CN113604687A - Method for removing aluminum from rare earth feed liquid by using extracting agent containing pivalic acid - Google Patents
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Abstract
The invention relates to the technical field of rare earth feed liquid treatment, and discloses a method for removing aluminum from a rare earth feed liquid by using an extracting agent containing pivalic acid, wherein pivalic acid is used as an extracting agent to replace naphthenic acid to remove aluminum from an aluminum-containing mixed rare earth chloride feed liquid. The organic extractant containing pivalic acid is used to treat the material liquid containing Al and RE without altering the technological process and equipment. The pivalic acid is a chemically synthesized unitary organic carboxylic acid, has sufficient synthetic raw material sources, stable market price and lower price than naphthenic acid, and is beneficial to reducing the purchase cost. The method for removing aluminum from the rare earth feed liquid by the extracting agent containing the pivalic acid has the advantages of simple process flow, high controllability, good adaptability and strong system stability, and can easily obtain the high-purity mixed rare earth feed liquid. The organic extracting agent of the pivalic acid has stable performance, low loss, high phase separation speed and high extraction efficiency, and can greatly reduce the production cost.
Description
Technical Field
The invention relates to the technical field of rare earth feed liquid treatment, in particular to a method for removing aluminum from a rare earth feed liquid by using an extracting agent containing pivalic acid.
Background
In the ion adsorption type rare earth ore, rare earth elements are adsorbed on the surface of the clay mineral in an ionic state, aluminum ions and other non-rare earth ions in the mineral are leached into a leaching solution together with rare earth during leaching of the rare earth ore, and a large amount of aluminum ions still exist after the leaching solution is pretreated into concentrate. The most widely used method for removing aluminum at present is naphthenic acid extraction, which comprises using 20-25% naphthenic acid, 20% isooctanol and sulfonated kerosene to form an organic extraction phase, adding alkali liquor to saponify, extracting and separating aluminum from rare earth chloride feed liquid in a single-stage or multi-stage extraction tank, back extracting the loaded organic phase with hydrochloric acid solution, and recovering rare earth in the back extraction raffinate by oxalic acid precipitation. Naphthenic acid is derived from byproducts of the petroleum refining industry, and no naphthenic acid byproduct is produced since the petroleum refining adopts the hydrocracking advanced process, so that a substitute of naphthenic acid is urgently needed in production to meet the requirement of the rare earth aluminum removal process.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method for removing aluminum from a rare earth feed liquid by using an extracting agent containing pivalic acid, which is characterized in that the extracting agent is prepared by using pivalic acid to replace naphthenic acid, and the aluminum removal rate is more than or equal to 99.9 percent and the rare earth recovery rate is more than or equal to 99 percent through the processes of 1-grade extraction, 1-grade washing and 1-grade back extraction from an aluminum-containing mixed rare earth chloride feed liquid, thereby overcoming the defects of an oxalic acid precipitation method, realizing the purposes of high-efficiency aluminum removal and high-efficiency rare earth recovery, and being applicable to the equipment and process conditions of the existing rare earth aluminum removal process.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
a method for removing aluminum from rare earth feed liquid by using an extracting agent containing pivalic acid comprises the following steps:
(1) subjecting the aluminum-containing mixed rare earth chloride feed liquid to a 1-level extraction process: the process is carried out in a monomer conical extraction tank, an extracting agent containing pivalic acid and an aluminum-containing mixed rare earth chloride feed liquid are added into the extraction tank according to the volume ratio of O/A = (2-5)/1, the mixture is stirred and mixed uniformly under the condition of keeping the temperature at 30-35 ℃, then a neutralizing agent is added dropwise while stirring, and the neutralizing agent and aluminum (Al) are controlled2O3) The total molar ratio of 9/1, stirring for 30-60 min, standing until complete phase separation is achieved to obtainAnd (3) obtaining an extract phase and a raffinate phase, wherein the extract phase is a high-aluminum low-rare earth loaded organic phase, the raffinate phase is the mixed rare earth chloride feed liquid after aluminum removal, the removal rate of aluminum is more than or equal to 99.9%, the raffinate phase is cut into an aluminum-removed rare earth feed liquid receiving tank, and the loaded organic phase is conveyed into a back extraction tank by a pump.
