CN113716757B - Method for removing zinc from extract liquid and application of rare earth saponification wastewater - Google Patents

Method for removing zinc from extract liquid and application of rare earth saponification wastewater Download PDF

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CN113716757B
CN113716757B CN202111119259.4A CN202111119259A CN113716757B CN 113716757 B CN113716757 B CN 113716757B CN 202111119259 A CN202111119259 A CN 202111119259A CN 113716757 B CN113716757 B CN 113716757B
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rare earth
organic phase
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saponification
stripping
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CN113716757A (en
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杨启山
马莹
杨叶平
刘赟
赵清元
李占明
杨卉
王延铭
丁艳蓉
赵小杨
江道宽
付东磊
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Guangxi Changming Environmental Protection Technology Co ltd
Inner Mongolia University of Science and Technology
Baotou Rare Earth Research Institute
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Guangxi Changming Environmental Protection Technology Co ltd
Inner Mongolia University of Science and Technology
Baotou Rare Earth Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G43/00—Compounds of uranium
    • C01G43/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G43/00—Compounds of uranium
    • C01G43/01—Oxides; Hydroxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a method for removing zinc from an extraction liquid for extracting europium by zinc reduction extraction. The method comprises the following steps: the device comprises a saponification section, a rare earth saponification section, an extraction section, a washing section, a first back extraction section and a second back extraction section; the first back extraction section: at least a part of the rare earth saponification wastewater from the rare earth saponification section is used as a first stripping agent to be conveyed to a first stripping section and contacted with the washed extraction liquid to obtain a first stripping liquid and a first load organic phase. The method can obtain Zn respectively 2+ Enrichment and Sm 3+ And Gd 3+ And (3) a back extraction solution for enriching trivalent rare earth ions. The invention also provides an application of the rare earth saponification wastewater in removing zinc from an extract liquid for extracting europium from zinc reduction extraction.

Description

Method for removing zinc from extract liquid and application of rare earth saponification wastewater
Technical Field
The invention relates to a method for removing zinc from an extraction liquid for extracting europium by zinc reduction and application of rare earth saponification wastewater.
Background
Europium oxide (Eu) 2 O 3 ) The method is mainly used for manufacturing fluorescent materials, laser materials, shielding materials, structural materials and the like, and can also be used as a raw material for synthesizing other europium compounds. With the development of scientific technology, europium oxide will show its importance in the field of special-purpose materials. At present, the main flow of the domestic high-purity europium oxide production process is as follows: adding zinc powder into europium-enriched solution to make Eu 3+ Reduction to Eu 2+ Zinc powder is converted into Zn 2+ Into rare earth solution containing Zn 2+ The rare earth solution of (2) is used as feed liquid for reduction extraction, and Zn is separated in the reduction extraction separation section 2+ As an easily extractable component with Sm 3+ 、Gd 3+ The trivalent rare earth ions enter an organic phase, and the stripping liquid obtained after stripping contains Zn 2+ And Sm 3+ 、Gd 3+ And the trivalent rare earth ions are separated from zinc ions and rare earth ions in the strip liquor, and then the rare earth ions are separated.
CN103922383a discloses a method for extracting and separating rare earth and zinc from a back raffinate for reducing, extracting and separating europium. Reducing, extracting and separating europium from the back raffinate to obtain mixed solution of rare earth chloride and zinc chloride, neutralizing residual acid with ammonia water, and adding NH 4 Cl is taken as feed liquid, and the organic phase is formed by P 507 Kerosene composition with addition of NH 4 GdCl of Cl 3 The solution is used as a washing liquid to obtain raffinate containing zinc and an organic phase loaded with rare earth. The method needs to carry out secondary treatment on the back raffinate for reducing, extracting and separating europium so as to separate rare earth from zinc.
CN105886761a discloses a method for separating rare earth and zinc from a reverse raffinate of reduction extraction europium. The back raffinate of the reduction extraction europium is mixed solution of rare earth chloride and zinc chloride, the acidity of the solution is regulated to pH value of 4 by solid ammonium bicarbonate, and then NH is added 4 And (3) taking the rare earth as a feed liquid after Cl, adding solid ammonium bicarbonate into the feed liquid when the temperature of the feed liquid reaches 70 ℃, completely converting the rare earth in the feed liquid into rare earth carbonate precipitate, and filtering to obtain rare earth carbonate precipitate and zinc-containing precipitate mother liquor. The method needs to carry out secondary treatment on the back raffinate for extracting europium by reduction extraction so as to separate rare earth from zinc.
