CN104603303A

CN104603303A - Processes for recovering rare earth elements and rare metals

Info

Publication number: CN104603303A
Application number: CN201380026281.1A
Authority: CN
Inventors: 理查德·鲍德劳尔特; 丹尼斯·普里茂; 海因茨·克里瓦奈克; 卡斯滕·迪特里奇; 玛丽-马克西姆·拉伯勒科库伊-吉尔伯特
Original assignee: Orbite Aluminae Inc
Current assignee: Orbite Technologies Inc
Priority date: 2012-03-19
Filing date: 2013-03-13
Publication date: 2015-05-06
Also published as: AU2013203668A1; RU2014141795A; JP2015516507A; WO2013138900A1; EP2828415A4; EP2828415A1; US20150104361A1; RU2595178C2

Abstract

There are provided processes for recovering at least one rare earth element. Such processes comprise obtaining an acidic composition comprising (i) at least one rare earth element and optionally at least one rare metal; and reacting the composition with a precipitating agent so as to substantially selectively precipitate a first rare earth element and optionally a first rare metal. For example, various rare earth elements (such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, etc) and various rare metals (such as indium, zirconium, lithium, gallium, etc.) can be extracted by using such processes.

Description

The method of recovering rare earth element and rare metal

The cross reference of related application

This application claims the US61/703 of the PCT/CA2012/000253 submitted on March 19th, 2012, the PCT/CA2012/000419 of submission on May 3rd, 2012, submission on September 19th, 2012, the right of priority of the US 61/705,807 that on September 26th, 219 and 2012 submits to.These files are incorporated herein by reference in their entirety.

Technical field

The disclosure relate to be applied to rare earth element (REE) and rare metal (RM) recovery, extraction and/or the improvement of chemical field that is separated.Such as, these class methods are used for obtaining rare earth element from various material and derivative thereof, this material and derivative thereof such as alumina-bearing material and derivative thereof, iron-bearing materials and derivative thereof, containing Zinc material and derivative, copper-bearing materials and derivative thereof, nickel-containing material and derivative thereof and titanium-containing materials and derivative thereof.

Background technology

In various technology, there is increasing demand to rare earth element.In some countries, carry out the work recovering the exploitation of rare earth element.In future, the supply of rare earth element quite can depend on the economic feasibility of extraction and production method and need the technological innovation of this kind of rare earth element.

Therefore, the replacement scheme of the existing solution that Extraction of rare earth element is provided is needed.

Summary of the invention

According to an aspect, provide the method reclaiming at least one rare earth element, the method comprises:

Obtain acidic composition, described acidic composition comprises (i) at least one rare earth element and optionally at least one rare metal; With

Said composition and precipitation agent are reacted, substantially optionally to precipitate the first rare earth element and optionally the first rare metal.

According to another aspect, provide the method reclaiming at least one rare earth element, the method comprises:

Obtain acidic composition, described acidic composition comprises (i) at least one rare earth element and optionally at least one rare metal and (ii) at least one metal ion;

Adopting extraction agent, ion exchange resin and/or by making said composition and reductive agent react, from this acidic composition, removing this at least one metal ion at least in part, obtain the composition of this at least one metal ion content reduction thus; And

The composition that this at least one metal ion content is reduced and precipitation agent react, with substantially optionally make the first rare earth element and optionally first rare metal precipitation.

Obtain acidic composition, described acidic composition comprises (i) at least one rare earth element and optionally at least one rare metal and (ii) at least one iron ion;

Adopting extraction agent, ion exchange resin and/or by making said composition and reductive agent react, from this acidic composition, removing this at least one iron ion at least in part, obtain the composition of this at least one iron ion content reduction thus; And

The composition that this at least one iron ion content is reduced and precipitation agent react, with substantially optionally make the first rare earth element and optionally first rare metal precipitation.

According to another aspect, provide the method reclaiming at least one rare earth element from least one material, the method comprises:

At least one acid is adopted to carry out lixiviate to this at least one material, to obtain the vat liquor comprising at least one metal ion and this at least one rare earth element;

From this vat liquor, substantially optionally precipitate, extract and/or be separated this at least one metal ion, and optionally obtain throw out; And

From this vat liquor and/or throw out, substantially optionally precipitate, extract and/or be separated this at least one rare earth element.

According to another aspect, provide the method from least one material extraction at least one rare earth element, the method comprises:

At least one acid is adopted to carry out lixiviate to this at least one material, to obtain the vat liquor comprising at least one metal ion and this at least one rare earth element; And

At least one being selected from this at least one rare earth element and this at least one metal ion is optionally precipitated.

According to an aspect, provide the method from least one salvage material at least one rare earth element, the method comprises:

At least one acid is adopted to carry out lixiviate to this at least one material, to obtain the vat liquor comprising at least one metal ion and at least one rare earth element;

Optionally substantially optionally precipitate, extract and/or be separated this at least one rare earth element from this vat liquor and/or throw out;

According to another embodiment, provide the method reclaiming at least one rare earth element from least one material, the method comprises:

Adopt at least one acid to carry out lixiviate to this at least one material, to obtain the vat liquor comprising at least one metal ion, this at least one rare earth element and solid, and vat liquor is separated with this solid;

From this vat liquor, substantially optionally remove at least one metal ion, and optionally obtain throw out; And

Substantially this at least one rare earth element is optionally removed from this vat liquor and/or throw out.

Adopt at least one acid to carry out lixiviate to this at least one material, to obtain the vat liquor comprising at least one metal ion and this at least one rare earth element and solid, and vat liquor is separated with this solid; And

At least one being selected from this at least one rare earth element and this at least one metal ion is substantially optionally removed from this vat liquor.

Accompanying drawing explanation

By means of only in the following drawings represented by example, each embodiment of the present disclosure:

Fig. 1 shows according to of the present disclosure for the preparation of aluminum oxide and the block diagram of an example of method of other products various comprising rare earth element;

Fig. 2 shows according to of the present disclosure for the preparation of aluminum oxide and the block diagram of another example of method of other products various comprising rare earth element;

Fig. 2 A with 2B shows the block diagram of the method similar to method shown in Fig. 2;

Fig. 3 shows the block diagram of another example according to the method for Extraction of rare earth element of the present disclosure;

Fig. 3 A shows the block diagram of the method similar to method shown in Fig. 3;

Fig. 4 A and 4B shows the block diagram of another example according to the method for Extraction of rare earth element of the present disclosure;

Fig. 4 C with 4D shows the block diagram of the method similar to method shown in Fig. 4 A with 4B;

Fig. 5 A, 5B, 5C and 5D show the block diagram of another example according to the method for Extraction of rare earth element of the present disclosure;

Fig. 5 E, 5F, 5G and 5H show the block diagram of the method similar with method shown in 5D to Fig. 5 A, 5B, 5C;

Fig. 6 to 11 represents the precipitation productive rate (%) of various rare earth element and the rare metal obtained during method according to the present invention;

Figure 12 to 25 shows the curve of the various results obtained when carrying out the extraction of compound during method according to the present invention; With

Figure 26 shows the block diagram of another example according to the method for Extraction of rare earth element of the present disclosure.

