping the constant temperature for 1.5-2 h.
In some embodiments, the cell disruptor has a frequency of 30KHz and a power of 800W.
In some embodiments, the small-particle-size cerium oxide has a particle size of D50 ≤ 4 μm and a particle size of D90 ≤ 8.2 μm.
In some embodiments, the cerium oxide has a specific surface area of 150-200m2(g), pore size concentration distribution, pore volume of 0.257-0.268cm3The pore diameters are concentrated and distributed at 3.6nm and 5.7 nm.
Briefly describing the principle of the invention for preparing small particle size, high dispersion and high specific surface area:
firstly, graphene is prepared by a typical hummer method, the preparation method is simple, a single-layer graphene sheet layer can be prepared easily, but the long side of the sheet layer is large and exceeds the particle size of cerium oxide, so that subsequent pore-forming is not facilitated, and meanwhile, the graphene sheet layer is large and is not beneficial to obtaining dispersed graphene and needs to be ground.
And then reducing the long side of the sheet layer by ball milling, dispersing the graphene sheet layer re-bonded by ball milling again by a cell disruptor, if the ultrasonic oscillation of the cell disruptor is cancelled, the thickness of the graphene sheet layer is extremely large, the aperture is larger than 100nm after the pore is formed by cerium oxide, and the contrast surface area does not contribute, so the long side, the thickness and the dispersity of the graphene sheet layer need to be controlled.
Secondly, through the aqueous ammonia backward flow, introduce the amino on graphite alkene surface, mainly there are three effects, one, improve the hydrophilicity of graphite alkene, make things convenient for the abundant contact of cerium oxide and graphite alkene, two, adsorbed amino, be favorable to cerium ion and graphite alkene to pass through amino and be connected, three, avoid agglomerating again through the graphite alkene of cell disruption appearance ultrasonic oscillation dispersion, should pay attention to the concentration of pH concentration and graphite alkene in this process, too high pH can lead to too big in the precipitate crystal of subsequent cerium chloride formation, the dispersity is low, during pH is too low can not form the precipitate crystal, the concentration of graphite alkene is too big, be unfavorable for the deposit to take place, the concentration of graphite alkene is too low, be unfavorable for the promotion of specific surface area.
Then, adding water into the cerium chloride stock solution to dilute until REO is 60-90g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution in the step (2), wherein the temperature is normal temperature, the dropping amount is 150-200ml, the dropping time is 20-30min, continuously stirring for 10-20min after dropping is finished, in the process, the titration should be slow, a needle tube which is pushed quantitatively is recommended to be used for titration, or gravity titration is carried out, after the titration is carried out, through stirring, metal ions in the cerium chloride are concentrated and directionally distributed on the amino surface of the graphene, and precipitation is carried out to form tiny Ce (OH)3Depositing seed particles, a process known as Ce (OH)3Primary precipitation seed crystal process.
Then heating the solution to 30-35 ℃, adding 7-8mol/L ammonia water according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.5-2, and continuously stirring; continuing to deposit large particles of Ce (OH) on the very small precipitated seed particles3Said particlesThe deposition process can coat the graphene, so that the deposition separation of the Graphene (GE) and the cerium oxide is effectively avoided, the high specific surface area of the cerium oxide is facilitated, and the CeCl3 is excessive in the process and is called Ce (OH)3And (5) secondary deposition and growth.
Then, after the solution obtained in the step (4) is heated to 45-55 ℃, according to the proportion of 1:0.7-1 of the REO mass (g) of the solution obtained in the step (4) and the mass (g) of the solid ammonium bicarbonate, slowly adding the solid ammonium bicarbonate while stirring, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6-7, and then centrifugally drying the precipitated precipitate to obtain off-white solid powder for later use, wherein the CeCl mainly reacts as follows in the process3+6NH4HCO3=Ce(CO3)3+NH4Cl; that is, Ce (CO) is mainly formed in the process3)3Precipitating as Ce (CO) in a secondary anisotropic precipitation3)3。
And finally, roasting, namely, temperature programmed roasting: 2-3oC/min, up to 300-oC, keeping the temperature for 1-2h, and then 10-15oC/min heating to 900-oC, roasting and keeping the constant temperature for 1.5-2 h. The oxidation combustion of ammoniated graphene mainly occurs in the first stage, the temperature rising speed is slow, the sufficient combustion of the graphene is convenient, the obtained pore channel is not more than 10nm, and in the second stage, the pore channel is 10-15 nmoC/min heating to 900-oC is kept at the constant temperature for 1.5-2h, the temperature rise speed is high, the situation that the 10nm pore channel is completely closed due to slow roasting is avoided, the 10nm pore channel is shrunk to 3.6nm through fast roasting, and Ce (CO) can also occur in the process3)3And Ce (OH)3By decomposition reactions in which fine gases, e.g. CO, are produced2The gas is effectively pore-formed, the pore diameters are concentrated and distributed at 5.7nm, as can be seen from figure 1, the pore diameter concentration of 3.6nm is good and is derived from graphene with uniform size and appearance, and the pore diameter concentration of 5.7nm is general and is derived from an uncontrollable gas release process.
