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CN1043156C - Rare earth electrolytic extracting process - Google Patents

Rare earth electrolytic extracting process Download PDF

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Publication number
CN1043156C
CN1043156C CN94100721A CN94100721A CN1043156C CN 1043156 C CN1043156 C CN 1043156C CN 94100721 A CN94100721 A CN 94100721A CN 94100721 A CN94100721 A CN 94100721A CN 1043156 C CN1043156 C CN 1043156C
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China
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electrolytic
rare earth
solution
extraction
earth
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CN1095111A (en
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孙都成
夏熙
鲁文杰
于媛
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Xinjiang University
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Xinjiang University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The present invention relates to an electrolytic rare earth (RE) extraction method by utilizing electrolytic conditions to extracting RE, which is realized through the following steps: A, the preparation of an RE liquor: RE salt is prepared into a water solution, and a strong electrolyte is added to the water solution to obtain the RE solution; B, an extraction agent: an acidic extraction agent is adopted; C, the RE solution obtained in the step A and the acidic extraction agent in the step B are poured in an electrolytic extraction reactor according to a volume ratio of 1: 1; D, an extractive reaction: the mixed solution is stirred and electrolyzed, the current density of electrolysis is larger than 1.5 A / dm<2>; E, separation: after the extractive reaction is thoroughly carried out, the solution is made to stand so as to be completely layered, the solution in layers is separated. Compared with a traditional extractive process, the present invention has the advantages of saponification step saving, production efficiency improvement, production cost reduction and notable comprehensive economic benefit.