Embodiment

According to the description of each embodiment such as illustrated by example, other feature and advantage can become more apparent.

Find such as each stage with the disclosure in the method that describes can complete rare earth element and reclaim.Find in addition, even if only there is the rare earth element of trace, these class methods are also useful.Also find that these class methods are particularly useful to Extraction of rare earth element in the solution from abundant refining or purifying.Such as, these methods can be useful, because they can be suitable for the solution that several main ingredient has therefrom been removed.They also can be suitable for the solution before several main ingredient is removed.

As used herein, statement " at least one metal ion " such as refer to be selected from this metal the ion of the likely at least one type of form.Such as, when metal " M " can be M ²⁺or M ³⁺time, at least one metal ion for metal M can be M ²⁺or M ³⁺.Such as, metal can be selected from aluminium, iron, zinc, copper, nickel, magnesium, titanium etc.

As used herein, statement " at least one aluminum ion " such as refer to be selected from Al ion the aluminum ion of the likely at least one type of form.Such as, at least one aluminum ion can be Al ³⁺.

As used herein, statement " at least one iron ion " such as refer to be selected from Fe ion the iron ion of the likely at least one type of form.Such as, at least one iron ion can be Fe ²⁺, Fe ³⁺or its mixture.

As used herein, statement " at least one zine ion " such as refer to be selected from Zn ion the zine ion of the likely at least one type of form.Such as, at least one zine ion can be Zn ²⁺.

As used herein, statement " at least one cupric ion " such as refer to be selected from Cu ion the cupric ion of the likely at least one type of form.Such as, at least one cupric ion can be Cu ¹⁺, Cu ²⁺or its mixture.

As used herein, statement " at least one nickel ion " such as refer to be selected from Ni ion the nickel ion of the likely at least one type of form.Such as, at least one nickel ion can be Ni ²⁺, Ni ³⁺or its mixture.

As used herein, statement " at least one magnesium ion " such as refer to be selected from Mg ion the magnesium ion of the likely at least one type of form.Such as, at least one magnesium ion can be Mg ²⁺.

As used herein, statement " at least one titanium ion " such as refer to be selected from Ti ion the titanium ion of the likely at least one type of form.Such as, at least one titanium ion can be Ti ³⁺, Ti ⁴⁺or its mixture.

As used herein, statement " at least one rare earth element " such as refer to be selected from all rare earth elements that describes in the disclosure the rare earth element of the likely at least one type of form.

As used herein, statement " at least one rare metal " such as refer to be selected from all rare metals of describing in the disclosure the rare metal of the likely at least one type of form.

As used herein, statement " not containing the solution of Ga " such as refers to the solution comprising the gallium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Ce " such as refers to the solution comprising the cerium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Sc " such as refers to the solution comprising the scandium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Sm " such as refers to the solution comprising the samarium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Eu " such as refers to the solution comprising the europium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Gd " such as refers to the solution comprising the gadolinium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Y " such as refers to the solution comprising the yttrium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Pr " such as refers to the solution comprising the praseodymium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Nd " such as refers to the solution comprising the neodymium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of La " such as refers to the solution comprising the lanthanum being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Er " such as refers to the solution comprising the erbium being less than about 5%, 2% or 1%w/v.

As used herein, statement " not containing the solution of Dy " such as refers to the solution comprising the dysprosium being less than about 5%, 2% or 1%w/v.

As used herein, statement " rare earth element " such as refers to the rare elements being selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.Abbreviation " REE " can be used as the synonym of " rare earth element " in the disclosure.

As used herein, statement " rare metal " such as refers to the rare metal being selected from indium, zirconium, lithium and gallium.These rare metals can be various forms of, such as element form (or metallic forms), the forms such as halogenide (such as muriate), oxide compound, vitriol, oxalate, oxyhydroxide.Abbreviation " RM " can be used as the synonym of " rare metal " in the disclosure.

Term " REEO or REE-O " as used in the disclosure refers to rare earth oxide.

Term " RMO or RM-O " as used in the disclosure refers to rare metal oxide.

As used herein, the term of degree, such as " approximately " and " being similar to " represent modify the reasonable amount of the error of term, it does not make net result obviously change.The term of these degree should be interpreted as comprising at least ± 5% of modified term or the error of at least ± 10% when error can not negate the meaning of the word that it is modified.

In method of the present disclosure, after lixiviate, at least one component substantially optionally removed from vat liquor and be selected from least one rare earth element and at least one metal can be completed in every way.At least one metal ion (or second metal ion) can be removed, then can remove the first metal ion, finally can remove at least one rare earth element.Alternately, at least the first metal ion can be removed, then can remove the second metal ion, finally can remove at least one rare earth element.According to another example, at least one rare earth element can be removed, then can remove the first metal ion, finally can remove the second metal ion.In addition, at least one rare earth element can be removed, then can remove the second metal ion, finally can remove the first metal ion.Other possible combinations various can also be designed.

At least one acid for lixiviate at least one material can be HCl, H ₂sO ₄, HNO ₃or its mixture.Can use as a mixture or individually more than a kind of acid.The solution adopting these acid to make can be used with various concentration.Such as, strong solution can be used.Such as, the HCl of 6M or 12M can be used.Such as, the H up to 98% or 100%wt can be used ₂sO ₄.Such as, 18wt% or 32wt% can be used.

Such as, can be about 15 % by weight to about 45 % by weight with concentration, HCl between about 20 % by weight to about 45 % by weight, about 25 % by weight to about 45 % by weight, about 26 % by weight to about 42 % by weight, about 28 % by weight to about 40 % by weight, about 30 % by weight to about 38 % by weight or 25 % by weight and 36 % by weight carries out lixiviate at least one material.