(2) Subjecting the aluminum-containing mixed rare earth chloride feed liquid to a loaded organic phase + 1-level extraction process: the process is carried out in a monomer conical back extraction tank, aluminum-containing mixed rare earth chloride feed liquid with the same volume as that in the step (1) is added into the back extraction tank to be mixed with the loaded organic phase in the step (1), the mixture is stirred with the loaded organic phase for 30-60 min under the condition of keeping the temperature at 30-35 ℃, then the mixture is kept stand until complete phase separation is achieved, the feed liquid at the lower layer is cut and conveyed into an extraction tank by a pump, and the loaded organic phase is left in the back extraction tank to be washed. In the process, the rare earth ions in the organic phase are exchanged with aluminum ions in the aluminum-containing mixed rare earth chloride feed liquid in an equivalent manner.
(3) Subjecting the loaded organic phase to an acidic detergent level 1 wash process: the process is carried out in a monomer conical stripping tank, acid detergent is added into the stripping tank according to 1/5 of the volume of the organic phase in the step (1) and mixed with the loaded organic phase in the step (2), the mixture is stirred for 30-60 min under the condition of keeping the temperature at 30-35 ℃, then the mixture is stood until complete phase separation, the lower-layer washing residual liquid is cut into a washing residual liquid receiving tank, and the loaded organic phase is still left in the stripping tank to be stripped. In the step, the acid detergent can clean the residual rare earth in the loaded organic matter, and the aluminum still remains in the loaded organic matter, so that the total recovery rate of the rare earth is more than or equal to 99 percent.
(4) Subjecting the loaded organic phase to a stripping agent level 1 stripping process: the process is carried out in a monomer conical stripping tank, a stripping agent is added into the stripping tank and mixed with the loaded organic phase in the step (3), the volume of the stripping agent is determined according to O/A =5/1, the stripping agent is stirred for 30-60 min under the condition of keeping the temperature at 25-30 ℃, then the mixture is kept stand until complete phase separation is achieved, blank organic and stripping raffinate are obtained, the stripping raffinate is cut into a stripping raffinate receiving tank, and the blank organic is conveyed into an extraction tank by a pump and is subjected to the next circulating 1-stage extraction aluminum removal process with the aluminum-containing mixed chlorinated rare earth material obtained in the step (2).
Further, the washing residual liquid of the step (3) can be recycled when the Rare Earth (RE) therein is used2O3) When the concentration reaches 0.15mol/L, the acid detergent is replaced by new acid detergent. The washing residual liquid is used for preparing aluminum-containing mixed rare earth chloride feed liquid and directly recovering rare earth.
Furthermore, the raffinate in the step (4) can be used for recovering hydrochloric acid and inorganic aluminum salt by an ion exchange-oxidation-precipitation method, the hydrochloric acid can be recycled, and the inorganic aluminum salt can be used as other raw materials for production.
Further, in the aluminum-containing mixed rare earth chloride feed liquid in the steps (1) and (2), Rare Earth (RE) is contained2O3) The concentration is 1.0-1.4 mol/L; aluminum (Al)2O3) The concentration of the sodium hydroxide is less than or equal to 10 g/L; and pH = 2.9-2.95.
Further, the extracting agent containing pivalic acid in the step (1) is prepared according to the volume ratio (8% of pivalic acid to 20% of isooctanol to 72% of sulfonated kerosene), and the acidity value is 0.7 mol/L.
Further, the neutralizing agent in the step (1) is ammonia water or sodium hydroxide aqueous solution, and the concentration of the neutralizing agent is 6 mol/L.
Further, the acidic detergent in the step (3) is 0.6mol/L hydrochloric acid aqueous solution.