CN103924075A discloses an NH-added device 4 Cl hydrochloric acid solution is used as washing liquid for extracting and separating samarium from zinc. Extractant P in organic phase 507 Extraction of Sm 3+ And Zn 2+ Then as a loaded organic phase, NH is added 4 Cl hydrochloric acid solution is used as washing liquid, and the washing liquid is mixed with Zn in the loaded organic phase 2+ The washing rate of (2) is 94.89-100%, sm 3+ The washing rate of (2) is 30-91.58%. The method cannot separate zinc ions from rare earth ions.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a method for removing zinc from an extract liquid of reduction extraction of europium from zinc, which method can separately obtain Zn 2+ Enrichment and Sm 3+ And Gd 3+ And (3) a back extraction solution for enriching trivalent rare earth ions. Furthermore, the method has good stability and can be suitable for various production scales. Another object of the invention is to provideThe method is used for the use of the rare earth saponification wastewater.
The technical aim is achieved through the following technical scheme.
In one aspect, the invention provides a method for removing zinc from an extract liquid for extracting europium from zinc reduction extraction, which is characterized by comprising the following steps:
saponification section: contacting the organic phase with ammonia water to obtain a saponified organic phase;
and (3) a rare earth saponification section: the saponification organic phase is contacted with a rare earth saponification agent to obtain a rare earth saponification organic phase and rare earth saponification wastewater;
extraction section: contacting a rare earth saponification organic phase from a rare earth saponification section with a zinc-reduced samarium-europium-gadolinium enriched solution to obtain raffinate and extract; wherein, in the zinc-reduced samarium-europium-gadolinium enriched solution, eu 2+ /Eu 3+ ≥99％；
Washing section: washing the extract to obtain a washed extract;
the first back extraction section: at least a part of rare earth saponification wastewater from the rare earth saponification section is used as a first stripping agent to be conveyed to a first stripping section and contacted with the washed extraction liquid to obtain a first stripping liquid and a first load organic phase;
the second back extraction section: performing second stripping on the first loaded organic phase by adopting a second stripping agent to obtain second stripping liquid and a second loaded organic phase;
wherein, the flow volume ratio of the organic phase to the rare earth saponification agent is 3.5-4.5:1; the volume flow ratio of the organic phase to the first stripping agent is 3.5-4.2:1.
The method according to the invention preferably further comprises a water wash section:
and (3) washing: washing the second loaded organic phase with water to obtain a blank organic phase; returning the blank organic phase to the saponification section for continuous use.
According to the process of the present invention, preferably, the flow volume ratio of the organic phase to the second stripping agent is from 10 to 30:1.
According to the process of the invention, the organic phase and the water used in the washing stage preferably have a flow volume ratio of 50 to 120:1.
Preferably, the organic phase comprises an extractant and a diluent, the extractant being selected from the group consisting of P 204 Or P 507 The diluent is kerosene, and the content of the extractant in the organic phase is 0.5-2.5 mol/L.
According to the method of the present invention, preferably, the concentration of ammonia water used in the saponification section is 6 to 12mol/L.
According to the method of the present invention, preferably, the rare earth saponification agent used in the rare earth saponification stage is raffinate obtained in the extraction stage.
According to the method of the present invention, preferably, the washing liquid used in the washing stage is hydrochloric acid of 2 to 4mol/L, and the second stripping agent used in the second stripping stage is hydrochloric acid of 4.5 to 7 mol/L.
According to the method of the present invention, preferably, the content of rare earth ions in the first stripping solution is not more than 0.0005mol/L, and Zn in the second stripping solution 2+ Less than or equal to 0.1g/L; wherein, the content of rare earth ions is calculated by the corresponding rare earth oxide, zn 2+ The content of (2) is calculated as zinc oxide.