Lixiviate can also be undertaken by being added in the aqueous solution by dry gas phase height concentrated acid (such as 85%, 90% or 95%).Alternately, lixiviate can also be undertaken by using weakly acid soln (such as <3wt%).

Such as, lixiviate can be the HCl of about 18wt% to 32wt% by working concentration in the first reactor, and the HCl being then about 90% to about 95% by working concentration in the second reactor carries out.

Such as, at least one material can carry out lixiviate at about 125 DEG C to about 225 DEG C, about 150 DEG C to about 200 DEG C, about 160 DEG C to about 180 DEG C or about 165 DEG C to the temperature of 170 DEG C.

Such as, lixiviate can be pressurizeed and be carried out.Such as, pressure can be about 100psig to about 300psig or about 150psig to about 200psig.Lixiviate can carry out about 30 minutes to about 5 hours.Such as, lixiviate can be carried out at the temperature of about 60 DEG C to about 200 DEG C.

Such as, lixiviate can be pressurizeed and be carried out in autoclave.Such as, it can carry out under 5KPag is to about 850KPag, 50KPag to about 800KPag, 100KPag to about 750KPag, 150KPag to about 700KPag, 200KPag pressure to about 600KPag or 250KPag to about 500KPag.

Such as, lixiviate can be carried out at the temperature of at least 80 DEG C, at least 90 DEG C or about 100 DEG C to about 110 DEG C.Under specific circumstances, it can carry out at higher temperatures, to improve the extraction efficiency of particular ore rare earth elements.Such as, lixiviate can be carried out at the temperature of at least 100 DEG C, at least 120 DEG C, at least 130 DEG C, at least 140 DEG C or about 140 DEG C to about 175 DEG C.

Such as, in vat liquor, at least one rare earth element can be ionic species.

Such as, after lixiviate, at least one rare earth element can be dissolved in solution, and finds that it can as the soluble ion associated with muriate, vitriol, nitrate or its hydrate etc.

Such as, after lixiviate, (if necessary) various alkali may be used for raising pH value, these alkali such as KOH, NaOH, Ca (OH) ₂, CaO, MgO, Mg (OH) ₂, CaCO ₃, Na ₂cO ₃, NaHCO ₃, CO ₂or its mixture.

Such as, at least one material can be selected from alumina-bearing material and derivative, iron-bearing materials and derivative thereof, containing Zinc material and derivative, copper-bearing materials and derivative thereof, nickel-containing material and derivative thereof, containing magnesium material and derivative thereof and titanium-containing materials and derivative thereof.

Such as, at least one alumina-bearing material can be at least one aluminous ore.

Such as, at least one iron-bearing materials can be at least one iron-stone.

Such as, at least one can be at least one zinc-containing ores containing Zinc material.

Such as, at least one copper-bearing materials can be at least one copper-containing ore.

Such as, at least one nickel-containing material can be at least one nickel-containing ore.

Such as, at least one can be at least one magnesium-containing ore containing magnesium material.

Such as, at least one titanium-containing materials can be at least one titaniferous ore.

Such as, at least one metal ion can comprise at least one aluminum ion, at least one zine ion, at least one cupric ion, at least one nickel ion, at least one magnesium ion, at least one titanium particle and/or at least one iron ion.

Such as, at least one metal ion can comprise the first metal ion and the second metal ion.

Such as, the first metal ion can comprise at least one aluminum ion, at least one zine ion, at least one cupric ion, at least one nickel ion, at least one titanium particle and/or at least one iron ion.

Such as, the second metal ion can comprise at least one aluminum ion, at least one zine ion, at least one cupric ion, at least one nickel ion, at least one titanium particle and/or at least one iron ion.

Such as, the first metal ion can be at least one aluminum ion.

Such as, the second metal ion can be at least one iron ion.

Such as, at least one metal ion can remove by making spent ion exchange resin or ion exchange system.Such as, this ion exchange resin can pass through wherein for the muriate of the muriate and rare metal that only allow rare earth element effectively, catches at least one metal ion simultaneously.

Such as, at least one precipitation of iron ions can be made.When making at least one precipitation of iron ions, it can adopt ion precipitation to precipitate, and it can precipitate with the form of various salt, oxyhydroxide, muriate or its hydrate.Such as, at least one iron ion can as FeCl ₂, FeCl ₃, Fe (OH) ₃, Fe (OH) ₂, rhombohedral iron ore, pyrrhosiderite (geotite), jarosite or its hydrate precipitate.

Such as, after the precipitation of at least one iron ion, at least one rare earth element can be dissolved in solution, and finds that it can as the soluble ion associated with oxyhydroxide or salt or its hydrate.

Such as, at least one aluminum ion can be made to precipitate.When making at least one aluminum ion precipitate, ion precipitation can be adopted to be precipitated, and it can precipitate with the form of various salt (such as muriate, vitriol), oxyhydroxide or its hydrate.Such as, at least one aluminum ion can as Al (OH) ₃, AlCl ₃6H ₂o, Al ₂(SO ₄) ₃or its hydrate precipitates.

Such as, after the precipitation of at least one metal ion, at least one rare earth element can be dissolved in solution, and finds that it can as the ion associated with oxyhydroxide or salt or its hydrate.

Such as, after the precipitation of at least one metal ion, remaining and at least one rare earth element can be covered residue soluble ion, such as Cl by fully purifying or refining solution ^-, SO ₄ ^2-, Na ⁺mixture in.

Method of the present disclosure can effectively for the treatment of various material.At least one material can be alumina-bearing material.Alumina-bearing material can be aluminous ore.Such as, clay, argillite, mud stone, beryl, sodium aluminum fluoride, garnet, spinel, bauxite or its mixture can be used as parent material.Alumina-bearing material can also be the industrial alumina-bearing material reclaimed, such as slag.Alumina-bearing material can also be red mud.

Method of the present disclosure can effectively for the treatment of various nickel-containing material.Such as, niccolite, kamacite, taenite, limonite, noumeite, laterite, pentlandite or its mixture can be used.

Method of the present disclosure can contain Zinc material for the treatment of various effectively.Such as, smithsonite, three oblique adamites (warikahnite), zink sulphide or its mixture can be used.

Method of the present disclosure can effectively for the treatment of various copper-bearing materials.Such as, the oxide compound ore of cupric can be used.Such as, chalcopyrite, copper glance, covellite, purple copper, tetrahedrite, malachite, copper lazur, ruby copper, chrysocolla or its mixture can also be used.