The invention has the advantages and positive effects that:
1. the preparation method of the small-granularity cerium oxide provided by the invention has the advantages of simple and convenient operation steps, high efficiency of producing the small-granularity cerium oxide, low temperature required by the whole reaction process and low cost.
The small-particle-size cerium oxide prepared by the method disclosed by the invention has the advantages that no dispersant additive is added in the process, the flowability is good, the particle size is uniform, the screening is easy, the raw material foundation is laid for large-scale preparation of a polishing agent, small-particle precipitated crystals are introduced through ammoniated graphene, and the particle size D50 of the prepared cerium oxide is less than or equal to 4 microns and the particle size D90 of the prepared cerium oxide is less than or equal to 8.2 microns through secondary and tertiary deposition.
2. The invention can produce cerium oxide with different particle sizes by adjusting the adding amount of ammonia water, has strong flexibility, and the prepared cerium oxide has good quality and can meet various production requirements.
3. The method can control the finishing process of the reaction by monitoring the change of the PH, is simple and convenient to operate, stops adding the solid ammonium bicarbonate when the PH value is 6-7, reduces the using amount of the solid ammonium bicarbonate, reduces the production cost, reduces the byproducts of the reaction, and improves the yield of the small-granularity cerium oxide.
4. After the solid ammonium bicarbonate is stopped being added, the precipitated precipitate is centrifugally dried to obtain white solid powder, and the white solid powder is calcined at high temperature in time, so that the white solid powder is prevented from being agglomerated, and the quality of cerium oxide is guaranteed.
6. The invention defines the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of ammonia water and the proportion range of the REO mass (g) of the solution to the mass (g) of solid ammonium bicarbonate, and lays theoretical and practical foundation for large-scale industrial production of small-granularity cerium oxide.
7. According to the invention, the specific surface area and pore volume of cerium oxide are improved by introducing the graphene to a very high degree, and when the cerium oxide is used as a polishing agent, the adsorption capacity is very good.
Drawings
Figure 1 shows the gas adsorption-desorption and pore size distribution of the sample of example 2 of the present invention.
Detailed Description
For a further understanding of the contents, features and effects of the present invention, the following embodiments are exemplified and explained in detail with reference to the accompanying drawings. It should be noted that the present embodiment is illustrative, not restrictive, and the scope of the invention should not be limited thereby.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
The invention adopts an Oumeca laser particle size analyzer to detect the particle size of the prepared cerium oxide. The laser particle size analyzer can detect the size and the distribution of particles and cover a plurality of wave bands of millimeter, micron, submicron and nanometer.
D50: the cumulative percent particle size distribution for a sample at 50% corresponds to the particle size. Its physical meaning is that the particle size is greater than 50% of its particles and less than 50% of its particles, D50 also being referred to as the median or median particle size.
D90: the cumulative particle size distribution of a sample reaches 90% of the corresponding particle size. Its physical meaning is that the particles have a size of less than 90% of its particle size.
Example 1
A preparation method of small-particle-size cerium oxide comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 25-28wt.%, carrying out ultrasonic oscillation of a cell disruptor, wherein the frequency of the cell disruptor is 30KHz, the power is 800W, the longest edge of a graphene sheet layer is controlled to be not more than 2 μm, the thickness is not more than 10nm, and when the ammonia water solution is oscillated and heated to 80 DEG, the ammonia water solution is subjected to ultrasonic oscillationoC, stopping ultrasonic oscillation, and keeping the temperature at 80 DEG CoC, refluxing for 4 h; naturally cooling, filtering once, diluting to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8, and the concentration of the ammoniated graphene is 2 g/L;
(3) and (3) adding water into the cerium chloride stock solution to dilute until the REO is 60g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 150ml/L, the dropping time is 20min, and continuously stirring for 10min after the dropping is finished.
(4) Heating the solution to 30 ℃, adding 7mol/L ammonia water according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.5, and continuously stirring;
(5) heating the solution obtained in the step (4) to 45 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of the REO mass (g) of the solution obtained in the step (4) to the mass (g) of the solid ammonium bicarbonate of 1:0.7, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6, and then carrying out centrifugal drying on the precipitated precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and the temperature programming calcination is carried out, wherein the temperature programming calcination is 2oC/min, increasing to 300oC, keeping the temperature for 1h, and then 10oC/min heating to 900oC roasting and keeping the constant temperature for 1.5 h.