Further, the stripping agent in the step (4) is 6mol/L hydrochloric acid aqueous solution.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
1. the method for removing aluminum from rare earth feed liquid by using the extracting agent containing the pivalic acid is characterized in that the organic extracting agent is prepared from the pivalic acid, isooctanol and sulfonated kerosene, the processes of extracting, separating and removing aluminum and recovering rare earth are extraction processes which are carried out simultaneously by neutralization reaction and cation exchange, the extraction capacity of the extracting agent depends on the size of a complex stability constant of extracted metal ions and pivalic acid salt, the larger the complex stability constant is, the easier the extraction is, and in the pivalic acid extraction process, the control of equilibrium acidity is the most basic means for realizing the separation between metal ions. Pivalic acid is an organic weak acid which extracts metal ionsThe half-extraction pH values are higher, when the pH value of the solution is close to the hydrolysis pH value of a certain metal ion, the highest extraction rate of the metal ion can be achieved, because of the aluminum ion (Al)3+) Rare earth ion (RE)3+) The pH at which the hydrolysis starts is low so that Al3+The extraction order of the common metal ions is arranged according to the half-extraction pH value of the pivalic acid extraction metal ions, and the order is as follows: al (Al)3+>Cu2+>Zn2+>Pb2+>RE3+Albeit Al3+And RE3+The pH at which the hydrolysis starts differs, but when (RE)3+) When the concentration is high, the pH value of the hydrolysis of the rare earth and the alkaline earth is quite close to each other, so that the extraction equilibrium acidity of the pivalic acid is controlled by controlling the concentration of the rare earth and adjusting the pH value of a reaction system, and the effect of efficiently removing aluminum is achieved.
2. In the method for removing aluminum from the rare earth feed liquid by using the extracting agent containing the pivalic acid, the pivalic acid can replace naphthenic acid to be used as the extracting agent for extracting aluminum ions in the mixed rare earth. The pivalic acid is used as extractant, and the original extraction technological process and equipment are not changed. The pivalic acid is a chemically synthesized unitary organic carboxylic acid, has sufficient synthetic raw material sources, stable market price and lower price than naphthenic acid, and is beneficial to reducing the purchase cost.
3. The method for removing aluminum from the rare earth feed liquid by using the extracting agent containing the pivalic acid has the advantages of simple process flow, high controllability, good adaptability and strong system stability, and can easily obtain the high-purity mixed rare earth feed liquid. The pivalic acid extractant has stable performance, low loss, fast phase separating speed, high extraction efficiency and low production cost.
Drawings
FIG. 1 is a schematic process flow diagram of a method for removing aluminum from a rare earth feed liquid by using an extracting agent containing pivalic acid.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples:
the method for removing aluminum from the rare earth feed liquid by using the extracting agent containing the pivalic acid comprises the following steps:
(1) preparing an extracting agent according to the volume ratio (8 percent of pivalic acid-20 percent of isooctanol-72 percent of sulfonated kerosene) and the acidity value of the extracting agent is 0.7 mol/L.
(2) Adjusting the pH of the aluminum-containing mixed rare earth chloride feed liquid to 2.9-2.95 by using concentrated hydrochloric acid, and controlling Rare Earth (RE)2O3) Has a concentration of 1.0 to 1.4mol/L, and aluminum (Al)2O3) The concentration of the water is less than or equal to 10 g/L.
(3) Sodium hydroxide or ammonia water and deionized water are used to prepare a neutralizer with the alkali concentration of 6 mol/L.
(4) Preparing an acidic detergent with the hydrochloric acid concentration of 0.6mol/L by using hydrochloric acid and deionized water.
(5) Preparing a stripping agent with the hydrochloric acid concentration of 6mol/L by using hydrochloric acid and deionized water.
(6) Subjecting the aluminum-containing mixed rare earth chloride feed liquid to a 1-level extraction process: adding the extracting agent (1) and the feed liquid (2) into an extraction tank according to the volume ratio of O/A = (2-5)/1, stirring and mixing uniformly under the condition of keeping the temperature at 30-35 ℃, then dropwise adding the neutralizing agent (3) while stirring, and controlling the neutralizing agent and aluminum (Al)2O3) Stirring for 30-60 min, standing until complete phase separation is achieved to obtain an extract phase and an raffinate phase, wherein the extract phase is a high-aluminum low-rare earth loaded organic phase, the raffinate phase is a mixed rare earth chloride feed liquid after aluminum removal, splitting the raffinate phase into an aluminum-removal rare earth feed liquid receiving tank, and conveying the loaded organic phase into a back extraction tank by a pump.
(7) Subjecting the aluminum-containing mixed rare earth chloride feed liquid to a loaded organic phase + 1-level extraction process: and (3) adding the aluminum-containing mixed rare earth chloride feed liquid with the same volume as that of the (6) into a back extraction tank to be mixed with the loaded organic phase of the (6), stirring the mixture with the loaded organic phase for 30-60 min under the condition of keeping the temperature at 30-35 ℃, standing the mixture until the phase is completely split, conveying the feed liquid at the lower layer of the split layer into an extraction tank by a pump, and leaving the loaded organic phase in the back extraction tank to be washed.
