CN101077790A - Method for preparing rare-earth oxide by homogenous precipitation method - Google Patents
Method for preparing rare-earth oxide by homogenous precipitation method Download PDFInfo
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- CN101077790A CN101077790A CN 200610080668 CN200610080668A CN101077790A CN 101077790 A CN101077790 A CN 101077790A CN 200610080668 CN200610080668 CN 200610080668 CN 200610080668 A CN200610080668 A CN 200610080668A CN 101077790 A CN101077790 A CN 101077790A
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- rare earth
- urease
- urea
- earth oxide
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- 238000000034 method Methods 0.000 title claims description 28
- 238000001556 precipitation Methods 0.000 title claims description 22
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 108010046334 Urease Proteins 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019764 Soybean Meal Nutrition 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004455 soybean meal Substances 0.000 claims description 4
- 108090000790 Enzymes Proteins 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- -1 rare earth carbonate Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention discloses homogeneous deposition process for preparing RE oxide. RE oxide precursor is first prepared through catalyzing urea with urease at 0-80 deg.c to hydrolyze and depositing RE salt solution as material homogeneously with urea as precipitant; and then treated through filtering, stoving and igniting to obtain RE oxide. The reaction may be completed at low temperature, and this can save energy source while obtain crystallized RE oxide precipitate with homogeneous granularity, compact structure, less adsorbed impurities, and easy filtering and washing.
Description
Technical Field
The invention belongs to the field of rare earth oxides, and particularly relates to a method for preparing rare earth oxides by a homogeneous precipitation method.
Background
The formation of the precipitate generally takes place through the formation of crystal nuclei and the growth of crystal nuclei, and when a precipitant is added to the feed solution, the ions aggregate by mutual collision to form minute crystal nuclei when the product of the concentrations of the precipitating ions exceeds the solubility product of the precipitate under the conditions. After the formation of the crystal nuclei, the crystal-forming ions in the solution are still diffusing toward the surface of the crystal nuclei and enter the crystal nuclei, so that crystals, i.e., precipitated particles, are gradually formed. In the formation of the precipitate, the rate at which the ions nucleate and further aggregate into precipitate particles is referred to as the aggregation rate. The rate at which the constituent ions align in a certain crystal lattice while being collected is called the orientation rate. The directional velocity is mainly determined by the nature of the precipitating species; the rate of aggregation is determined primarily by the conditions at which precipitation occurs, the most significant of which is the degree of supersaturation of the solution at which the precipitated material is formed. The precipitation method is generally divided into a direct precipitation method, a coprecipitation method and a homogeneous precipitation method, wherein the direct precipitation method and the coprecipitation method are both characterized in that a precipitant is added into a feed liquid to generate precipitation instantly, so that a local over-concentration phenomenon is easy to occur, and thus, precipitated particles are uneven and are seriously mixed. The homogeneous precipitation method is characterized in that certain conditions are controlled firstly, so that the added precipitant does not precipitate with the feed liquid immediately, but the precipitant is uniformly released in the whole solution firstly, and then crystal forming particles are slowly and uniformly generated from the solution through a chemical reaction, so that the precipitate is slowly and uniformly separated out in the whole solution. Compared with the former two precipitation methods, the method can avoid the phenomenon of local over-concentration, and the supersaturation degree of the structure crystal particle size is relatively uniform in the whole solution, so the obtained precipitate is a crystal form precipitate which has uniform and compact particles, less adsorbed impurities and easy filtration and washing.
Chinese patent CN1230582 adopts a homogeneous precipitation method, and combines the homogeneous precipitation method with an ultrasonic chemical method to manufacture a precursor, and has the defects that the product is easy to agglomerate, the particles are not uniform, and the product quality is influenced; the previous homogeneous precipitation method has been studied to some extent, but generally, the solution is heated to above 70 ℃, the pH value slowly increases, which is not favorable for the generation of crystal nuclei in the same environment, thereby affecting the monodispersity of the particles.