In another aspect, the invention provides a use of rare earth saponification wastewater in removing zinc from an extract liquid of reduction extraction of europium from zinc, the rare earth saponification wastewater is used as a stripping agent to strip the extract liquid of reduction extraction of europium from zinc, and the extract liquid contains Zn 2+ 、Sm 3+ And Gd 3+ 。
The invention uses rare earth saponification wastewater as a first stripping agent and controls each parameter of samarium-europium-gadolinium extraction and separation to ensure that Zn in extraction liquid obtained by the extraction and separation of samarium-europium-gadolinium 2+ Is enriched into the back extraction liquid, thereby realizing Zn in the extraction liquid in the extraction and separation process of samarium-europium-gadolinium 2+ Separating from other rare earth ions to make Zn in the extract liquid 2+ And the rare earth ions respectively form strip liquor, so that the subsequent work is convenient, the industrial practical value is extremely high, and the cost is reduced. The method of the invention can be suitable for various production-scale samarium-europium-gadolinium reduction extraction separation processes, has good process stability and is convenient for industrial application.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
In the invention, the extraction liquid for extracting europium by zinc reduction refers to the extraction liquid generated in the separation process of extracting europium by reduction extraction by taking zinc reduced samarium-europium-gadolinium enriched material liquid as a raw material.
< method for removing Zinc from an extract of europium extracted by Zinc reduction extraction >
The method for removing zinc from the extraction liquid for extracting europium from zinc reduction comprises the following steps: the device comprises a saponification section, a rare earth saponification section, an extraction section, a washing section, a first back extraction section and a second back extraction section. Optionally, a water wash section is also included. The invention can be carried out by fractional extraction. The saponification section, the rare earth saponification section, the extraction section, the washing section, the first back extraction section, the second back extraction section and the washing section can be performed in a water-sealed mixing-clarifying extraction tank under the protection of inert gas. The inert gas may be argon.
Saponification section
The organic phase is contacted with ammonia water to obtain a saponified organic phase.
In the present invention, the organic phase may include an extractant and a diluent. In certain embodiments, the organic phase consists of an extractant and a diluent. The extractant may be selected from P 204 Or P 507 One or more of the following; preferably, the extractant is P 507 . The diluent may be kerosene. The content of the extractant in the organic phase can be 0.5-2.5 mol/L; preferably 1.0 to 2.0mol/L; more preferably 1.3 to 1.8mol/L.
The concentration of the ammonia water can be 6-12 mol/L; preferably 7 to 11mol/L; more preferably 8 to 10mol/L.
The saponification mode can be continuous and parallel flow. The number of saponification stages can be 3 or more; preferably 3 to 5.
Rare earth saponification section
And (3) contacting the saponification organic phase with a rare earth saponification agent to obtain a rare earth saponification organic phase and rare earth saponification wastewater.
The rare earth saponification agent adopted in the rare earth saponification section can be raffinate obtained in the extraction section. The flow volume ratio of the organic phase to the rare earth saponification agent can be 3.5-4.5:1; preferably 3.6 to 4.2:1; more preferably 3.8 to 4.1:1. Thus, the whole system can stably operate, and Eu can be added 2+ Can be separated from rare earth ions and can obtain rare earth saponification wastewater with proper components, and the rare earth saponification wastewater can successfully treat Zn in the extract liquid 2+ Separated from other rare earth ions.
The rare earth saponification mode can be continuous countercurrent. The number of the rare earth saponification sections can be more than 5; preferably 5 to 9.
Extraction section
And conveying the rare earth saponification organic phase from the rare earth saponification section to an extraction section, and contacting with a zinc-reduced samarium-europium-gadolinium enriched solution to obtain raffinate and extract. The extraction mode can be continuous countercurrent.
Eu in the zinc-reduced samarium-europium-gadolinium enriched solution of the invention 2+ /Eu 3+ More than or equal to 99 percent. Zinc is added into the samarium-europium-gadolinium enriched solution, and Eu in the samarium-europium-gadolinium enriched solution 3+ Reduction to Eu 2+ 。
In samarium europium gadolinium enriched solution, eu 3+ The content of (2) is more than or equal to 10wt%. In certain embodiments, eu 3+ The content of (C) is 5-15 wt%. In other embodiments, eu 3+ The content of (C) is 45-55wt%. Eu (Eu) 3+ Is Eu in samarium-europium-gadolinium enriched solution 3+ Ratio of mass to total mass of rare earth ions. Wherein, the mass of each rare earth ion is calculated by the corresponding trivalent rare earth oxide.