Example 2
A preparation method of small-particle-size cerium oxide comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 25-28wt.%, carrying out ultrasonic oscillation of a cell disruptor, wherein the frequency of the cell disruptor is 30KHz, the power is 800W, the longest edge of a graphene sheet layer is controlled to be not more than 2 μm, the thickness is not more than 10nm, and when the ammonia water solution is oscillated and heated to 85 DEG, the ammonia water solution is subjected to ultrasonic oscillationoC, stopping ultrasonic oscillation, and keeping the temperature at 85 DEGoC, refluxing for 5 hours; naturally cooling, filtering once, diluting to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8.25, and the concentration of the ammoniated graphene is 4.5 g/L;
(3) and (3) adding water into the cerium chloride stock solution to dilute until the REO is 75g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 175ml/L, the dropping time is 25min, and continuously stirring for 15min after the dropping is finished.
(4) Heating the solution to 32.5 ℃, adding 7.5mol/L ammonia water according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.75, and continuously stirring;
(5) heating the solution obtained in the step (4) to 50 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of the REO mass (g) of the solution obtained in the step (4) to the mass (g) of the solid ammonium bicarbonate of 1:0.85, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6.5, and then carrying out centrifugal drying on the precipitated precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and the temperature programming calcination is carried out, wherein the temperature programming calcination is 2.5oC/min, increasing to 325oC, keeping the temperature for 1.5h, and then 12.5oC/min heating to 950oAnd C, roasting and keeping the constant temperature for 1.75 h.
Example 3
A preparation method of small-particle-size cerium oxide comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 25-28wt.%, carrying out ultrasonic oscillation of a cell disruptor, wherein the frequency of the cell disruptor is 30KHz, the power is 800W, the longest edge of a graphene sheet layer is controlled to be not more than 2 μm, the thickness is not more than 10nm, and when the ammonia water solution is oscillated and heated to 90 DEG, the ammonia water solution is heated to be in a temperature range of 90 nmoC, stopping ultrasonic oscillation, and keeping the temperature at 90 DEGoC, refluxing for 6 h; naturally cooling, filtering once, diluting to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8.5, and the concentration of the ammoniated graphene is 7 g/L;
(3) and (3) adding water into the cerium chloride stock solution to dilute until REO is 90g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 200ml/L, the dropping time is 30min, and continuously stirring for 20min after the dropping is finished.
(4) Heating the solution to 35 ℃, adding 8mol/L ammonia water according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.5-2, and continuously stirring;
(5) heating the solution obtained in the step (4) to 55 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of the REO mass (g) of the solution obtained in the step (4) to the mass (g) of the solid ammonium bicarbonate in a ratio of 1:1, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 7, and then carrying out centrifugal drying on the separated precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and the temperature programming calcination is carried out, wherein the temperature programming calcination is 3oC/min, increased to 350oC, keeping the temperature for 2 hours, and then 15oC/min heating to 1000oAnd C, keeping the constant temperature for 2 hours.
Comparative example 1
Step 1: preparing a cerium chloride solution, namely adding water into a cerium chloride stock solution to dilute until REO is 75g/L to prepare the cerium chloride solution for later use;
step 2: heating the cerium chloride solution obtained in the step 1 to 32.5 ℃, then adding ammonia water with the concentration of 7.5mol/L according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.75, and continuously stirring;
and step 3: heating the solution obtained in the step 2 to 50 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of the REO mass (g) of the solution obtained in the step 2 to the mass (g) of the solid ammonium bicarbonate of 1:0.85, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6.5, and then carrying out centrifugal drying on the precipitated precipitate to obtain white solid powder for later use;
and 4, step 4: the white powder is sent into a kiln for high-temperature calcination, and temperature programming calcination is carried out, wherein the temperature programming calcination is 2.5oC/min, increasing to 325oC, keeping the temperature for 1.5h, and then 12.5oC/min heating to 950oAnd C, roasting and keeping the constant temperature for 1.75 h.
Comparative example 2
A preparation method of small-particle-size cerium oxide comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) placing the graphene in an aqueous solution, and carrying out ultrasonic oscillation on a cell disruptor, wherein the frequency of the cell disruptor is 30KHz, the power of the cell disruptor is 800W, and the longest edge of a graphene sheet layer is controlled to be not more than 2 mu m, and the thickness of the graphene sheet layer is controlled to be not more than 10 nm;
(3) and (3) adding water into the cerium chloride stock solution to dilute until the REO content is 75g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 175ml, the dropping time is 25min, and continuously stirring for 15min after the dropping is finished.