Method of the present disclosure can contain magnesium material for the treatment of various effectively.Such as, this class methods process serpentine can be passed through.In addition, this class methods process antigorite, the rejected material of chrysotile and lizardite and various magnesium and waste, such as industry or mine wastes and composition thereof can also be passed through.

Method of the present disclosure can effectively for the treatment of various titanium-containing materials.Such as, titanium ferrous manganese ore (ecandrewsite), geikielite, pyrophanite, ilmenite, rutile or its mixture can be used.

Such as, at least one rare earth element can be selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

Such as, at least one rare metal can be selected from indium, zirconium, lithium and gallium.

Such as, rare earth element can be divided into two classes sometimes, light rare earths (LRE) and heavy rare earth element (HRE).Light rare earths can comprise lanthanum, cerium, praseodymium, neodymium and samarium (ordination number 57 to 62), and they are usually abundanter than heavy rare earth element.

Such as, at least one rare elements can extract with the form of various salt, oxide compound, oxyhydroxide and hydrate thereof.

Such as, at least one rare earth element can be selected from scandium, gallium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium and composition thereof.

Such as, at least one rare earth element is selected from scandium, gallium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, dysprosium and composition thereof.

Such as, at least one rare earth element is selected from scandium, gallium, yttrium, cerium and composition thereof.

Such as, at least one rare earth element can be yttrium.

Such as, at least one rare earth element can be scandium.

Such as, at least one rare earth element can be gallium.

Such as, at least one rare earth element can be cerium.

Such as, the method can comprise:

Adopt HCl to carry out lixiviate at least one material, to obtain the vat liquor comprising at least one metal ion and this at least one rare earth element and solid, and vat liquor is separated with this solid;

From this vat liquor, substantially optionally remove at least one metal ion, thus obtain the composition comprising metal ion and this at least one rare earth element; And

From this vat liquor, substantially optionally remove at least one metal ion at least partly, thus obtain the solution comprising at least one rare earth element.

Such as, at least one metal ion optionally can be removed from vat liquor substantially by following steps: make it substantially optionally precipitate from vat liquor, and it removed from vat liquor by carrying out solid-liquid separation.

Such as, at least one metal ion optionally can be removed from vat liquor substantially by following steps: make it with AlCl ₃6H ₂the form of O optionally precipitates substantially, and it is removed from vat liquor by carrying out solid-liquid separation.

Such as, composition can comprise HCl, at least one metal ion and this at least one rare earth element.

Such as, composition can be the acidic composition comprising at least one metal ion and this at least one rare earth element.

Such as, acidic composition can comprise (i) at least one rare earth element and optionally at least one rare metal and (ii) FeCl ₃.

Such as, at least one iron ion optionally can be removed from composition substantially by following steps: be hydrolyzed that at least one iron ion is converted to Fe ₂o ₃, and from composition, the Fe of precipitation is removed by carrying out solid-liquid separation ₂o ₃, thus obtain the solution (liquor) comprising at least one rare earth element.

Such as, at the Fe removing precipitation ₂o ₃after, the recycling solution comprising at least one rare earth element being gone back, making for concentrated further in precipitation at least one aluminum ion for passing through.

Such as, at the Fe removing precipitation ₂o ₃after, the recycling solution comprising at least one rare earth element is gone back, for by with AlCl ₃6H ₂make for concentrated further in the form precipitation at least one aluminum ion of O.

Such as, at least one iron ion can be Fe ³⁺, its can from composition substantially optionally part remove, wherein, reductive agent can also be adopted to carry out treatment compositions, with by Fe ³⁺be converted to Fe ²⁺, then can remove FeCl by carrying out solid-liquid separation from composition ₂the Fe of form ²⁺, thus obtain the solution comprising at least one rare earth element.

Such as, at least one rare earth element can adopt liquid-liquid extraction substantially optionally to precipitate from solution, extract and/or be separated.

Such as, at least one rare earth element can adopt liquid-liquid extraction to extract from solution.

Such as, at least one rare earth element can adopt liquid-liquid extraction to reclaim from solution.

Such as, at least one extraction agent can be selected from two-(2-ethylhexyl) phosphoric acid (HDEHP), single (2-ethylhexyl) 2-ethylhexyl phosphonic acid ester (HEH/EHP), two (2, 4, 4-tri-methyl-amyl) hypophosphorous acid, octylphenylphosphoric acid ester (OPAP), 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester (PC88A) and optionally toluene, Tributyl phosphate ester, two-isopentyl methylphosphonate, 7-(4-ethyl-1-Methyl Octyl)-oxine, two-(2-ethylhexyl) phospho acid, two (2, 4, 4-tri-methyl-amyl) phospho acid, oxine and (2-ethylhexyl) phosphonic acids and composition thereof.

Such as, at least one extraction agent can be two-(2-ethylhexyl) phosphoric acid.

Such as, at least one extraction agent can be 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester.

Such as, at least one extraction agent can be octylphenylphosphoric acid ester.

Such as, at least one extraction agent can be Tributyl phosphate ester.

Such as, at least one extraction agent can be selected from DTPA (DTPA), ethylenediamine tetraacetic acid (EDTA) (EDTA), 1,4,7,10-tetraazacyclododecanand-Isosorbide-5-Nitrae, 7,10-tetraacethyl (DOTA), two (2,4,4-tri-methyl-amyl) hypophosphorous acid and composition thereof.

According to an example, when substantially optionally precipitate from vat liquor and/or throw out, extract and/or separating at least one rare earth element time, discovery can be made to precipitate as at least one rare earth element of ion.

Such as, scandium can with Sc (OH) ₃, ScCl ₃, ScF ₃and/or [ScF ₆] ^3-the form of (positively charged ion) precipitates, and wherein said positively charged ion can be sodium, potassium, magnesium, calcium etc.

Scandium can about 7 to about 9 or about 7 to about 8 pH value under precipitate.

Such as, lixiviate can be carried out under about 0.5 pH value to about 2.5, about 0.5 to about 1.5 or about 1; Then the second metal ion can precipitate under at least about the pH value of 9.5,10,10.5,11 or 11.5; Then the first metal ion can precipitate under the pH value of about 8 to about 9.

Such as, the second metal ion can precipitate to about 11.5, about 10.8 to about 11.2, about 11.5 about 10 to about 12.5,10.5 to about 12.5 or pH value between 10 and 11.