(8) Subjecting the loaded organic phase to an acidic detergent level 1 wash process: adding the acidic detergent of (4) into a stripping tank according to 1/5 times of the volume of the extractant of (6), mixing with the loaded organic phase of (7), and stirring at 30 to 35 DEG CStanding for 60min, separating the lower layer of the washing residual liquid into a washing residual liquid receiving tank, and remaining the loaded organic phase in a stripping tank to be stripped. The raffinate can be recycled, when the Rare Earth (RE) therein2O3) When the concentration reaches 0.15mol/L, the new acidic washing agent is replaced, and the replaced washing residual liquid is used for preparing the aluminum-containing mixed rare earth chloride feed liquid.
(9) Subjecting the loaded organic phase to a stripping agent level 1 stripping process: adding the stripping agent in the step (5) into a stripping tank to be mixed with the loaded organic phase in the step (8), determining the volume of the stripping agent according to O/A =5/1, stirring for 30-60 min under the condition that the temperature is kept at 30-35 ℃, standing until complete phase separation is achieved, obtaining blank organic and stripping raffinate, cutting the stripping raffinate into a stripping raffinate receiving tank, conveying the blank organic into the extraction tank by a pump, and carrying out the next circulating 1-stage extraction and aluminum removal process with the aluminum-containing mixed chlorinated rare earth material in the step (7). The back raffinate can be used for recovering hydrochloric acid and inorganic salts of aluminum by an ion exchange-oxidation-precipitation method, the hydrochloric acid is recycled, and the inorganic salts of the aluminum can be used as raw materials for other production.
The technical scheme of the embodiment of the invention will be clearly and completely described below by combining with the process flow schematic diagram of the 'method for removing aluminum from rare earth feed liquid by using an extracting agent containing pivalic acid' of the invention, and obviously, the described embodiment is only a part of the embodiment of the invention, but not the whole embodiment. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing an extracting agent according to the volume ratio (8 percent of pivalic acid-20 percent of isooctanol-72 percent of sulfonated kerosene) and the acidity value of the extracting agent is 0.7 mol/L.
(2) An aluminum-containing mixed rare earth chloride feed liquid, pH =2.95, Rare Earth (RE)2O3) Concentration =1.38 mol/L, aluminum (Al)2O3) Concentration =9792 mg/L.
(3) And preparing a neutralizing agent with the concentration of 6mol/L of sodium hydroxide by using sodium hydroxide and deionized water.
(4) Preparing an acidic detergent with hydrochloric acid concentration of 0.6mol/L by using hydrochloric acid and deionized water.
(5) Preparing a stripping agent with the hydrochloric acid concentration of 6mol/L by using hydrochloric acid and deionized water.
(6) Subjecting the aluminum-containing mixed rare earth chloride feed liquid to a 1-level extraction process: adding 3000L of the extractant (1) and 1000L of the feed liquid of the extractant (2) into an extraction tank, stirring and mixing uniformly under the condition of keeping the temperature at 30 ℃, then dropwise adding 144L of the neutralizer (3) while stirring, continuously stirring for 60min, standing until complete phase separation is achieved, cutting the raffinate phase into an aluminum-removing rare earth feed liquid receiving tank, conveying the loaded organic phase into a back extraction tank by using a pump, wherein the analysis result of the aluminum-removing rare earth feed liquid is shown in Table 1, and the calculated primary aluminum removal rate is 99.96% and the primary rare earth recovery rate is 96.15%.
(7) Subjecting the aluminum-containing mixed rare earth chloride feed liquid to a loaded organic phase + 1-level extraction process: adding 1000L of the feed liquid in the step (2) into a stripping tank, mixing the feed liquid with the loaded organic phase in the step (6), stirring the mixture with the organic phase for 60min under the condition of keeping the temperature at 30 ℃, standing the mixture until the phases are completely separated, conveying the feed liquid in the lower layer of the split mixture into an extraction tank by a pump, leaving the loaded organic phase in the stripping tank for washing, and obtaining the analysis result of the aluminum-containing mixed rare earth chloride feed liquid after the + 1-stage extraction process, wherein the analysis result is shown in table 1.
