CN107697942B - Method for preparing cerium carbonate by precipitating rare earth ions - Google Patents
Method for preparing cerium carbonate by precipitating rare earth ions Download PDFInfo
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- CN107697942B CN107697942B CN201711181315.0A CN201711181315A CN107697942B CN 107697942 B CN107697942 B CN 107697942B CN 201711181315 A CN201711181315 A CN 201711181315A CN 107697942 B CN107697942 B CN 107697942B
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- cerium
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- cerium carbonate
- ammonia water
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- 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 title claims abstract description 66
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 33
- -1 rare earth ions Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000001376 precipitating effect Effects 0.000 title claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 78
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 63
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 63
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 10
- 239000010413 mother solution Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 2
- 239000002244 precipitate Substances 0.000 abstract description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001099 ammonium carbonate Substances 0.000 abstract description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract description 7
- 239000012452 mother liquor Substances 0.000 abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000002386 leaching Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 229910002493 Ce2(CO3)3 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 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
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/247—Carbonates
-
- 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
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for preparing cerium carbonate by precipitating rare earth ions, which comprises the steps of taking carbonized ammonia water as a cerium ion precipitator, adopting a cocurrent flow precipitation mode with a cerium chloride solution, controlling the pH value of a precipitation mother liquor to completely precipitate cerium ions, filtering by a centrifuge, washing and spin-drying to obtain the cerium carbonate. The method has the advantages that the cerium ions are precipitated by using the carbonized ammonia water, and the utilization rate of the carbon dioxide is 62.5-96.8%, which is far higher than 50% of that of the carbon dioxide which is obtained by using ammonium bicarbonate as a precipitant.
Description
The technical field is as follows:
the invention relates to a method for preparing cerium carbonate, in particular to a method for preparing cerium carbonate by precipitating rare earth ions.
Background art:
the mixed rare earth chloride is mainly separated by a solvent extraction method, and the separated single rare earth or component rare earth is generally precipitated by precipitants such as ammonium bicarbonate, sodium carbonate, oxalic acid and the like.
With the development of the rare earth industry in China, a mainstream method for preparing rare earth oxide through ammonium bicarbonate precipitation and conversion is formed in China. The method takes rare earth carbonate as an intermediate to prepare rare earth oxide by burning, and 418 kg of carbon dioxide is discharged in the precipitation process of cerium carbonate with the total amount of 1 ton of the prepared rare earth calculated from the conversion process of the material. Because of global attention on the problem of carbon dioxide emission reduction, the preparation method which is lower in manufacturing cost, less in carbon dioxide emission and better in rare earth oxide dispersion performance is sought, and the preparation method is increasingly paid more attention by rare earth separation enterprises. Although no carbon dioxide is generated by adopting sodium carbonate to precipitate rare earth, the production cost is increased by 1 time, and simultaneously, the pollution of sodium salt wastewater is also brought. The rare earth precipitated by oxalic acid does not generate carbon dioxide, but the oxalic acid is expensive and is not beneficial to the development of the rare earth industry.
Therefore, it is necessary to select a new type of precipitant to overcome or reduce the generation of carbon dioxide and reduce the manufacturing cost.
The invention content is as follows:
the invention aims to provide a method for precipitating rare earth ions, which has low carbon dioxide emission and low cost.
The purpose of the invention is implemented by the following technical scheme: a method for preparing cerium carbonate by precipitating rare earth ions comprises the steps of taking carbonized ammonia water as a cerium ion precipitator, adopting a cocurrent flow precipitation mode with a cerium chloride solution, controlling the pH value of a precipitation mother liquor to enable cerium ions to be completely precipitated, filtering by a centrifugal machine, washing and drying by a drying method to obtain the cerium carbonate.
The method for preparing cerium carbonate by precipitating rare earth ions comprises the following specific operation steps: (1) preparing; (2) parallel flow precipitation; (3) obtaining a finished product of cerium carbonate; wherein,
(1) preparation work: adding a reaction bottom solution into the reaction tank, and adding cerium carbonate accounting for 10-20% of the total amount of the pre-precipitated cerium oxide into the reaction bottom solution to serve as seed crystals; wherein, the total amount of the pre-precipitated cerium oxide is calculated by a conventional method.