The invention utilizes the characteristic that urease can catalyze urea hydrolysis to induce homogeneous precipitation at room temperature or low temperature to prepare the precursor of the rare earth oxide, and the rare earth oxide with uniform particles and good dispersibility is prepared by controlling the concentration of reactants and a precipitator, the reaction time, the reaction temperature, the roasting temperature of the precursor and the roasting time. Its advantages are high catalytic activity and short time to generate the conditions needed by homogeneous deposition: a large amount of crystal-forming ions are generated simultaneously under the same chemical environment, the nucleation speed is far greater than the crystal nucleus growth speed, so the obtained particles are uniform, the product purity is high, the filtration is easy, the reaction can be carried out at room temperature or low temperature, and the energy is saved.
Disclosure of Invention
In order to achieve that the rare earth oxide precursor is a crystalline form precipitate which has uniform and compact particles, less adsorbed impurities and easy filtration and washing, the invention adopts the following scheme:
a method for preparing rare earth oxide by a homogeneous precipitation method comprises the following steps: taking rare earth salt solution as a raw material, adding urea with different amounts as a precipitator into the solution, wherein the adding amount of the urea is 1.5: 1-5: 1 of the molar ratio of the urea to the rare earth, adding a certain amount of urease or urease-containing substance as a catalyst, reacting for 0.5-24 hours at 0-80 ℃, washing and filtering the obtained precipitate, washing the water at 10-90 ℃, drying the obtained precursor at 40-90 ℃ for 0.5-8 hours, and roasting at 300-900 ℃ for 1-4 hours to obtain the rare earth oxide.
Further, the raw material rare earth salt solution can be one of nitrate, chloride, sulfate, etc., or rare earth carbonate, hydroxide, etc. dissolved by acid such as nitric acid, hydrochloric acid or sulfuric acid.
Furthermore, urea is used as a precipitator in the precipitation process, and urease or urease-containing substances such as bean pulp and the like or urease extract is used as a catalyst.
Further, the crude enzyme solution is extracted from soybean meal or other substances with organic solvent such as ethanol, glycerol, acetone, etc. or water as extractant.
The invention adopts an enzyme-induced homogeneous precipitation method, so that the reaction can be carried out at low temperature, the energy is saved, and the obtained rare earth oxide precursor is a crystalline precipitate which has uniform and compact particles, less adsorbed impurities and easy filtration and washing.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following is a description of the specific aspects of the invention:
the invention prepares rare earth oxide by urease catalysis urea hydrolysis homogeneous precipitation, and the main reaction is as follows:
urea hydrolysis:
ammonia water ionization: NH (NH)3·H2O-NH4 ++OH-
Precipitation reaction: RE3+3OH-+CO2-RE(OH)CO3·H2O
And (3) calcining reaction: RE (OH) CO3·H2O-RE(OH)CO3+H2O
2RE(OH)CO3-RE2O(CO3)2+H2O
RE2O(CO3)2-RE2O3+2CO2
The invention is realized by the following processes:
taking rare earth salt solution as a raw material, adding different amounts of urea as a precipitator, wherein the molar ratio of the added amount of urea to rare earth is 1.5: 1-5: 1, adding a certain amount of urease or urease-containing substance under stirring to catalyze urea hydrolysis, the reaction time is 0.5-24 hours, the reaction temperature is 0-80 ℃, washing and filtering the obtained precipitate, the washing water temperature is 10-90 ℃, drying the obtained precursor at 40-90 ℃, the drying time is 0.5-8 hours, and roasting at 300-900 ℃ for 1-4 hours to obtain rare earth oxide.
The specific implementation mode is as follows:
the first embodiment is as follows: 1L of lanthanum chloride solution with the concentration of 0.8mol/L is used as a raw material, 144g of urea is added, the mass ratio of the added soybean meal to the urea is 1: 2, the mixture is stirred and reacted for 6 hours at the temperature of 18 ℃, filtered, washed and precipitated for 3 times by water at the temperature of 80 ℃, dried for 120 minutes at the temperature of 60 ℃, calcined for 2 hours at the temperature of 800 ℃, the obtained lanthanum oxide powder has uniform granularity, D50 is 2.0014um, and the yield of the product reaches more than 98 percent.