(8) Subjecting the loaded organic phase to an acidic detergent level 1 wash process: adding 600L of the acidic detergent (4) into a stripping tank, mixing with the loaded organic phase (7), stirring for 60min under the condition of keeping the temperature at 30 ℃, standing until complete phase separation, splitting the lower-layer washing residual liquid into a washing residual liquid receiving tank, remaining the loaded organic phase in the stripping tank for back extraction, and calculating to obtain the total rare earth recovery rate of 99.91 percent, wherein the analysis result of the primary washing residual liquid is shown in Table 1,
(9) subjecting the loaded organic phase to a stripping agent level 1 stripping process: adding 600L of the stripping agent (5) into a stripping tank, mixing with the loaded organic phase (8), stirring for 60min under the condition of keeping the temperature at 30 ℃, standing until complete phase separation is achieved, obtaining blank organic and stripping raffinate, cutting the stripping raffinate into a stripping raffinate receiving tank, conveying the blank organic into an extraction tank by a pump, and carrying out the next cycle of 1-stage extraction aluminum removal process with the aluminum-containing mixed chlorinated rare earth material in the step (7), wherein the analysis result of the first stripping raffinate is shown in table 1, and the stripping raffinate is subjected to post-treatment.
Example 2
(1) Subjecting the aluminum-containing mixed rare earth chloride feed liquid to a 1-level extraction process: starting an extraction tank stirrer, stirring and uniformly mixing 1000L of aluminum-containing mixed rare earth chloride feed liquid input in the step (7) of the example 1 and 3000L of blank organic input in the step (9) under the condition of keeping the temperature at 30 ℃, then dropwise adding 64L of neutralizing agent input in the step (3) of the example 1 while stirring, standing for 30min until complete phase separation is achieved, cutting raffinate phase into an aluminum-removing rare earth feed liquid receiving tank, conveying a loaded organic phase into a back extraction tank by using a pump, and calculating the analysis result of the aluminum-removing rare earth feed liquid according to the table 2, wherein the primary aluminum-removing rate is 99.98% and the primary rare earth recovery rate is 98.05%.
(2) Subjecting the aluminum-containing mixed rare earth chloride feed liquid to a loaded organic phase + 1-level extraction process: 1000L of the feed liquid obtained in the step (2) of the example 1 is added into a stripping tank, mixed with the loaded organic phase obtained in the example (1), stirred for 60min under the condition of keeping the temperature at 30 ℃, then kept stand until complete phase separation, the feed liquid at the lower layer of the segmentation is conveyed into an extraction tank by a pump, the loaded organic phase is left in the stripping tank for washing, and the analysis result of the aluminum-containing mixed rare earth chloride feed liquid after the + 1-stage extraction process is shown in Table 2.
(3) Subjecting the loaded organic phase to an acidic detergent level 1 wash process: the acidic detergent 600L of step (4) of example 1 was added to the strip bath and mixed with the loaded organic phase of example (2), stirred at 30 ℃ for 60min, and then allowed to stand until complete phase separation, the lower layer of the raffinate was cut into the raffinate receiving tank, the loaded organic phase remained in the strip bath for strip extraction, the analytical results of the second raffinate are shown in table 2, and the total recovery of rare earth was calculated to be 99.96%.
(4) Subjecting the loaded organic phase to a stripping agent level 1 stripping process: adding 600L of the stripping agent obtained in the step (5) in the example 1 into a stripping tank, mixing the stripping agent with the loaded organic phase in the example (3), stirring the mixture for 60 minutes under the condition of keeping the temperature at 30 ℃, standing the mixture until complete phase separation is achieved, obtaining blank organic and stripping raffinate, cutting the stripping raffinate into a stripping raffinate receiving tank, conveying the blank organic into an extraction tank by a pump, and carrying out the next cycle of 1-stage extraction aluminum removal process with the aluminum-containing mixed chlorinated rare earth material in the step (2), wherein the analysis result of the primary stripping raffinate is shown in table 2, and the stripping raffinate is subjected to post-treatment.