(2) And (3) parallel flow precipitation: after the preparation work is finished, adding a cerium chloride solution into the reaction tank for 5-10 min; then, synchronously adding a cerium chloride solution and a carbonized ammonia water solution into the reaction tank, stirring to perform a precipitation reaction, wherein the molar concentration of the cerium chloride solution is 0.4-1.6 mol/L, and the pH value is 1.5-2.5; the molar ratio of carbon dioxide to ammonia gas in the carbonized ammonia water is 0.47-0.91, the total alkalinity of the carbonized ammonia water is 3-13 mol/L, the pH value is 8.6-10.0, and the pH value of the solution in the reaction tank is controlled to be 6.6-7.4; wherein the total alkalinity of the carbonized ammonia water refers to HCO contained in each liter of carbonized ammonia water3-、CO3 2-、NH2COO-And a very small amount of hydroxyl groups.
(3) Preparing a finished cerium carbonate product: stopping adding materials, continuing stirring until the reaction is complete, filtering by a centrifugal machine, washing, and drying by spin-drying to obtain a cerium carbonate finished product.
The reaction base solution is pure water or cerous carbonate leaching water, and the temperature of the reaction base solution is 30-55 ℃.
Preferably, in the step (3), the charging is stopped, the stirring reaction is continued for 30min, and then the cerium carbonate finished product is obtained by filtering, washing and spin-drying through a centrifuge.
Specifically, in the step (2), the reaction temperature is controlled to be 30-55 ℃.
Specifically, the adding flow rate of the carbonized ammonia water solution is 0.26-2.90L/min; the adding flow rate of the cerium chloride solution is 0.80-4.70L/min.
Specifically, the temperature of the carbonized ammonia water solution is 20-30 ℃, and the temperature of the cerium chloride solution is 30-55 ℃.
Specifically, the adding time of the carbonized ammonia water solution is 3.0-10.4 hours, and the adding time of the cerium chloride solution is 3.0-10.3 hours.
Preferably, the molar ratio of carbon dioxide to ammonia gas in the carbonated ammonia water is preferably 0.47-0.84, and the pH of the carbonated ammonia water is preferably 9-10.0.
Preferably, the molar ratio of carbon dioxide to ammonia gas in the carbonated ammonia water is preferably 0.47-0.53, and the pH of the carbonated ammonia water is preferably 9.7-10.0.
The carbonized ammonia water is a mixed solution containing carbonate, bicarbonate, carbamate and free ammonia obtained by absorbing carbon dioxide by ammonia water, and the form of carbon-containing ions in the solution is correspondingly converted along with the change of the pH value of the system solution. The dosage of the carbonized ammonia water is 105-110% of the theoretical dosage.
The reaction principle of the invention is as follows:
the reaction equation of the present invention is as follows:
(1)3(NH4)2CO3+2CeCl3→Ce2(CO3)3+6NH4Cl
(2)6NH4HCO3+2CeCl3→Ce2(CO3)3+6NH4Cl+3CO2↑+3H2O
(3)3NH2COONH4+3H2O+2CeCl3→Ce2(CO3)3+6NH4Cl
(4)3NH4HCO3+3NH3+2CeCl3→Ce2(CO3)3+6NH4cl (when the content of free ammonia in carbonized ammonia water is high)
(5)H++NH3→NH4 +
The carbonic ions in the carbonized ammonia water are all precipitated in the form of cerium carbonate, bicarbonate and carbamate react with the cerium ions respectively, and the utilization rates of carbon dioxide are 100%, 50% and 100% respectively. CO when the pH of the carbonized aqueous ammonia solution is 9.803 2-、HCO3 -、NH2COO-The molar concentrations of (a) to (b) are 25%, 40% and 35%, respectively, of the total carbon molar concentration, and approximately 95.4% of carbon dioxide is utilized when reacting with cerium ions. The solubility of ammonium bicarbonate in water at 20 ℃ is 21.7g/L, the solubility of ammonium carbonate is 100g/L, and the solubility of ammonium carbamate is 66.6g/L, which is the fundamental reason why the precipitant concentration can be greatly increased.