Example two: taking 1L of lanthanum chloride solution with the concentration of 0.6mol/L as a raw material, adding 72g of urea, adding bean pulp with the mass ratio of 1: 1 to the urea, stirring and reacting for 4h at 20 ℃, filtering, washing and precipitating for 3 times at 80 ℃, drying for 120min at 60 ℃, calcining for 2h at 800 ℃, and obtaining lanthanum oxide powder with uniform particle size, wherein D50 is 7.3217um, and the yield of the product reaches more than 98%.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (4)
1. A method for preparing rare earth oxide by a homogeneous precipitation method is characterized by comprising the following steps: taking rare earth salt solution as a raw material, adding urea with different amounts as a precipitator into the solution, wherein the adding amount of the urea is 1.5: 1-5: 1 of the molar ratio of the urea to the rare earth, adding a certain amount of urease or urease-containing substance as a catalyst, reacting for 0.5-24 hours at 0-80 ℃, washing and filtering the obtained precipitate, washing the water at 10-90 ℃, drying the obtained precursor at 40-90 ℃ for 0.5-8 hours, and roasting at 300-900 ℃ for 1-4 hours to obtain the rare earth oxide.
2. The method for producing a rare earth oxide according to claim 1, characterized in that: the raw material rare earth salt solution can be one of nitrate, chloride and sulfate, or obtained by dissolving rare earth carbonate, hydroxide, etc. with acid such as nitric acid, hydrochloric acid or sulfuric acid, etc.
3. The method for producing a rare earth oxide according to claim 1 or 2, characterized in that: in the precipitation process, urea is used as a precipitator, urease or urease-containing substances such as soybean meal or urease extracting solution is used as a catalyst.
4. The method for producing a rare earth oxide according to claim 3, characterized in that: the urease extractive solution is crude enzyme solution extracted from soybean meal with organic solvent such as ethanol, glycerol, acetone, etc. or water as extractant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610080668 CN101077790A (en) | 2006-05-25 | 2006-05-25 | Method for preparing rare-earth oxide by homogenous precipitation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610080668 CN101077790A (en) | 2006-05-25 | 2006-05-25 | Method for preparing rare-earth oxide by homogenous precipitation method |
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| CN101077790A true CN101077790A (en) | 2007-11-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260524A (en) * | 2010-05-24 | 2011-11-30 | 中国石油天然气股份有限公司 | Chemical precipitation method for removing calcium from crude oil |
| CN108658115A (en) * | 2018-08-02 | 2018-10-16 | 重庆元和精细化工股份有限公司 | It is a kind of to produce spherical strontium carbonate and sodium aluminate method using production strontium waste residue |
| CN109735575A (en) * | 2019-01-18 | 2019-05-10 | 东南大学 | A method of plant urase, which is directly extracted, from soil prepares calcium carbonate |
| CN111115675A (en) * | 2018-10-11 | 2020-05-08 | 有研稀土新材料股份有限公司 | High-purity light lanthanum carbonate or lanthanum oxide and preparation method thereof |
-
2006
- 2006-05-25 CN CN 200610080668 patent/CN101077790A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260524A (en) * | 2010-05-24 | 2011-11-30 | 中国石油天然气股份有限公司 | Chemical precipitation method for removing calcium from crude oil |
| CN102260524B (en) * | 2010-05-24 | 2013-11-06 | 中国石油天然气股份有限公司 | Chemical precipitation method for removing calcium from crude oil |
| CN108658115A (en) * | 2018-08-02 | 2018-10-16 | 重庆元和精细化工股份有限公司 | It is a kind of to produce spherical strontium carbonate and sodium aluminate method using production strontium waste residue |
| CN108658115B (en) * | 2018-08-02 | 2020-03-17 | 重庆元和精细化工股份有限公司 | Method for producing spherical strontium carbonate and sodium aluminate by using strontium-producing waste residues |
| CN111115675A (en) * | 2018-10-11 | 2020-05-08 | 有研稀土新材料股份有限公司 | High-purity light lanthanum carbonate or lanthanum oxide and preparation method thereof |
| CN109735575A (en) * | 2019-01-18 | 2019-05-10 | 东南大学 | A method of plant urase, which is directly extracted, from soil prepares calcium carbonate |
| CN109735575B (en) * | 2019-01-18 | 2022-04-22 | 东南大学 | Method for preparing calcium carbonate by directly extracting plant urease from soil |
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