Such as, the first metal ion precipitation can about 7 to about 11, about 8 to about 10.5, about 8.8 to about 10 or about 9 to about 10 pH value under carry out.

Such as, the second metal ion precipitation can about 3 to about 6, about 3.0 to about 5.5, about 3 to about 5, about 3 to about 4, about 3.0 to about 3.5, about 3.5 to about 4.0, about 4.0 to about 5.0, about 4.0 to about 4.5 or about 4.5 to about 5.0 pH value under carry out.

Such as, the first metal ion precipitation can about 5 to about 6, about 5.0 to about 5.5 or about 5.5 to about 6.0 pH value under carry out.

Such as, as precipitate A lCl ₃time, make the highly enriched dry gas HCl of about 90% to about 98% form bubble and enter in the composition comprising at least one iron ion, at least one aluminum ion and at least one rare earth element.

Such as, when carrying out the hydrolysis of at least one iron ion so that at least one iron ion is converted to Fe ₂o ₃and remove Fe ₂o ₃time, during hydrolysis, pH value can be less than about greatly 2.5,2.0,1.5 or 1.0.

According to another example, solution can comprise at least one rare earth element of chloride form, solution and extraction agent wherein can be made to react substantially optionally therefrom extract gallium, thus obtain not containing the solution of Ga and the Gallium solution of extraction, and make solution separated from one another.Such as, the gallium in solution can be GaCl ₃form.Such as, this extraction agent can be octylphenylphosphoric acid ester, 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester and toluene, Tributyl phosphate ester or its mixture.Such as, the GaCl of extraction ₃then can precipitate, then be converted to Ga ₂o ₃.Ga ₂o ₃can by plasma torch process further for higher than 99.5% purifying.

Such as, then can make react substantially optionally therefrom extract cerium containing solution and the another kind of extraction agent of Ga, thus acquisition does not contain the solution of Ce and the cerium solution of extraction, and make solution separated from one another.Such as, the cerium do not contained in the solution of Ga can be CeCl ₃form.Such as, this another kind of extraction agent can be Tributyl phosphate ester, diisoamyl methylphosphonate, two-(2-ethylhexyl) phosphonic acids, 7-(4-Methyl Octyl)-oxine or its mixture.Such as, the method can also comprise the cerium of extraction is converted to Ce ₂o ₃.Such as, the cerium of extraction can be calcined as Ce ₂o ₃.If the cerium extracted is chloride form, then can reclaim (or regeneration) HCl from this calcining process.Such as, can with its azeotrope concentration regeneration HCl.

Such as, the method can also comprise to be made react substantially optionally therefrom extract scandium containing solution and the other extraction agent of Ce, thus acquisition does not contain the solution of Sc and the scandium solution of extraction, and makes solution separated from one another.Such as, the scandium do not contained in the solution of Ce can be ScCl ₃form.Such as, this other extraction agent can be two-(2-ethylhexyl) phosphoric acid, two-(2-ethylhexyl) phospho acid or its mixture.Such as, the method can also comprise the scandium of extraction is converted to Sc ₂o ₃.Such as, the scandium of extraction can be converted to Sc by means of NaOH ₂o ₃.The scandium extracted can be calcined to obtain Sc ₂o ₃.If the scandium extracted is chloride form, then can reclaim (or regeneration) HCl from this calcining process.Such as, can with its azeotrope concentration regeneration HCl.

Such as, the method can also comprise to be made not react substantially optionally extract samarium, europium or its mixture containing the solution of Sc and another extraction agent, thus obtain containing the solution of Sm and/or containing the solution of Eu and the samarium solution of extraction and/or europium solution, and make solution separated from one another.Such as, this another extraction agent can be selected from two (2,4,4-tri-methyl-amyl) phospho acid, two-(2-ethylhexyl) phosphoric acid and composition thereof.

Such as, the method can also comprise make not containing Sm solution and/or react substantially optionally extract gadolinium containing solution and another extraction agent of Eu, thus acquisition does not contain the solution of Gd and the gadolinium solution of extraction, and makes solution separated from one another.Such as, this another extraction agent can be oxine.

Such as, the method can also comprise to be made react substantially optionally extract yttrium containing solution and another extraction agent of Gd, thus acquisition does not contain the solution of Y and the yttrium solution of extraction, and makes solution separated from one another.Such as, this another extraction agent can be (2-ethylhexyl) phosphoric acid, two-(2-ethylhexyl) phosphoric acid or its mixture.

Such as, the method can also comprise to be made not react substantially optionally extract dysprosium and/or erbium containing the solution of Y and another extraction agent, thus obtain containing the solution of Dy and/or containing the solution of Er and the dysprosium solution of extraction and/or erbium solution, and make solution separated from one another.

According to another example, solution and the first extraction agent can be made to react substantially optionally therefrom extract gallium, thus obtain not containing the solution of Ga and the Gallium solution of extraction, and make solution separated from one another.

Such as, the gallium in solution can be GaCl ₃form.Such as, the first extraction agent can be the Tributyl phosphate ester optionally in kerosene.

Such as, can make react containing solution and the precipitation agent of Ga, for precipitating at least one rare earth element not containing and exist in the solution of Ga, thus acquisition comprises the throw out of this at least one rare earth element and reclaims this throw out by solid-liquid separation.

Such as, the method can also comprise adopt at least one acid lixiviate is carried out to this throw out, to obtain the extracting solution comprising this at least one rare earth element.Such as, this acid can be HCl.Such as, this extracting solution and the second extraction agent can be made to react, substantially optionally to extract the first group rare-earth element, thus acquisition comprises the solution of the first group rare-earth element of extraction and comprises the raffinate of the second group rare-earth element, and solution is separated with raffinate.Such as, first group can comprise yttrium and scandium.Such as, second group can comprise cerium, neodymium, europium and praseodymium.Such as, the second extraction agent can be selected from two-(2-ethylhexyl) phosphoric acid and di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester.

Such as, the method can also comprise the solution of the first group rare-earth element making to comprise extraction and HCl reacts at least one times, therefrom to remove impurity.Such as, HCl can be azeotrope concentration, or it can be very high density, such as 95wt%.

Such as, the method can also comprise adopt at least one acid the solution of the first group rare-earth element comprising extraction is stripped, to obtain first group of strip liquor.Such as, this at least one acid can be HCl.

Such as, the method can also comprise employing second extraction agent repeat extract at least one times.