The invention has the advantages that:
1. precipitating cerium ions by using carbonized ammonia water, wherein the utilization rate of carbon dioxide is 62.5-96.8%, which is far higher than that of carbon dioxide which is obtained by using ammonium bicarbonate as a precipitant;
2. the invention can greatly reduce the processing cost of the cerium dioxide, firstly, carbonized ammonia water is directly used to replace ammonium bicarbonate, and the production cost can be reduced by 210 yuan by measuring and calculating 1 ton of the cerium dioxide; secondly, because the concentration of the carbonized ammonia water is far higher than that of the ammonium bicarbonate, the concentration of the ammonium chloride mother liquor generated by precipitation is higher, and the production of 1 ton of cerium dioxide can reduce the production wastewater by 4m through calculation3Indirectly reduce the subsequent wastewater treatment cost by 600 yuan;
3. the method has mild reaction conditions, simple operation, environmental protection and easy butt joint with the prior art;
4. the total amount of rare earth in the cerium carbonate prepared by the method is 44.82-53.02%, the content of chlorine radicals is 0.0200-0.0660%, and the quality requirement of the cerium carbonate is completely met;
5. in the process of rare earth ion precipitation reaction, the utilization rate of carbon dioxide is greatly improved, the emission of carbon dioxide is greatly reduced, and the method has important significance for energy conservation and emission reduction of enterprises.
The specific implementation mode is as follows:
example 1: taking carbonized ammonia water 672L with the molar ratio of carbon dioxide to ammonia gas of 0.47, the pH value of 10.0, the temperature of 30 ℃ and the total alkalinity of 3.0mol/L, wherein NH2COO-/TCO2＝39％，CO3 2-/TCO2＝30％，HCO3 -/TCO231%. Using a 2500LPP reaction tank, 300L of pure water at 40 ℃ was added without stirring the blades, and 22 kg of cerium carbonate (REO ═ 48.56%) was added as seed crystals. A640L volume cerium chloride solution having a concentration of 1.0mol/L, pH of 1.5 was heated to 40 ℃. Starting a reaction tank for stirring, adding a cerium chloride solution at a flow rate of 2.10L/min, after 10min, synchronously adding the cerium chloride solution and a carbonized ammonia water solution into the reaction tank, wherein the flow rate of the cerium chloride solution is 2.10L/min, the flow rate of the carbonized ammonia water solution is 2.20L/min, the feeding time is 5.1 hours, the amount of the carbonized ammonia water is 5% excessive, controlling the pH of the solution in the reaction tank to be 6.6-7.4, stopping feeding, continuing stirring for 30 minutes, and the final pH of a mother solution is 7.0. And separating the slurry by a centrifugal machine, leaching the precipitate by pure water with the temperature of 40 ℃ and the volume of 770L, and drying for 10min to obtain the cerium carbonate. Cerium carbonate sample analysis shows that the rare earth content is 48.62 percent, and Cl-And 0.0494 percent of the carbon dioxide/M meets the quality requirement of the cerium carbonate, and the utilization rate of the carbon dioxide is calculated to be 96.8 percent.
Example 2: taking 274L of carbonized ammonia water with the molar ratio of carbon dioxide to ammonia gas of 0.49, the pH value of 9.9, the temperature of 25 ℃, and the total alkalinity of 7.5mol/L, wherein NH2COO-/TCO2＝37％，CO3 2-/TCO2＝28％，HCO3 -/TCO235%. Using a 2500LPP reaction tank, 300L of pure water at 40 ℃ was added without stirring the blades, and 16.5 kg of cerium carbonate (REO ═ 48.56%) was added as seed crystals. A cerium chloride solution having a concentration of 1.6mol/L, pH of 2.0 and a volume of 400L was heated to 40 ℃. Starting the reaction tank to stir, and adding chlorine at the flow rate of 0.90L/minAnd (2) dissolving a cerium solution, after 5min, synchronously adding a cerium chloride solution and a carbonized ammonia water solution into the reaction tank, wherein the flow rate of the cerium chloride solution is 0.90L/min, the feeding time is 7.4 hours, the flow rate of the carbonized ammonia water solution is 0.60L/min, the feeding time is 7.6 hours, the excess carbonized ammonia water is 7%, controlling the pH value of the solution in the reaction tank to be 6.6-7.4, continuing stirring for 30 minutes after feeding is stopped, and the final pH value of the mother liquor is 7.2. And separating the slurry by a centrifugal machine, leaching the precipitate by pure water with the temperature of 40 ℃ and the volume of 770L, and drying for 10min to obtain the cerium carbonate. Cerium carbonate sample analysis shows that the rare earth content is 50.44 percent, and Cl-And the/M is 0.0480 percent, meets the quality requirement of cerium carbonate, and the calculated utilization rate of the carbon dioxide is 96.2 percent.