TABLE 1 analysis results of feed liquid and aqueous phase in example 1
Table 2 analysis results of feed liquid and aqueous phase in example 2
Claims (8)
1. A method for removing aluminum from rare earth feed liquid by using an extracting agent containing pivalic acid is characterized by comprising the following steps: the method comprises the following steps:
(1) subjecting the aluminum-containing mixed rare earth chloride feed liquid to a 1-level extraction process: the process is carried out in a monomer conical extraction tank, an extracting agent containing pivalic acid and an aluminum-containing mixed rare earth chloride feed liquid are added into the extraction tank according to the volume ratio of O/A = (2-5)/1, the mixture is stirred and mixed uniformly under the condition of keeping the temperature at 30-35 ℃, then a neutralizing agent is added dropwise while stirring, and the neutralizing agent and aluminum (Al) are controlled2O3) Stirring for 30-60 min, standing until complete phase separation is achieved to obtain an extract phase and a raffinate phase, wherein the extract phase is a high-aluminum low-rare earth loaded organic phase, the raffinate phase is a mixed rare earth chloride feed liquid after aluminum removal, the removal rate of primary aluminum is more than or equal to 99%, the recovery rate of rare earth is more than or equal to 95%, the raffinate phase is cut into an aluminum-removed rare earth feed liquid receiving tank, and the loaded organic phase is conveyed into a back extraction tank by a pump;
(2) subjecting the aluminum-containing mixed rare earth chloride feed liquid to a loaded organic phase + 1-level extraction process: adding aluminum-containing mixed rare earth chloride feed liquid with the same volume as that in the step (1) into a monomer conical back extraction tank to be mixed with the loaded organic phase in the step (1), stirring the mixture with the loaded organic phase for 30-60 min under the condition of keeping the temperature at 30-35 ℃, standing the mixture until complete phase separation is achieved, cutting the feed liquid at the lower layer, conveying the cut feed liquid into an extraction tank by a pump, and keeping the loaded organic phase in the back extraction tank to be washed;
in the process, the equivalent exchange is carried out between the rare earth ions in the organic phase and the aluminum ions in the aluminum-containing mixed rare earth chloride feed liquid;
(3) subjecting the loaded organic phase to an acidic detergent level 1 wash process: the process is carried out in a monomer conical stripping tank, acid detergent is added into the stripping tank according to 1/5 of the volume of the organic phase in the step (1) to be mixed with the loaded organic phase in the step (2), the mixture is stirred for 30-60 min under the condition of keeping the temperature at 30-35 ℃, then the mixture is stood until complete phase separation is achieved, the lower-layer washing residual liquid is cut into a washing residual liquid receiving tank, and the loaded organic phase is still left in the stripping tank to be subjected to back extraction; in the step, the acid detergent can clean the residual rare earth in the loaded organic matter, and the aluminum still remains in the loaded organic matter, so that the total recovery rate of the rare earth is more than or equal to 99 percent;
(4) subjecting the loaded organic phase to a stripping agent level 1 stripping process: the process is carried out in a monomer conical stripping tank, a stripping agent is added into the stripping tank and mixed with the loaded organic phase in the step (3), the volume of the stripping agent is determined according to O/A =5/1, the stripping agent is stirred for 30-60 min under the condition of keeping the temperature at 25-30 ℃, then the mixture is kept stand until complete phase separation is achieved, blank organic and stripping raffinate are obtained, the stripping raffinate is cut into a stripping raffinate receiving tank, and the blank organic is conveyed into an extraction tank by a pump and is subjected to the next circulating 1-stage extraction aluminum removal process with the aluminum-containing mixed chlorinated rare earth material obtained in the step (2).
2. The method for removing aluminum from rare earth feed liquid by using the extracting agent containing pivalic acid as claimed in claim 1, wherein the extracting agent comprises: the washing residual liquid in the step (3) can be recycled when the Rare Earth (RE) in the washing residual liquid2O3) When the concentration reaches 0.15mol/L, the new acidic washing agent is replaced, and the washing residual liquid is used for preparing aluminum-containing mixed rare earth chloride feed liquid to directly recover rare earth.
3. The method for removing aluminum from rare earth feed liquid by using the extracting agent containing pivalic acid as claimed in claim 1, wherein the extracting agent comprises: the raffinate in the step (4) can be used for recovering hydrochloric acid and inorganic aluminum salt by an ion exchange-oxidation-precipitation method, the hydrochloric acid can be recycled, and the inorganic aluminum salt can be used as a raw material for other production.