Description

Rare earth electrolytic extracting process and electrolytic extraction reactor
The present invention relates to utilize electrolytic condition to carry out method of extraction and electrolytic extraction reactor, particularly a kind of rare earth electrolytic extracting process and electrolytic extraction reactor that utilizes electrolytic condition to carry out rare earth extraction.
At present, being usually used in rare earth element enrichment or isolating extraction agent is acidic extractant, but it is very big influenced by the aqueous phase acidity of extraction system, and the acidity of extraction system is big more, the rare earth content of extraction is more little, and this mainly is the reaction below existing in extraction process:
M 3+ + nHL = ML n + nH +
Rare earth ion extraction agent extract hydrogen ion can draw from following formula, carried out along with extracting, hydrogen ion concentration constantly increases, and extractive reaction is restricted, so extracted species generates and also is restricted, the maximum extraction amount that extraction agent can not reach by theoretical calculated value is saturated extraction.For the extracting rare-earth element that reaches capacity, during tradition acidic extractant extracting rare-earth element, the way that solves the influence of extraction system acidity is: after earlier extraction agent being carried out saponification, promptly with in the alkaline matters such as sodium hydroxide and the hydrogen ion of extraction agent, make extraction agent be transformed into corresponding salt, and then with the extraction agent extracting rare-earth element after the saponification, whole like this extraction system just there is not hydrogen ion to participate in, therefore, the acidity of extraction system can not change yet.
But the saponification process of acidic extractant must consume a large amount of industrial chemicals, and the industrial chemicals that is consumed be disposable consumption and can not reuse; And production process many one step of saponification, increased operation steps like this, make the production cycle elongated, therefore, traditional rare earth acid extract method production cycle is long, cost is high.
The objective of the invention is to overcome the deficiency of above-mentioned prior art and propose a kind of improved rare earth extraction method is rare earth electrolytic extracting process and electrolytic extraction reactor.
The objective of the invention is to realize by following steps:
A. earth solution preparation: the salt of rare earth is mixed with the aqueous solution, and the adding strong electrolyte obtains earth solution in this solution, the amount that contains strong electrolyte in its earth solution is greater than 1.0 moles/every liter, more preferably greater than 2.0 moles/every liter; Strong electrolyte is preferably sodium-chlor;
B. extraction agent: select acidic extractant for use;
C. be 1 to 1 to put in the electrolytic extraction reactor by volume with the earth solution of gained among the A and acidic extractant among the B;
D. extractive reaction: stir and electrolysis, electrolytic current density is greater than 1.5 amperes/every square decimeter, more preferably greater than 3.0 amperes/every square decimeter (A/dm 2);
E. separate: after treating that extractive reaction fully, staticly again each layer solution is separated after making the complete layering of solution.
Wherein, the salt of rare earth is chlorination single rare earth or chlorination mishmetal or nitric acid single rare earth or nitric acid mishmetal or their mixture; Acidic extractant is C for containing oxygen extraction agent or phosphorous, oxygen extraction agent or chelating extractant and contain the oxygen extraction agent 7To C 16Carboxylic-acid or the naphthenic acid or the isomeric acid of synthetic fatty acid, phosphorous, oxygen extraction agent is that di-(2-ethylhexyl)phosphoric acid (is P 204) or 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene (be P 507) or two (1-methylheptyl) phosphoric acid, chelating extractant is oxine or 2-methyl-oxine or methyl ethyl diketone or thenyltrifluoroacetone or hydroxyl oximes;
Electrolytic extraction reactor used in rare earth electrolytic extracting process comprises direct supply, positive electrode, negative electrode, extraction reactor, constructional feature is positive electrode and negative electrode are installed in the extraction reactor, and positive electricity very Graphite Electrodes or platinum electrode or titanium electrode; Negative electricity is Graphite Electrodes or platinum electrode or the ferroelectric utmost point or copper electrode very.
Accompanying drawing is a principle schematic of the present invention:
Coding in the accompanying drawing is respectively: 1 is direct supply, and 2 is positive electrode, and 3 is negative electrode, and 4 is extraction reactor, and 5 is whipping appts, and 6 is lead.
As shown in drawings, principle of the present invention is: be on the basis of extraction reactor 4, again at the traditional extraction device Adding a whole set of electrolysis unit is dc source 1, positive electrode 2 and negative electrode 3 etc., in the extractive reaction process by electrolysis Make the hydrogen ion that produces be electrolyzed to produce hydrogen and overflow, extraction equilibrium is carried out to the direction that generates extracted species, thus real Existing saturated extraction. Because extraction and electrolysis are carried out synchronously in whole extraction process, so this Rare Earth Electrolysis The extraction method is the extraction that reaches capacity in a step.
Below in conjunction with most preferred embodiment the present invention is described in further detail:
A. earth solution preparation: the salt (can be chlorination single rare earth or chlorination mishmetal or nitric acid single rare earth or nitric acid mishmetal or their mixture) of rare earth is mixed with the aqueous solution, and adding strong electrolyte sodium-chlor obtains earth solution in this solution, and the amount of sodium chloride-containing is greater than 2.0 moles/every liter in its earth solution;
B. extraction agent: the acidic extractant of selecting for use can be naphthenic acid or P 204Or P 507
C. be 1 to 1 to put in the electrolytic extraction reactor by volume with the earth solution of gained among the A and acidic extractant among the B;
D. extractive reaction: the whipping appts 5 that starts in the extraction reactor 4 stirs, and powers up for positive electrode 2 and negative electrode 3 and carry out electrolysis, and electrolytic current density is greater than 3.0 amperes/every square decimeter;
E. separate: after treating that extractive reaction fully, staticly again each layer solution is separated after making the complete layering of solution.
Wherein, the electrolytic extraction reactor is that positive electrode 2 and negative electrode 3 are installed in extraction reactor 4.And positive electrode 2 and negative electrode 3 are conducted by the positive pole and the negative pole of lead 6 with direct supply 1 respectively, as shown in drawings.
The present invention can be used for the analysis (as the acidic extractant extracting rare-earth time, the mensuration of saturated collection dosage) of the production of enrichment of rare earth elements or production of Chemicals (as the production of rare earth naphthenic acid siccative) or rare earth.
The present invention compares with traditional extraction technology, has saved saponification step, and it is ashamed not simplified behaviour, and economizes Removed the necessary industrial chemicals of saponification, and only needed one-time investment, installed at traditional extraction equipment Electrolysis unit namely can be used as the electrolytic extraction device and uses, and therefore, has improved production efficiency, has reduced production cost, Overall economic efficiency is remarkable.