Example 3: taking 163L of carbonized ammonia water with the molar ratio of carbon dioxide to ammonia gas of 0.50, the pH value of 9.8, the temperature of 20 ℃ and the total alkalinity of 13mol/L, wherein NH2COO-/TCO2＝35％，CO3 2-/TCO2＝25％，HCO3 -/TCO240%. Using a 2500LPP reaction tank, 300L of 45 ℃ rinse water was added without stirring the leaves, and 11 kg of cerium carbonate (REO ═ 48.56%) was added as seed crystals. A800L cerium chloride solution having a concentration of 0.8mol/L, pH ═ 2.5 was heated to 45 ℃. Starting a reaction tank for stirring, adding a cerium chloride solution at a flow rate of 1.30L/min, after 5min, synchronously adding the cerium chloride solution and a carbonized ammonia water solution into the reaction tank, wherein the flow rate of the cerium chloride solution is 1.30L/min, the feeding time is 10.3 hours, the flow rate of the carbonized ammonia water solution is 0.26L/min, the feeding time is 10.4 hours, the amount of the carbonized ammonia water is 10% excessive, controlling the pH of the solution in the reaction tank to be 6.6-7.4, continuing stirring for 30min after the feeding is stopped, and the end-point pH of a mother solution is 7.4. And separating the slurry by a centrifugal machine, leaching the precipitate by pure water with the temperature of 40 ℃ and the volume of 770L, and drying for 10min to obtain the cerium carbonate. Cerium carbonate sample analysis shows that the rare earth content is 53.02 percent, and Cl-And the content of the carbon dioxide/M is 0.0476 percent, meets the quality requirement of cerium carbonate, and the calculated utilization rate of the carbon dioxide is 95.4 percent.
Example 4: taking carbonized ammonia water 211 with the molar ratio of carbon dioxide to ammonia gas of 0.53, the pH value of 9.7, the temperature of 25 ℃ and the total alkalinity of 10mol/LL, wherein NH2COO-/TCO2＝32％，CO3 2-/TCO2＝24％，HCO3 -/TCO244%. Using a 2500LPP reaction tank, 300L of 40 ℃ rinse water was added without stirring the leaves, and 22 kg of cerium carbonate (REO ═ 48.56%) was added as seed crystals. A cerium chloride solution having a concentration of 1.2mol/L, pH of 1.5 and a volume of 533L was heated to 40 ℃. Starting a reaction tank for stirring, adding a cerium chloride solution at a flow rate of 1.50L/min, after 10min, synchronously adding the cerium chloride solution and a carbonized ammonia water solution into the reaction tank, wherein the flow rate of the cerium chloride solution is 1.50L/min, the flow rate of the carbonized ammonia water solution is 0.60L/min, the feeding time is 5.9 hours, the amount of the carbonized ammonia water is 10% excessive, controlling the pH of the solution in the reaction tank to be 6.6-7.4, stopping feeding, continuing stirring for 30 minutes, and the final pH of a mother solution is 7.2. And separating the slurry by a centrifugal machine, leaching the precipitate by pure water with the temperature of 40 ℃ and the volume of 770L, and drying for 10min to obtain the cerium carbonate. Cerium carbonate sample analysis shows that the rare earth content is 49.24 percent, and Cl-And the utilization rate of the carbon dioxide is calculated to be 95.0 percent, wherein the/M is 0.0460 percent and meets the quality requirement of the cerium carbonate.
Example 5: taking 403L of carbonized ammonia water with a molar ratio of carbon dioxide to ammonia gas of 0.61, a pH value of 9.5, a temperature of 30 ℃ and a total alkalinity of 5mol/L, wherein NH2COO-/TCO2＝29％，CO3 2-/TCO2＝23％，HCO3 -/TCO248%. Using a 2500LPP reaction tank, 300L of pure water at 50 ℃ was added without stirring the blades, and 22 kg of cerium carbonate (REO ═ 48.56%) was added as seed crystals. A cerium chloride solution having a concentration of 1.6mol/L, pH of 2.0 and a volume of 400L was heated to 50 ℃. Starting a reaction tank for stirring, adding a cerium chloride solution at a flow rate of 0.80L/min, after 5min, synchronously adding the cerium chloride solution and a carbonized ammonia water solution into the reaction tank, wherein the flow rate of the cerium chloride solution is 0.80L/min, the feeding time is 8.3 hours, the flow rate of the carbonized ammonia water solution is 0.80L/min, the feeding time is 8.4 hours, the amount of the carbonized ammonia water is 5% excessive, controlling the pH of the solution in the reaction tank to be 6.6-7.4, continuing stirring for 30 minutes after stopping feeding, and the end point pH of a mother solution is 6.6. The slurry is separated by a centrifuge and usedAnd leaching the precipitate by pure water with the temperature of 40 ℃ and the volume of 770L, and drying for 10min to obtain the cerium carbonate. Cerium carbonate sample analysis shows that the rare earth content is 49.40 percent, and Cl-And the utilization rate of the carbon dioxide is calculated to be 83.2 percent, wherein the/M is 0.0486 percent and meets the quality requirement of the cerium carbonate.