(4) Heating the solution to 32.5 ℃, adding 7.5mol/L ammonia water according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.75, and continuously stirring;
(5) heating the solution obtained in the step (4) to 50 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of the REO mass (g) of the solution obtained in the step (4) to the mass (g) of the solid ammonium bicarbonate of 1:0.85, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6.5, and then carrying out centrifugal drying on the precipitated precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and the temperature programming calcination is carried out, wherein the temperature programming calcination is 2.5oC/min, increasing to 325oC, keeping the temperature for 1.5h, and then 12.5oC/min heating to 950oAnd C, roasting and keeping the constant temperature for 1.75 h.
Table 1 tests were conducted as for example 2 (S-2), comparative example 1(D-1), comparative example 2 (D-2).
As is apparent from Table 1, the cerium oxide prepared according to the present invention has a small particle size of cerium oxide D50 ≤ 4 μm, D90 ≤ 8.2 μm, a high specific surface area, and a bimodal pore size distribution, and compared to comparative example 1, in which graphene is added but there is no adsorption process of cerium ions, i.e., conduction process, since graphene is not added, i.e., there is no primary in-crystal deposition and pore formation process, i.e., the specific surface area is extremely low, the pore size distribution is a single broad peak, and the particle size of cerium oxide D-1 is not in-crystal neutralized graphene D50=19.33, and D90=28.13, compared to D-2, in comparative example 1, in which graphene is added, i.e., there is no adsorptionIn the deposition process, graphene and Ce (CO)3)3And Ce (OH)3The graphene cannot be effectively mixed, and interface separation occurs, namely the graphene and the sediment are mixed by simple mechanical stirring, so that D50=14.39, D90=23.17 and the specific surface area is low.
Based on the above, it can be clearly obtained that the method comprises the steps of ball milling and cell disruption ultrasonic pretreatment of graphene, ammonia water reflux preparation of ammoniated graphene, primary seed crystal deposition, secondary Ce (OH)3Deposit, cubic Ce (CO)3)3And temperature programmed roasting are indispensable means.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (6)
1. A preparation method of small-particle-size cerium oxide is characterized by comprising the following steps of:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 25-28wt.%, carrying out ultrasonic oscillation of a cell disruption instrument, and raising the temperature of the ammonia water solution to 80-90 ℃ when the ammonia water solution is oscillatedoC, stopping ultrasonic oscillation, and keeping the temperature at 80-90 DEGoC, refluxing for 4-6 h; naturally cooling, filtering once, diluting to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8-8.5, and the concentration of the ammoniated graphene is 2-7 g/L;
(3) adding water into the cerium chloride stock solution to dilute until REO is 60-90g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 150-;
(4) heating the solution to 30-35 ℃, adding 7-8mol/L ammonia water according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.5-2, and continuously stirring;
(5) heating the solution obtained in the step (4) to 45-55 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of REO mass (g) of the solution obtained in the step (4) to solid ammonium bicarbonate mass (g) of 1:0.7-1, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6-7, and then carrying out centrifugal drying on the precipitate to obtain off-white solid powder for later use;
(6) and (4) delivering the grey white powder into a kiln for high-temperature calcination, and performing temperature programmed calcination.
2. The method for preparing small-particle-size cerium oxide as claimed in claim 1, wherein after the ball milling and cell disruption ultrasonic treatment, the longest side of the graphene sheet layer is controlled to be not more than 2 μm and the thickness is controlled to be not more than 10 nm.
3. The method for preparing small particle size cerium oxide as claimed in claims 1-2, wherein the temperature-programmed calcination is 2-3oC/min, up to 300-oC, keeping the temperature for 1-2h, and then 10-15oC/min heating to 900-oAnd C, keeping the constant temperature for 1.5-2 h.
4. The method for preparing small-particle-size cerium oxide as claimed in claims 1 to 3, wherein the frequency of the cell disruptor is 30KHz and the power is 800W.
5. The method for preparing small-particle-size cerium oxide as claimed in claims 1 to 4, wherein the small-particle-size cerium oxide has D50 ≤ 4 μm and D90 ≤ 8.2 μm.
6. The method for preparing small-particle-size cerium oxide as claimed in claims 1 to 5, wherein the specific surface area of the cerium oxide is 150-200m2(g), pore size concentration distribution, pore volume of 0.257-0.268cm3The pore diameters are concentrated and distributed at 3.6nm and 5.7 nm.
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