Claims (8)

1. rare earth electrolytic extracting process that utilizes the electrolytic condition extracting rare-earth is characterized in that carrying out according to the following steps:
A. earth solution preparation: the salt of rare earth is mixed with the aqueous solution, and the adding strong electrolyte obtains earth solution in this solution, the amount that contains strong electrolyte in its earth solution is greater than 1.0 moles/every liter;
B. extraction agent: select acidic extractant for use;
C. the earth solution of gained among the A is put in the electrolytic extraction reactor than 1 for l by volume with the acidic extractant among the B;
D. extractive reaction: stir and electrolysis, electrolytic current density is greater than 1.5 amperes/every square decimeter;
E. separate: after treating that extractive reaction fully, staticly again each layer solution is separated after making the complete layering of solution.
2. rare earth electrolytic extracting process according to claim 1, the salt that it is characterized in that rare earth are chlorination single rare earth or chlorination mishmetal or nitric acid single rare earth or nitric acid mishmetal or their mixture.
3. rare earth electrolytic extracting process according to claim 1 is characterized in that strong electrolyte is a sodium-chlor.
4. rare earth electrolytic extracting process according to claim 1 is characterized in that acidic extractant is for containing oxygen extraction agent or phosphorous, oxygen extraction agent or chelating extractant.
5. rare earth electrolytic extracting process according to claim 4, it is characterized in that containing the oxygen extraction agent is C 7To C 16Carboxylic-acid or the naphthenic acid or the isomeric acid of synthetic fatty acid; Phosphorous, oxygen extraction agent is di-(2-ethylhexyl)phosphoric acid or 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene or two (1-methylheptyl) phosphoric acid: chelating extractant is that oxine or 2-methyl-oxine or methyl ethyl diketone or thiophene are expected formyl radical trifluoroacetone or hydroxyl oximes.
6. rare earth electrolytic extracting process according to claim 1 is characterized in that containing in the earth solution amount of strong electrolyte greater than 2.0 moles/every liter; Electrolytic current density is greater than 3.0 amperes/every square decimeter.
7. the electrolytic extraction reactor in the rare earth electrolytic extracting process according to claim 1 comprises that direct supply 1, positive electrode 2, negative electrode 3, extraction reactor 5. is characterized in that being equipped with in the extraction reactor 4 positive electrode 2 and negative electrode 3.
8. electrolytic extraction reactor according to claim 7 is characterized in that positive electrode 2 is Graphite Electrodes or platinum electrode or titanium electrode; Negative electrode 3 is Graphite Electrodes or platinum electrode or the ferroelectric utmost point or copper electrode.
CN94100721A 1994-01-21 1994-01-21 Rare earth electrolytic extracting process Expired - Fee Related CN1043156C (en)

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Application Number Priority Date Filing Date Title
CN94100721A CN1043156C (en) 1994-01-21 1994-01-21 Rare earth electrolytic extracting process

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Application Number Priority Date Filing Date Title
CN94100721A CN1043156C (en) 1994-01-21 1994-01-21 Rare earth electrolytic extracting process

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CN1095111A CN1095111A (en) 1994-11-16
CN1043156C true CN1043156C (en) 1999-04-28

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056194C (en) * 1995-08-01 2000-09-06 新疆大学 Method and apparatus for separating several metal chlorides by electrolysis and extraction

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1047346A (en) * 1990-07-09 1990-11-28 吉林省地质实验测试研究所 Cl-carrier chlorination process for extracting Au and silver
BR9202490A (en) * 1992-07-07 1994-02-01 Metalmax Produtos Quimicos E M HYDROMETALURGICAL PROCESS FOR THE PRODUCTION OF ELECTRIC ZINC

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1047346A (en) * 1990-07-09 1990-11-28 吉林省地质实验测试研究所 Cl-carrier chlorination process for extracting Au and silver
BR9202490A (en) * 1992-07-07 1994-02-01 Metalmax Produtos Quimicos E M HYDROMETALURGICAL PROCESS FOR THE PRODUCTION OF ELECTRIC ZINC

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