Sm in Sm-Eu-Gd concentrate solution 3+ The content of (2) may be 1 to 90wt%; preferably 20 to 60wt%. Sm (Sm) 3+ Is Sm in Sm-europium-gadolinium enriched solution 3+ Ratio of mass to total mass of rare earth ions. Wherein, the mass of each rare earth ion is calculated by the corresponding trivalent rare earth oxide.
Gd in samarium-europium-gadolinium enriched solution 3+ The content of (2) may be 1 to 90wt%; preferably 20 to 50% by weight. Gd (Gd) 3+ Is Gd in samarium-europium-gadolinium enriched solution 3+ Ratio of mass to total mass of rare earth ions. Wherein, the mass of each rare earth ion is calculated by the corresponding trivalent rare earth oxide.
The pH value of the samarium-europium-gadolinium enriched solution is 1.5-2.0. The content of rare earth ions in the samarium-europium-gadolinium enriched solution is 0.5-1.0 mol/L, and the content of the rare earth ions is calculated by the corresponding rare earth oxide.
In certain embodiments, the volume flow ratio of the organic phase to the zinc-reduced samarium europium gadolinium concentrate solution is 3.0 to 4.0:1; preferably 3.4 to 3.8:1. In other embodiments, the volume flow ratio of the organic phase to the zinc-reduced samarium europium gadolinium concentrate solution is 2.0 to 3.0:1; preferably 2.3 to 2.7:1. Thus not only reducing the dosage of the organic phase, but also separating high-purity Eu-rich Eu 2+ Raffinate ensures the stable operation of the whole system.
Eu in samarium europium gadolinium enriched solution reduced by extraction stage zinc 2+ Ion separation into raffinate, while Zn 2+ And Sm 3+ 、Gd 3+ And other rare earth ions are in the extract liquid. The raffinate is further passed through H 2 O 2 Oxidation can produce Eu with purity more than or equal to 99.999 percent 2 O 3 。Eu 2 O 3 Eu is adopted as the purity of (C) 2 O 3 The mass ratio of the rare earth oxide to the mass of the rare earth oxide.
Washing section
Washing the extract to obtain a washed extract. The washing mode can be continuous countercurrent.
The washing liquid adopted in the washing section can be hydrochloric acid with the concentration of 2-4 mol/L; preferably 3 to 4mol/L hydrochloric acid.
In certain embodiments, the volume flow ratio of the zinc-reduced samarium europium gadolinium concentrate solution to the wash solution is 80 to 100:1; preferably 85 to 95:1. In other embodiments, the volume flow ratio of the zinc-reduced samarium europium gadolinium concentrate solution to the wash solution is 450 to 550:1; preferably 480 to 520:1.
The total of the extraction section and the washing section can be 30-60 grades; preferably 35 to 45.
First back extraction section
And (3) conveying the rare earth saponification wastewater from the rare earth saponification section to a first stripping section as a first stripping agent, and contacting with the washed extraction liquid to obtain a first stripping liquid and a first loaded organic phase. The invention takes the rare earth saponification wastewater as the reverse liquid, which can not only enable Zn in the extract liquid to be used 2+ The rare earth saponification wastewater is separated from other rare earth ions, the post-treatment process of the rare earth saponification wastewater is omitted, and the method has extremely high process practical value.
In the invention, the volume flow ratio of the organic phase to the first stripping agent can be 3.5-4.2:1; preferably 3.7 to 4.2:1; more preferably 3.8-4.1:1, which not only ensures the stable operation of the whole system, but also can lead Zn in the extract liquid to be more stable 2+ Separating into the first stripping solution to realize Zn 2+ And separating the rare earth ions from other rare earth ions.
In the present invention, the volume flow ratio of the rare earth saponification agent to the first stripping agent may be 1:1. Thus, all the rare earth saponification wastewater can be used as the first stripping agent, and Zn can be used as the second stripping agent 2+ Separated into the first stripping liquid, and reduces the burden of post-treatment of the rare earth saponification wastewater.
