CN102992377A

CN102992377A - Method for preparing nano rare earth oxide through microwave sol-gel technology

Info

Publication number: CN102992377A
Application number: CN2012103372609A
Authority: CN
Inventors: 姜亚昌
Original assignee: RARE-CHEM HI-TECH Co Ltd
Current assignee: RARE-CHEM HI-TECH Co Ltd
Priority date: 2012-09-12
Filing date: 2012-09-12
Publication date: 2013-03-27

Abstract

The invention relates to a preparation method of nano rare earth oxide, and discloses a method for preparing nano rare earth oxide through a microwave sol-gel technology. According to the method for preparing nano rare earth oxide through the microwave sol-gel technology, the characteristic of high complexing capability of rare earth is utilized, and the microwave is adopted and used for uniformly heating and catalyzing, thus the organic complex of the rare earth can quickly form polymer colloid, and as a result, the time for forming the colloid and dewatering is greatly shortened, the phenomenon of 'paste on pot' is avoided, the production efficiency is improved nearly 10 times, and the producing cost is reduced; the prepared nano rare earth oxide through the microwave sol-gel technology is high in quality and loose and uniform in appearance, and the crystal nucleus granularity is up to 20 to 30 nanometers; and the nano rare earth oxide disclosed by the invention is narrow in distribution, high in dispersibility, high in specific surface area, low in cost, easy to industrialize, stable in various physical and chemical indexes, free from pollution, and excellent in purity.

Description

A kind of method of utilizing the microwave sol-gel technique to prepare oxide nano rare earth

Technical field

The present invention relates to the preparation technology of oxide nano rare earth, particularly a kind of method of utilizing the microwave sol-gel technique to prepare oxide nano rare earth.

Background technology

Rare earth is exactly lanthanon in the periodic table of chemical element---lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and with closely-related two elements of 15 elements of group of the lanthanides---scandium (Sc) and yttrium (Y) be totally 17 kinds of elements, be called rare earth element (Rare Earth), be called for short rare earth (RE); Oxide nano rare earth is to belong to nano-powder material, and preparation method commonly used has at present: mechanical crushing method, the precipitator method, hydrothermal method, vapor phase process etc.Because the special chemical character of rare earth element, when preparing its nano powder, there is different defectives in these preparation methods, introduce easily impurity such as mechanical disintegration, are difficult to obtain the high nanometer product of purity; Precipitator method complex operation, product are easily reunited; Hydrothermal method equipment requirements High Temperature High Pressure, power consumption be large, have potential safety hazard; It is raw material that vapor phase process needs rare earth metal, and cost is higher, high deficiency consumes energy.

Summary of the invention

The object of the invention is to: the strong characteristics of complex ability of utilizing rare earth, adopt homogeneous heating and the catalysis of microwave, make rare earth organic complex can form fast polymer colloid, become like this time of glue, dehydration just greatly to shorten, and can " not be burned ", production efficiency improves nearly 10 times, and production cost is just naturally very low.Good product quality, outward appearance is loose evenly, and the nucleus granularity reaches 20-30nm, and narrow, the good dispersity of distributing, specific surface are large, and cost is low, easily realizes industrialization, and every physics, chemical index are stablized, and product is not contaminated, and purity is good.

The preparation process of oxide nano rare earth provided by the invention is as follows:

1, with rare earth oxide or rare earth carbonate (Re ₂O ₃Or Re ₂(CO ₃) ₃) be raw material, wherein Re belongs to La element, Ce element, Pr element, Nd element, Sm element, Eu element, Gd element, Tb element, Dy element, Ho element, Er element, Tm element, Yb element, Lu element, Sc element or Y element, also is rare earth element;

2, adopt nitric acid or the acetic acid of 1:1 that rare earth compound is prepared into corresponding solution under the room temperature, concentration is designated as solution A at 5%-20%;

3, gelatinizing agent preparation: gelatinizing agent comprises citric acid, phenylformic acid, Whitfield's ointment, oxyacetic acid, Padil, L-GLUTAMICACID, urea, trolamine, Virahol, ethylenediamine tetraacetic acid (EDTA), Mierocrystalline cellulose, xylogen, starch, sucrose, glucose, the such organic compound of methyl ethyl diketone, one or more mixture with above-mentioned gelatinizing agent, water or ethanol are made into the solution of 5%-20%, are designated as solution B;

4, be 1:(0.1-5 according to rare earth and gelatinizing agent mol ratio), B is slowly joined among the A, stirred 3-5 minute, mix, be designated as solution C;

5, with the microwave heating solution C of 2450MHz, be 2-15 minute heat-up time, makes it to form colloidal sol, stirs, and continues microwave heating, and the control temperature is 80 ℃-120 ℃, until form solid gel;

6, with solid gel in 500 ℃-900 ℃ High Temperature Furnaces Heating Apparatus calcination 1-4 hour, obtain nano RE oxide powder.

Description of drawings

Fig. 1 is nano-cerium oxide particle electromicroscopic photograph figure, and this figure shows that obvious particle circle is arranged, and small-particle is in the 20-30 nanometer, and macrobead also is that agglomerating particles is in the 100-200 nanometer;

Fig. 2 is nm Y ₂O ₃Laser particle-size distribution figure, wherein D ₅₀=153nm, survey is dispersible agglomerating particles;

Fig. 3 is nm Yb ₂O ₃Laser particle-size distribution figure, wherein D ₅₀=188nm;

Fig. 4 is nm CeO ₂Nm Y ₂O ₃BET specific surface figure;

Fig. 5 is nm Y ₂O ₃X-small-angle diffraction crystal grain distribution plan D ₅₀=31nm.