Such as, first group of strip liquor and the 3rd extraction agent can be made to react with at least one substantially optionally extracted from first group of strip liquor in scandium, erbium and dysprosium, thus obtain solution and the yttrium raffinate of at least one in scandium, erbium and the dysprosium comprising extraction, and solution is separated with raffinate.Such as, the 3rd extraction agent can be Tributyl phosphate ester.

Such as, the method can also comprise and adopts the solution of at least one acid at least one comprised in the scandium of extraction, erbium and dysprosium to strip, to obtain another first group of strip liquor.Such as, this at least one acid can be HCl.

Such as, another first group of strip liquor and the 4th extraction agent can be made to react substantially optionally from another first group of strip liquor, extract erbium and dysprosium, thus obtain and comprise the erbium of extraction and the solution of dysprosium and scandium raffinate, and solution is separated with raffinate.

Such as, another first group of strip liquor and the 4th extraction agent can be made to react substantially optionally from another first group of strip liquor, extract scandium, thus acquisition comprises the solution of the scandium of extraction and comprises the raffinate of erbium and dysprosium, and solution is separated with raffinate.

Such as, this at least one rare earth element substantially optionally can precipitate, extract and/or be separated by absorption on the gac optionally adopting Tributyl phosphate ester modified or in the upper absorption of polyurethane polyethers foam (PUF).

Such as, this at least one rare earth element can optionally adopt liquid-liquid extraction to remove substantially.Such as, can extract by using extraction agent to carry out liquid-liquid.

Such as, the method can also comprise at least two kinds of compositions optionally precipitating at least one rare earth element, the second metal ion and the first metal ion that are selected from ionic species.Such as, each in this composition can precipitate separately or coprecipitation.

According to another example, the method can comprise:

Adopt HCl to carry out lixiviate at least one material, to obtain the vat liquor comprising the first metal ion, the second metal ion and this at least one rare earth element and solid, and vat liquor is separated with this solid;

From this vat liquor, substantially optionally remove the second metal ion, thus obtain the composition comprising the first metal ion and this at least one rare earth element; With

From this vat liquor, substantially optionally remove the first metal ion at least partly, thus obtain the solution comprising this at least one rare earth element.

According to another example, the method can comprise:

According to an example, lixiviate can be carried out in the pH value of about 0.5 to about 2.5, then the second metal ion can precipitate in the pH value at least about 9.5, and then the first metal ion can the pH value in about 8 to about 9 precipitate, and then at least one scandium ion can the pH value in about 7 to about 8 precipitate.

According to an example, lixiviate can be carried out in the pH value of about 0.5 to about 1.5, then the second metal ion can precipitate in the pH value at least about 10.5, and then the first metal ion can the pH value in about 8 to about 9 precipitate, and then at least one scandium ion can the pH value in about 7 to about 8 precipitate.

According to an example, lixiviate can be carried out in the pH value of about 0.5 to about 1.5, then the second metal ion can precipitate in the pH value at least about 11, and then the first metal ion can the pH value in about 8 to about 9 precipitate, and then at least one scandium ion can the pH value in about 7 to about 8 precipitate.

Such as, scandium can precipitate from the by product generated during the method.

Such as, scandium can precipitate from the solution generated during the method.Such as, scandium can use HNO ₃precipitate.

Such as, this at least one rare earth element can by being selected from ion exchange resin, adopting solvent substantially optionally to precipitate with at least one technology of the extraction of absorption, extract and/or be separated.

Such as, this at least one rare earth element can adopt ion exchange resin substantially optionally to precipitate from solution, extract and/or be separated.

Such as, this at least one rare earth element can adopt liquid-liquid extraction substantially optionally to precipitate, extract and/or be separated.

Such as, this at least one rare earth element can adopt strike substantially optionally to precipitate, extract and/or be separated.

According to another example, lixiviate can be carried out in the pH value of about 0.5 to about 2.5, then the second metal ion can precipitate in the pH value at least about 9.5, and then the first metal ion can the pH value in about 8 to about 9 precipitate, and then this at least one rare earth element can optionally extract substantially.

According to another example, lixiviate can be carried out in the pH value of about 0.5 to about 1.5, then the second metal ion can precipitate in the pH value at least about 10.5, and then the first metal ion can the pH value in about 8 to about 9 precipitate, and then this at least one rare earth element can optionally extract substantially.

According to another example, lixiviate can be carried out in the pH value of about 0.5 to about 1.5, then the second metal ion can precipitate in the pH value at least about 11, and then the first metal ion can the pH value in about 8 to about 9 precipitate, and then this at least one rare earth element can optionally extract substantially.

Such as, the ratio of at least one material/acid by volume weighing scale can be about 1/10.

According to another example, the method can also comprise following at least one:

From vat liquor, the second metal ion is removed at least in part by making the second metal ion and extraction agent complexing fully;

Optionally precipitate the second metal ion;

Optionally precipitate the first metal ion; With

From vat liquor, the first metal ion is removed at least in part by making the first metal ion and another kind of extraction agent complexing fully.

According to another example, the method comprises:

Adopt HCl to carry out lixiviate at least one material, to obtain the vat liquor comprising the first metal ion and the second metal ion and solid residue, and vat liquor is separated with this solid residue;

Substantially optionally precipitate the second metal ion by making vat liquor and alkali reaction and remove the second metal ion at least in part from vat liquor, be rich in the first metal ion and the waterborne compositions and the throw out that comprise this at least one rare elements to obtain, and from said composition, remove this throw out;

Carry out this waterborne compositions of purifying by substantially optionally precipitating the first metal ion, thus obtain another composition and another throw out of comprising this at least one rare elements, and from said composition, remove this throw out; And

Substantially this at least one rare elements is optionally extracted from this another composition.

According to another example, the method can comprise:

Adopt HCl to carry out lixiviate to obtain the vat liquor and the solid residue that comprise the first metal ion and the second metal ion to this at least one material, and this vat liquor be separated with this solid residue,

By removing the second metal ion by making vat liquor and substantially optionally precipitating the second metal ion with alkali reaction at least in part from vat liquor, be rich in the first metal ion and the waterborne compositions and the throw out that comprise this at least one rare elements to obtain, and from said composition, remove this throw out;

Adopt hollow-fibre membrane or extracted by liquid-liquid and substantially optionally extract the first metal ion from this waterborne compositions, and remove the first metal ion extracted, thus it is poor and comprise the waterborne compositions of this at least one rare elements to obtain the first metal ion; And

Substantially this at least one rare elements is optionally extracted from this waterborne compositions.