In the first back extraction liquid, zn 2+ The content of (3) to (10) g/L. In certain embodiments, zn 2+ The content of (C) is 4-8 g/L. Zn (zinc) 2+ The content of (2) is calculated as ZnO.
In the first stripping liquid, the content of rare earth ions is less than or equal to 0.0005mol/L. The content of rare earth ions is calculated by the corresponding rare earth oxide.
The first stripping mode may be a continuous countercurrent. The number of stages of the first stripping section is more than 4; preferably 4 to 12 grades; more preferably 5 to 10. Thus, the first stripping liquid with stable quality can be obtained, and the organic phase and rare earth backlog in the extraction tank body are reduced.
Second back extraction section
And carrying out second stripping on the first loaded organic phase by adopting a second stripping agent to obtain second stripping liquid and a second loaded organic phase.
The second stripping agent adopted in the second stripping section can be 4.5-7 mol/L hydrochloric acid; preferably 5.5 to 6.5mol/L hydrochloric acid.
In the invention, the volume flow ratio of the organic phase to the second stripping agent can be 10-30:1; preferably 10 to 25:1; more preferably 12 to 22:1.
In the second back extraction liquid, zn 2+ The content of (2) is less than or equal to 0.1g/L. In the second stripping solution, the content of rare earth ions can be 1.2-2 mol/L. In certain embodiments, the rare earth ion content is 1.4 to 1.8mol/L. The content of rare earth ions is calculated by the corresponding rare earth oxide. Zn (zinc) 2+ The content of (2) is calculated as ZnO. The second stripping liquid obtained by the method can be used as feed liquid to directly carry out rare earth separation treatment.
The second stripping mode may be a continuous countercurrent. The number of stages of the second stripping section is more than 4; preferably from 6 to 16 stages; more preferably 10 to 13. Thus, the second stripping liquid with stable quality can be obtained, and the organic phase and rare earth backlog in the extraction tank body are reduced.
Water washing section
Washing the second loaded organic phase with water to obtain a blank organic phase; returning the blank organic phase to the saponification section for continuous use.
In the invention, the flow volume ratio of the organic phase to the water used in the water washing section can be 50-120:1; preferably 70-110:1; more preferably 90 to 110:1.
The water washing mode can be continuous semi-countercurrent. The number of stages of the water washing section can be more than 3 stages; preferably 3 to 4.
< use of rare-earth saponification waste Water >
Zn in the extraction liquid for extracting europium from zinc by reduction extraction by taking rare earth saponification wastewater as back extractant 2+ Separated from other rare earth ions. The invention provides the use of rare earth saponification wastewater in removing zinc from an extraction liquid for extracting europium from zinc reduction extraction, the extraction liquid for extracting europium from zinc reduction extraction is back extracted by taking the rare earth saponification wastewater as a back extractant, and the extraction liquid contains Zn 2+ 、Sm 3+ And Gd 3+ . Extraction liquidMedium except Zn 2+ 、Sm 3+ And Gd 3+ In addition, other trivalent rare earth ions can be contained. The content of rare earth ions in the obtained stripping solution is less than or equal to 0.0005mol/L. The content of rare earth ions is calculated by the corresponding rare earth oxide. Zn (zinc) 2+ The content of (3) to (10) g/L. In certain embodiments, zn 2+ The content of (C) is 4-8 g/L. Zn (zinc) 2+ The content of (2) is calculated as ZnO.
The method specifically comprises the following steps:
saponification section: contacting the organic phase with ammonia water to obtain a saponified organic phase;
and (3) a rare earth saponification section: the saponification organic phase is contacted with a rare earth saponification agent to obtain a rare earth saponification organic phase and rare earth saponification wastewater;
extraction section: contacting a rare earth saponification organic phase from a rare earth saponification section with a zinc-reduced samarium-europium-gadolinium enriched solution to obtain raffinate and extract; wherein, in the zinc-reduced samarium-europium-gadolinium enriched solution, eu 2+ /Eu 3+ ≥99％；
Washing section: washing the extract to obtain a washed extract;
the first back extraction section: at least a part of rare earth saponification wastewater from the rare earth saponification section is used as a first stripping agent to be conveyed to a first stripping section and contacted with the washed extraction liquid to obtain a first stripping liquid and a first load organic phase;
the second back extraction section: and carrying out second stripping on the first loaded organic phase by adopting a second stripping agent to obtain second stripping liquid and a second loaded organic phase.