Embodiment

The present invention will be further described below by drawings and Examples:

Among Fig. 4, used test method: directly comparing method; The full-automatic nitrogen absorption of instrument: JW-004 specific surface instrument; Adsorbate: nitrogen; Carrier gas: helium; P/PO:0.204821; Sample preparation condition: 120 ℃ of vacuum dryings 1 hour; Flow (ml/min): 69.90; Decay: 1; Magnification: 1.

The sample title	Sample mass (mg)	Peak area	Specific surface area
				Standard test specimen	648.100	1874410	36.0000
G5	1010.000	736248	9.0737
				Y07-10-22	288.100	880102	38.0250-CeO ₂
Y06-9-10 (in vain)	177.700	428482	30.0141-Y ₂O ₃

Among Fig. 5, use international standard ISO/TS13762 and standard GB/T/T13221, sample is: Y ₂O ₃YO-GH0801-CP uses instrument: x ray diffractometer x, spectrograph, small-angle scattering method goniometer, radiation: CO KA; Load: 35KV, 30MA; Interval: 0.04mm 0.1mm 0.02 mm.

Figure DEST_PATH_RE-GDA00002717749400041

The result shows, mean sizes D=59.4(nm) median size d=31.1(nm) expansion distribution B=65.

Case study on implementation one:

1, Y ₂O ₃HNO with 1:1 ₃Dissolving, being made into concentration is 10% solution, is designated as solution A;

2, gelatinizing agent preparation: take citric acid as main body, add a small amount of quadrol and urea, be made into 10% solution with pure water, be designated as B solution;

3, get 50 gram A solution, 58 gram B solution join B among the A, mix, and are designated as solution C;

4, with the microwave heating solution C of 2450MHz, be 9 minutes heat-up time, makes it to form colloidal sol, stirs, and continues microwave heating, and the control temperature is 80 ℃-120 ℃, until form solid gel;

5, with solid gel calcination 2.5 hours in 650 ℃ High Temperature Furnaces Heating Apparatus, obtain nanometer Y ₂O ₃RE oxide powder.

This embodiment effect sees that Fig. 2, Fig. 4, Fig. 5 characterize.

Case study on implementation two:

1, with CeO ₂: Gd ₂O ₃The mixed rare-earth oxide of=4:1 is with the HNO of 1:1 ₃Dissolving, being made into concentration is 10% solution, is designated as solution A;

2, gelatinizing agent preparation: take Padil and starch as main body, add a small amount of glucose, be made into 15% solution with pure water, be designated as B solution;

3, get 50 gram A solution, 36 gram B solution join B among the A, mix, and are designated as solution C;

4, with the microwave heating solution C of 2450MHz, be 8 minutes heat-up time, makes it to form colloidal sol, stirs, and continues microwave heating, and the control temperature is 80 ℃-120 ℃, until form solid gel;

5, with solid gel calcination 2.5 hours in 700 ℃ High Temperature Furnaces Heating Apparatus, obtain nano Ce O ₂-Gd ₂O ₃Composite powder.

This embodiment effect sees that Fig. 1, Fig. 4 characterize.

Case study on implementation three:

1, Yb ₂O ₃HNO with 1:1 ₃Dissolving, being made into concentration is 15% solution, is designated as solution A;

2, gelatinizing agent preparation: take glucose, methylcellulose gum as main body, add a small amount of trolamine, be made into 15% solution with pure water, be designated as B solution;

3, get 50 gram A solution, 44 gram B solution join B among the A, mix, and are designated as solution C;

4, with the microwave heating solution C of 2450MHz, be 7-8 minute heat-up time, makes it to form colloidal sol, stirs, and continues microwave heating, and the control temperature is 80 ℃-120 ℃, until form solid gel;

5, with solid gel calcination 2.5 hours in 750 ℃ High Temperature Furnaces Heating Apparatus, obtain nanometer Yb ₂O ₃Powder.

This embodiment effect sees that Fig. 3 characterizes.

Claims

1. a microwave prepares the method for oxide nano rare earth, it is characterized in that step is as follows:

(1) take rare earth oxide or rare earth carbonate as raw material, Re ₂O ₃, Re ₂(CO ₃) ₃, described Re belongs to the La element, comprises Ce element, Pr element, Nd element, Sm element, Eu element, Gd element, Tb element, Dy element, Ho element, Er element, Tm element, Yb element, Lu element, Sc element or Y element, also is rare earth element;

(2) adopt nitric acid or the acetic acid of 1:1 that rare earth compound is prepared into corresponding solution under the room temperature, concentration is designated as solution A at 5%-20%;

(3) gelatinizing agent preparation: gelatinizing agent comprises citric acid, phenylformic acid, Whitfield's ointment, oxyacetic acid, Padil, L-GLUTAMICACID, urea, trolamine, Virahol, ethylenediamine tetraacetic acid (EDTA), Mierocrystalline cellulose, xylogen, starch, sucrose, glucose, the such organic compound of methyl ethyl diketone, one or more mixture with above-mentioned gelatinizing agent, water or ethanol are made into the solution of 5%-20%, are designated as solution B;

(4) be 1:(0.1-5 according to rare earth and gelatinizing agent mol ratio), B is slowly joined among the A, stirred 3-5 minute, mix, be designated as solution C;

(5) with the microwave heating solution C of 2450MHz, be 2-15 minute heat-up time, makes it to form colloidal sol, stirs, and continues microwave heating, and the control temperature is 80 ℃-120 ℃, until form solid gel;

(6) with solid gel in 500 ℃-900 ℃ High Temperature Furnaces Heating Apparatus calcination 1-4 hour, obtain nano RE oxide powder.