According to another example, the method can comprise:

Adopt HCl to carry out lixiviate to obtain the vat liquor and the solid residue that comprise the first metal ion and the second metal ion to this at least one material, and this vat liquor is separated with this solid residue;

By substantially optionally making the second metal ion and extraction agent complexing remove the second metal ion at least in part from vat liquor, be rich in the first metal ion and the waterborne compositions comprising this at least one rare earth element to obtain;

Carry out this waterborne compositions of purifying by substantially optionally precipitating the first metal ion, thus obtain another composition and another throw out of comprising this at least one rare elements, from said composition, remove this throw out; And

According to another example, the method can comprise:

Adopt hollow-fibre membrane or extracted by liquid-liquid and substantially optionally extract the first metal ion from this waterborne compositions, and remove the first metal ion extracted, thus it is poor and comprise the waterborne compositions of this at least one rare elements to obtain the first metal ion; With

Substantially this at least one rare elements is optionally extracted from this waterborne compositions that the first metal ion is poor.

According to another example, the method can comprise:

From vat liquor, the first metal ion is removed at least in part by substantially optionally precipitating the first metal ion, be rich in the second metal ion and the waterborne compositions and the throw out that comprise this at least one rare elements to obtain, and from said composition, remove this throw out;

From this waterborne compositions being rich in the second metal ion, substantially optionally precipitate the second metal ion, and therefrom remove throw out, thus it is poor and comprise the waterborne compositions of this at least one rare elements to obtain the second metal ion; And

Substantially this at least one rare elements is optionally extracted from this waterborne compositions that the second metal ion is poor.

Such as, the first metal ion can comprise at least one aluminum ion.

Such as, the second metal ion can comprise at least one iron ion.

Such as, this at least one aluminum ion can in a crystallizer with AlCl ₃6H ₂the form precipitation of O, such as, by using gas HCl bubbling.

Such as, this at least one aluminum ion can in a crystallizer with AlCl ₃6H ₂the form precipitation of O, such as, by adding the HCl that concentration is about 26wt% to about 32wt%.

Such as, this at least one iron ion can such as by being hydrolyzed with Fe ₂o ₃form precipitation.

Such as, the waterborne compositions being rich in the first metal ion can carry out purifying by following steps: make the first metal ion and extraction agent complexing to obtain complex compound, complex compound is separated with composition, and precipitates the first metal ion.

Such as, the waterborne compositions being rich in the first metal ion can carry out purifying by following steps: make to be rich in the impurity and extraction agent complexing that comprise in the waterborne compositions of the first metal ion, from composition, remove the impurity of complexing at least in part, and precipitate the first metal ion.

Such as, the rare earth element obtained by method of the present disclosure and rare metal can be further purified by using plasma torch.Such as, once be separated, rare earth element and rare metal just can be injected in plasma torch to be further purified individually.The example of this kind of optional purification step can be seen in Fig. 4 C, 4D, 5F, 5G and 5H.

Such as, acidic composition of the present disclosure can adopt ion exchange resin to process before the extraction of at least one rare earth element and/or at least one rare metal.Such as, this kind of step can be seen in Fig. 3 A, 4C, 5E and 5F.

Such as, this acidic composition and Fe (0) can be made to react, thus obtain Fe ³⁺the composition that content reduces.

Such as, the first rare earth element can be scandium.

Such as, this acidic composition can comprise at least one rare metal.

Such as, the method can comprise composition that this at least one iron ion content is reduced and precipitation agent reacts, substantially optionally to precipitate the first rare earth element and the first rare metal.

Such as, the first rare metal can be gallium.

Such as, this precipitation agent can be selected from oxalic acid, NaOH, MgO, CaCO ₃and composition thereof.

Such as, this precipitation agent can be CaCO ₃.

Such as, come substantially optionally to precipitate the first rare earth element and optionally the first rare metal by maintaining lower than the pH value of 2 or the pH value of about 1 to about 2.

Such as, come substantially optionally to precipitate the first rare earth element and optionally the first rare metal by maintaining the redox-potential of about+380mV.

Such as, the method can comprise composition that at least one iron ion content is reduced and precipitation agent and react substantially optionally precipitate the first rare earth element in the throw out that is included in and formed thus and the first rare metal, and reclaims this throw out.

Such as, the method can also comprise and carries out lixiviate to this throw out and obtain extracting solution.

Such as, HCl can be adopted to carry out lixiviate to this throw out.

Such as, HCl can have the concentration of about 5mol/L to about 15mol/L.

Such as, extraction agent can be adopted to extract further extracting solution, substantially optionally to extract the first rare earth element and the first rare metal, and obtain load organic phases.

Such as, this extraction agent can be the Tributyl phosphate ester in the Tributyl phosphate ester in Tributyl phosphate ester, kerosene or the kerosene under the existence of isodecyl alcohol.

Such as, the method can also comprise employing washing soln and wash this load organic phases, with the organic phase reclaiming the first rare earth element and obtain through washing.

Such as, this washing soln can be comprise the acidic aqueous solution that concentration is the HCl of about 2mol/L to about 12mol/L.

Such as, can with the washing soln of about 1:1: the ratio of load organic phases uses this washing soln.

Such as, the method can also comprise adopt stripping solution to this through washing organic phase strip, to reclaim the first rare metal.

Such as, this stripping solution can be water.

Such as, can with the stripping solution of about 1:2: the ratio of load organic phases uses this stripping solution.

Such as, the composition that at least one iron ion content can be made to reduce and precipitation agent react, comprise the liquid of the other rare earth element of at least one to obtain and comprise the throw out of the first rare earth element and the first rare metal, the method also comprises makes this liquid be separated with this throw out.

Such as, the method can also comprise makes this liquid and another precipitation agent react to obtain another throw out, and reclaims this another throw out.

Such as, this liquid and another precipitation agent can be reacted in the pH value of about 7.8 to about 8.2 or about 7.9 to about 8.1.

Such as, at about+340mV or about+380mV, this liquid and another precipitation agent can be reacted by maintaining redox-potential.

Such as, this liquid and another precipitation agent can be reacted by the temperature maintaining about 50 DEG C to about 70 DEG C.

Such as, this another precipitation agent can be selected from oxalic acid, NaOH, MgO, CaCO ₃and composition thereof.