In certain embodiments, a water wash section may also be included.
The materials and parameters adopted in the saponification section, the rare earth saponification section, the extraction section, the washing section, the first back extraction section, the second back extraction section and the washing section are specifically described in the foregoing, and are not described in detail herein.
The test method is described as follows:
the content of each rare earth ion in the samarium-europium-gadolinium enriched solution is tested by adopting the following method:
chemical analysis method of samarium-europium-gadolinium enrichment of GB/T23594.2-2009, part 2: measuring the distribution of fifteen rare earth element oxides, and performing inductive coupling plasma emission spectrometry;
zn in back extraction liquid 2+ The content of (2) is tested by the following method:
the chemical analysis method of non-rare earth impurities in rare earth metals and oxides thereof of GB/T12690.5-2017, the 5 th part of the method comprises the steps of measuring cobalt, manganese, lead, nickel, copper, zinc, aluminum, chromium, magnesium, cadmium, vanadium and iron;
the content of rare earth ions in the stripping solution is tested by adopting the following method:
method for chemical analysis of rare earth metals and compounds thereof, and determination of the total amount of rare earth.
Examples 1 to 3
Zinc powder is adopted to reduce the samarium-europium-gadolinium enriched solution, and the zinc-reduced samarium-europium-gadolinium enriched solution is obtained. Reduction ratio Eu in zinc-reduced samarium-europium-gadolinium enriched solution 2+ /Eu 3+ More than or equal to 99 percent. The parameters of the samarium europium gadolinium enriched solution are detailed in Table 1.
Saponification section: the organic phase is P 507 And kerosene, P in the organic phase 507 The content of (C) was 1.5mol/L. The organic phase was contacted with aqueous ammonia having a concentration of 9mol/L to obtain a saponified organic phase. The saponification mode is continuous and parallel flow.
And (3) a rare earth saponification section: and (3) taking part of raffinate generated in the extraction section as a rare earth saponification agent, and contacting the saponification organic phase with the rare earth saponification agent to obtain a rare earth saponification organic phase and rare earth saponification wastewater. The saponification mode of rare earth is continuous countercurrent. The rare earth saponification wastewater is transported to a first stripping section as a first stripping agent.
Extraction section: and (3) contacting the rare earth saponification organic phase from the rare earth saponification section with a zinc-reduced samarium-europium-gadolinium enriched solution to obtain an extract and raffinate. A portion of the raffinate is returned to the rare earth saponification stage as a rare earth saponification agent. Another part of raffinate is recovered and can be used for preparing high-purity Eu 2 O 3 Is a raw material of (a) a powder. The extraction mode is continuous countercurrent.
Washing section: washing the extract by using 3.6mol/L hydrochloric acid as washing liquid to obtain washed extract. The washing mode is continuous countercurrent.
The first back extraction section: at least a part of the rare earth saponification wastewater from the rare earth saponification section is used as a first stripping agent to be conveyed to a first stripping section and contacted with the washed extraction liquid to obtain a first stripping liquid and a first load organic phase. The first stripping mode is continuous countercurrent.
The second back extraction section: and carrying out second stripping on the first loaded organic phase by taking 6.0mol/L hydrochloric acid as a second stripping agent to obtain second stripping liquid and a second loaded organic phase. The second stripping mode is continuous countercurrent.
And (3) washing: and washing the second loaded organic phase with water to obtain a blank organic phase. The blank organic phase is returned to the saponification stage for further use. The water washing mode is continuous countercurrent.
The saponification section, the rare earth saponification section, the extraction section, the washing section, the first back extraction section, the second back extraction section and the washing section are carried out in a water-sealed mixing-clarifying extraction tank under the protection of argon. The method is carried out by adopting a fractional extraction mode.