4. The method for removing aluminum from rare earth feed liquid by using the extracting agent containing pivalic acid as claimed in claim 1, wherein the extracting agent comprises: rare Earth (RE) in the aluminum-containing mixed rare earth chloride feed liquid in the step (1)2O3) The concentration is 1.0-1.4 mol/L; aluminum (Al)2O3) The concentration is less than or equal to 10 g/L; and (3) pH = 2.90-2.95.
5. The method for removing aluminum from rare earth feed liquid by using the extracting agent containing pivalic acid as claimed in claim 1, wherein the extracting agent comprises: the extracting agent containing pivalic acid in the step (1) is prepared according to the volume ratio of pivalic acid (8 percent-isooctanol 20 percent-sulfonated kerosene 72 percent), and the acidity value is 0.7 mol/L.
6. The method for removing aluminum from rare earth feed liquid by using the extracting agent containing pivalic acid as claimed in claim 1, wherein the neutralizing agent in the step (1) is ammonia water or sodium hydroxide aqueous solution with the concentration of 6 mol/L.
7. The method for removing aluminum from rare earth feed liquid by using the extracting agent containing pivalic acid as claimed in claim 1, wherein the extracting agent comprises: the acidic detergent in the step (3) is 0.6mol/L hydrochloric acid aqueous solution.
8. The method for removing aluminum from rare earth feed liquid by using the extracting agent containing pivalic acid as claimed in claim 1, wherein the extracting agent comprises: the stripping agent in the step (4) is 6mol/L hydrochloric acid aqueous solution.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773955A (en) * | 2013-11-04 | 2014-05-07 | 中铝广西有色金源稀土股份有限公司 | Method for removing aluminium in tombarthite feed liquid |
| CN103966441A (en) * | 2014-05-08 | 2014-08-06 | 广东省工业技术研究院(广州有色金属研究院) | Method for continuously extracting aluminum from rare earth liquid |
| CN104058948A (en) * | 2014-07-03 | 2014-09-24 | 河北华旭化工有限公司 | Method for recycling sulfuric acid and pivalic acid from byproduct waste acid in pivalic acid synthetic process |
| CN106544506A (en) * | 2015-09-16 | 2017-03-29 | 金发科技股份有限公司 | A kind of extractant composition and preparation method and application |
| CN111440945A (en) * | 2020-05-18 | 2020-07-24 | 中国科学院过程工程研究所 | Method for removing aluminum by refining rare earth gadolinium with ionic liquid method |
| CN112280981A (en) * | 2020-11-23 | 2021-01-29 | 中国科学院过程工程研究所 | Ionic liquid extractant for efficient rare earth aluminum removal and preparation method thereof |
| CN113373304A (en) * | 2021-06-09 | 2021-09-10 | 江西理工大学 | Method for removing aluminum from rare earth feed liquid by complexing-cloud point extraction |
-
2021
- 2021-08-18 CN CN202110946266.5A patent/CN113604687B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773955A (en) * | 2013-11-04 | 2014-05-07 | 中铝广西有色金源稀土股份有限公司 | Method for removing aluminium in tombarthite feed liquid |
| CN103966441A (en) * | 2014-05-08 | 2014-08-06 | 广东省工业技术研究院(广州有色金属研究院) | Method for continuously extracting aluminum from rare earth liquid |
| CN104058948A (en) * | 2014-07-03 | 2014-09-24 | 河北华旭化工有限公司 | Method for recycling sulfuric acid and pivalic acid from byproduct waste acid in pivalic acid synthetic process |
| CN106544506A (en) * | 2015-09-16 | 2017-03-29 | 金发科技股份有限公司 | A kind of extractant composition and preparation method and application |
| CN111440945A (en) * | 2020-05-18 | 2020-07-24 | 中国科学院过程工程研究所 | Method for removing aluminum by refining rare earth gadolinium with ionic liquid method |
| CN112280981A (en) * | 2020-11-23 | 2021-01-29 | 中国科学院过程工程研究所 | Ionic liquid extractant for efficient rare earth aluminum removal and preparation method thereof |
| CN113373304A (en) * | 2021-06-09 | 2021-09-10 | 江西理工大学 | Method for removing aluminum from rare earth feed liquid by complexing-cloud point extraction |
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