Example 6: taking 274L of carbonized ammonia water with the molar ratio of carbon dioxide to ammonia gas of 0.74, the pH value of 9.3, the temperature of 20 ℃ and the total alkalinity of 7.5mol/L, wherein NH2COO-/TCO2＝28％，CO3 2-/TCO2＝20％，HCO3 -/TCO252%. Using a 2500LPP reaction tank, 300L of pure water at 55 ℃ was added without stirring the blades, and 22 kg of cerium carbonate (REO ═ 48.56%) was added as seed crystals. A cerium chloride solution having a concentration of 2.5 in 0.4mol/L, pH and a volume of 1600L was heated to 55 ℃. Starting a reaction tank for stirring, adding a cerium chloride solution at a flow rate of 4.70L/min, after 10min, synchronously adding the cerium chloride solution and a carbonized ammonia water solution into the reaction tank, wherein the flow rate of the cerium chloride solution is 4.70L/min, the feeding time is 5.7 hours, the flow rate of the carbonized ammonia water solution is 0.80L/min, the feeding time is 5.7 hours, the amount of the carbonized ammonia water is 7% excess, controlling the pH of the solution in the reaction tank to be 6.6-7.4, continuing stirring for 30min after stopping feeding, and the end-point pH of mother liquor is 7.0. And separating the slurry by a centrifugal machine, leaching the precipitate by pure water with the temperature of 40 ℃ and the volume of 770L, and drying for 10min to obtain the cerium carbonate. Cerium carbonate sample analysis shows that the rare earth content is 52.80 percent, and Cl-And the/M is 0.0418 percent, meets the quality requirement of cerium carbonate, and the utilization rate of the carbon dioxide is 77.8 percent through calculation.
Example 7: taking 528L of carbonized ammonia water with the molar ratio of carbon dioxide to ammonia gas of 0.84, the pH value of 9.0, the temperature of 25 ℃ and the total alkalinity of 4.0mol/L, wherein NH2COO-/TCO2＝23％，CO3 2-/TCO2＝15％，HCO3 -/TCO262 percent. Using a 2500LPP reaction tank, 300L of pure water at 45 ℃ was added without stirring the blades, and 22 kg of cerium carbonate (REO ═ 48.56%) was added as seed crystals. A640L volume cerium chloride solution having a concentration of 1.0mol/L, pH of 1.5 was heated to 45 ℃. Starting the reaction tank to stirAdding a cerium chloride solution at a flow rate of 3.50L/min, synchronously adding the cerium chloride solution and a carbonized ammonia water solution into a reaction tank after 10min, controlling the flow rate of the cerium chloride solution to be 3.50L/min, the flow rate of the carbonized ammonia water solution to be 2.90L/min, and the feeding time to be 3.0 hours, wherein the carbonized ammonia water is excessive by 10%, controlling the pH of the solution in the reaction tank to be 6.6-7.4, stopping feeding, continuing stirring for 30 minutes, and controlling the end-point pH of the mother liquor to be 7.4. And separating the slurry by a centrifugal machine, leaching the precipitate by pure water with the temperature of 40 ℃ and the volume of 770L, and drying for 10min to obtain the cerium carbonate. Cerium carbonate sample analysis shows that the rare earth content is 44.82 percent, and Cl-0.0240% of/M, which meets the quality requirement of cerium carbonate, and the calculated utilization rate of carbon dioxide is 70.4%.