The raffinate obtained from the extraction section adopts H 2 O 2 Oxidizing to obtain Eu 2 O 3 。
TABLE 1
Note that: the content of each rare earth ion is the ratio of the mass of each rare earth ion in the samarium-europium gadolinium enriched solution to the total mass of the rare earth ions, and the mass of each rare earth ion is calculated by the corresponding trivalent rare earth oxide.
TABLE 2
Note that: eu (Eu) 2 O 3 Is Eu 2 O 3 The ratio of the mass of (c) to the mass of rare earth oxide.
The content of rare earth ions in the first and second stripping solutions is calculated by the rare earth oxide corresponding to the rare earth ions, zn 2+ The content of (2) is calculated as ZnO.
Comparative examples 1 and 2
The flow rates of the materials are shown in Table 3, and the rest is the same as in example 1. Eu obtained 2 O 3 The purity of the first stripping solution and the second stripping solution, zn 2+ And the rare earth ion concentrations are shown in table 3.
TABLE 3 Table 3
Note that: eu (Eu) 2 O 3 Is Eu 2 O 3 The ratio of the mass of (c) to the mass of rare earth oxide.
The content of rare earth ions in the first and second stripping solutions is calculated by the rare earth oxide corresponding to the rare earth ions, zn 2+ The content of (2) is calculated as ZnO.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.

Claims (8)

1. A method for removing zinc from an extract of europium extracted by zinc reduction extraction, comprising the steps of:
saponification section: contacting the organic phase with ammonia water to obtain a saponified organic phase;
and (3) a rare earth saponification section: the saponification organic phase is contacted with a rare earth saponification agent to obtain a rare earth saponification organic phase and rare earth saponification wastewater;
extraction section: contacting the rare earth saponification organic phase from the rare earth saponification section with a zinc-reduced samarium-europium-gadolinium enriched solution to enable Eu in the zinc-reduced samarium-europium-gadolinium enriched solution 2+ Ion separation into raffinate, zn 2+ And other rare earth ions in the extract; wherein, in the zinc-reduced samarium-europium-gadolinium enriched solution, eu 2+ /Eu 3+ ≥99％；
Washing section: washing the extract to obtain a washed extract;
the first back extraction section: at least a part of rare earth saponification wastewater from the rare earth saponification section is used as a first stripping agent to be conveyed to a first stripping section and contacted with the washed extraction liquid to obtain a first stripping liquid and a first load organic phase;
the second back extraction section: performing second stripping on the first loaded organic phase by adopting a second stripping agent to obtain second stripping liquid and a second loaded organic phase; the second stripping agent is hydrochloric acid with the concentration of 4.5-7 mol/L;
wherein, the flow volume ratio of the organic phase to the rare earth saponification agent is 3.5-4.5:1; the volume flow ratio of the organic phase to the first stripping agent is 3.5-4.2:1;
the content of rare earth ions in the first stripping solution is less than or equal to 0.0005mol/L, and Zn in the second stripping solution 2+ Less than or equal to 0.1g/L; wherein, the content of rare earth ions is calculated by the corresponding rare earth oxide, zn 2+ The content of (2) is calculated as zinc oxide.
2. The method of claim 1, further comprising a water wash stage:
and (3) washing: washing the second loaded organic phase with water to obtain a blank organic phase; returning the blank organic phase to the saponification section for continuous use.
3. The process according to claim 1, wherein the flow volume ratio of the organic phase to the second stripping agent is from 10 to 30:1.
4. The method according to claim 2, wherein the volume ratio of the flow rates of water used in the organic phase and the water wash stage is 50-120:1.
5. The method of claim 1, wherein the organic phase comprises an extractant and a diluent, the extractant being selected from the group consisting of P 204 Or P 507 The diluent is kerosene, and the content of the extractant in the organic phase is 0.5-2.5 mol/L.
6. The method according to claim 1, wherein the concentration of ammonia used in the saponification section is 6 to 12mol/L.
7. The process of claim 1, wherein the rare earth saponification agent used in the rare earth saponification stage is a raffinate from the extraction stage.
8. The process of claim 1, wherein the washing liquid used in the washing stage is 2 to 4mol/L hydrochloric acid and the second stripping agent used in the second stripping stage is 5.5 to 6.5mol/L hydrochloric acid.
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