Example 8: taking 422L of carbonized ammonia water with a molar ratio of carbon dioxide to ammonia gas of 0.91, a pH value of 8.6, a temperature of 25 ℃, and a total alkalinity of 5.0mol/L, wherein NH2COO-/TCO2＝15％，CO3 2-/TCO2＝10％，HCO3 -/TCO275%. Using a 2500LPP reaction tank, 300L of 30 ℃ rinse water was added without stirring the leaves, and 16.5 kg of cerium carbonate (REO ═ 48.56%) was added as seed crystals. A640L volume cerium chloride solution having a concentration of 1.0mol/L, pH of 2.0 was heated to 30 ℃. Starting a reaction tank for stirring, adding a cerium chloride solution at a flow rate of 2.20L/min, after 5min, synchronously adding the cerium chloride solution and a carbonized ammonia water solution into the reaction tank, wherein the flow rate of the cerium chloride solution is 2.20L/min, the feeding time is 4.8 hours, the flow rate of the carbonized ammonia water solution is 1.40L/min, the feeding time is 5.0 hours, the amount of the carbonized ammonia water is 10% excessive, controlling the pH of the solution in the reaction tank to be 6.6-7.4, continuing stirring for 30 minutes after the feeding is stopped, and the end point pH of a mother solution is 6.8. And separating the slurry by a centrifugal machine, leaching the precipitate by pure water with the temperature of 40 ℃ and the volume of 770L, and drying for 10min to obtain the cerium carbonate. Cerium carbonate sample analysis shows that the rare earth content is 46.50 percent, and Cl-And the content of the carbon dioxide/M is 0.0200%, the mass requirement of the cerium carbonate is met, and the calculated utilization rate of the carbon dioxide is 62.5%.
The difference in chemical composition-mass between cerium carbonate produced according to examples 1 to 8 and cerium carbonate produced according to a conventional method is shown in Table 1:
table 1: chemical composition-mass difference
Claims (6)
1. A method for preparing cerium carbonate by precipitating rare earth ions is characterized in that carbonized ammonia water is used as a cerium ion precipitator, the carbonized ammonia water and a cerium chloride solution are precipitated in a parallel flow manner, the pH value of a precipitation mother solution is controlled, so that cerium ions are completely precipitated, and the cerium carbonate is obtained by filtering, washing and spin-drying through a centrifuge;
the specific operation steps are as follows: (1) preparing; (2) parallel flow precipitation; (3) obtaining a finished product of cerium carbonate; wherein,
(1) preparation work: adding a reaction bottom solution into the reaction tank, and adding cerium carbonate accounting for 10-20% of the total amount of the pre-precipitated cerium oxide into the reaction bottom solution to serve as seed crystals;
(2) and (3) parallel flow precipitation: after the preparation work is finished, adding a cerium chloride solution into the reaction tank for 5-10 min; then, synchronously adding a cerium chloride solution and a carbonized ammonia water solution into the reaction tank, stirring to perform a precipitation reaction, wherein the molar concentration of the cerium chloride solution is 0.4-1.6 mol/L, and the pH value is 1.5-2.5; the molar ratio of carbon dioxide to ammonia gas in the carbonized ammonia water is 0.47-0.53, the total alkalinity of the carbonized ammonia water is 3-13 mol/L, the pH value is 9.7-10.0, and the pH value of the solution in the reaction tank is controlled to be 6.6-7.4; the temperature of the carbonized ammonia water solution is 20-30 ℃, and the temperature of the cerium chloride solution is 30-55 ℃; (3) preparing a finished cerium carbonate product: stopping adding materials, continuing stirring until the reaction is complete, filtering by a centrifugal machine, washing, and drying by spin-drying to obtain a cerium carbonate finished product.
2. The method for preparing cerium carbonate by precipitating rare earth ions according to claim 1, wherein the reaction bottom liquid is pure water or washing water of cerium carbonate, and the temperature of the reaction bottom liquid is 30-55 ℃.
3. The method for preparing cerium carbonate by precipitating rare earth ions according to claim 1, wherein in the step (3), the addition is stopped, the stirring reaction is continued for 30min, and the cerium carbonate product is obtained by filtering, washing and drying through a centrifuge.
4. The method for preparing cerium carbonate by precipitating rare earth ions according to claim 1, wherein in the step (2), the reaction temperature is controlled to be 30-55 ℃.
5. The method for preparing cerium carbonate by precipitating rare earth ions according to claim 1, wherein the addition flow rate of the carbonated aqueous ammonia solution is 0.26-2.90L/min; the adding flow rate of the cerium chloride solution is 0.80-4.70L/min.
6. The method for preparing cerium carbonate by precipitating rare earth ions according to claim 1, wherein the addition time of the carbonated aqueous ammonia solution is 3.0-10.4 hours, and the addition time of the cerium chloride solution is 3.0-10.3 hours.
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