Such as, this another precipitation agent can be CaCO ₃.

Such as, the method can also comprise and carries out lixiviate and obtain comprising the extracting solution of the second rare earth element to this another throw out.

Such as, HCl can be adopted to carry out lixiviate to this another throw out.

Such as, extraction agent can be adopted to extract the extracting solution comprising the second rare earth element, comprise the load organic phases of the second rare earth element substantially optionally to extract the second rare earth element and to obtain and comprise the aqueous phase of at least one light rare earths.

Such as, this extraction agent is two (ethylhexyl) phosphonic acids in two (ethylhexyl) phosphonic acids or kerosene.

Such as, the method can also comprise remove the 3rd rare earth element at least in part from the load organic phases comprising the second rare earth element.

Such as, the method can also comprise by adopting acidic cleaning solution-treated load organic phases to remove the 3rd rare earth element at least in part from the load organic phases comprising the second rare earth element.Such as, this washing soln can comprise the HCl of 1N.

Such as, the 3rd rare earth element can be cerium.

Such as, the method can also comprise adopt acidic strip to get load organic phases that solution-treated comprises the second rare earth element to obtain the strip liquor comprising the second rare earth element, and reclaims this strip liquor.Such as, this strip liquor can comprise the HCl of 3.5N.

Such as, the method can comprise and adopts extraction agent pack processing containing the strip liquor of the second rare earth element substantially optionally to extract the 4th rare earth element and optionally the 5th rare earth element from this strip liquor, and acquisition comprises the raffinate of the second rare earth element.Such as, this extraction agent can be Tributyl phosphate ester or the Tributyl phosphate ester in kerosene.

Such as, the 4th rare earth element can be dysprosium.

Such as, the 5th rare earth element can be erbium.

Such as, the method can also comprise and makes to comprise the 4th rare earth element and optionally the organic phase of the 5th rare earth element and stripping solution react, to obtain the strip liquor comprising the 5th rare earth element and optionally the 5th rare earth element.Such as, this stripping solution can be water.

Such as, the second rare earth element is yttrium.

Such as, extraction agent can be adopted to extract the vat liquor comprising the second rare earth element, comprise the load organic phases of the second rare earth element substantially optionally to extract the second rare earth element and to obtain and comprise the raffinate of at least one light rare earths.Such as, this extraction agent can be two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

Such as, the method can also comprise by adopting acidic cleaning solution-treated load organic phases to remove the 3rd rare earth element at least in part from the load organic phases comprising the second rare earth element.Such as, this washing soln comprises the HCl of about 1N to about 2N.

Such as, the method can also comprise the strip liquor adopting stripping solution pack processing to comprise the second rare earth element with acquisition containing the load organic phases of the second rare earth element.This stripping solution can comprise the HCl of about 3M to about 4M.

Such as, extraction agent can be adopted to extract to remove the 4th rare earth element and optionally the 5th rare earth element to the strip liquor comprising the second rare earth element, thus obtain the raffinate that comprises the second rare earth element and comprise the load organic phases of the 4th rare earth element and optionally the 5th rare earth element.Such as, this extraction agent is Tributyl phosphate ester or the Tributyl phosphate ester in kerosene.

Such as, the method can comprise the raffinate reclaiming and comprise the second rare earth element.

Such as, the second rare earth element can be yttrium.

Such as, the 4th rare earth element can be dysprosium.

Such as, the 5th rare earth element can be erbium.

Such as, the method can also comprise the load organic phases that makes to comprise the 4th rare earth element and the 5th rare earth element and stripping solution reacts, to obtain the strip liquor comprising the 4th rare earth element and the 5th rare earth element.Such as, this stripping solution can be water.

Such as, the method can also comprise makes strip liquor and extraction agent react substantially optionally extract the 5th rare earth element from this strip liquor, thus acquisition comprises the raffinate of the 4th rare earth element and comprises the load organic phases of the 5th rare earth element.Such as, this extraction agent can be two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

Such as, the method can also comprise makes raffinate be separated with the load organic phases comprising the 5th rare earth element, adopt this load organic phases of washing soln process therefrom to remove impurity, then adopt this load organic phases of stripping solution process to obtain the strip liquor comprising the 5th rare earth element.Such as, this washing soln can comprise the HCl of about 2M to about 4M.

Such as, this raffinate and oxidant reaction can be made to be oxidized the 3rd rare earth element.Such as, this oxygenant can be clorox.Such as, this raffinate and oxidant reaction can be made in the pH value of about 0.5 to about 1.5.

Such as, the method can also comprise the 3rd rare earth element through oxidation removing precipitated form from this raffinate, thus obtains the filtrate comprising the 6th rare earth element.

Such as, the method can also comprise makes this filtrate and extraction agent react substantially optionally extract the 6th rare earth element from this filtrate, thus acquisition comprises the load organic phases of the 6th rare earth element and comprises another raffinate of the 7th rare earth element and the 8th rare earth element, and the load organic phases comprising the 6th rare earth element is separated with this raffinate.Such as, this extraction agent can be two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

Such as, the method can also comprise employing washing soln process load organic phases therefrom to remove impurity, then adopts this load organic phases of stripping solution process to obtain the strip liquor comprising the 6th rare earth element.Such as, this washing soln can comprise the HCl of about 0.5M to about 1.5M.Such as, this stripping solution can comprise the HCl of about 2M to about 3M.

Such as, the 6th rare earth element can be erbium.

Such as, the 7th rare earth element can be praseodymium.

Such as, the 8th rare earth element can be neodymium.

Such as, the method can also comprise and adopts reductive agent to reduce the 6th rare earth element.Such as, this reductive agent can be zinc (0).

Such as, the method can also comprise makes the 6th rare earth element and sodium sulfate react its sulfate-derivatives to obtain precipitated form, and reclaims this throw out.

Such as, the method can also comprise the raffinate that makes to comprise the 7th rare earth element and the 8th rare earth element and extraction agent reacts, substantially optionally to extract the 8th rare earth element from this raffinate, thus acquisition comprises the load organic phases of the 8th rare earth element and comprises the raffinate of the 7th rare earth element, and the load organic phases comprising the 8th rare earth element is separated from this raffinate.Such as, this extraction agent can be two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

Such as, the method can also comprise employing washing soln process load organic phases therefrom to remove impurity, then adopts this load organic phases of stripping solution process to obtain the strip liquor comprising the 8th rare earth element.Such as, this washing soln can comprise the HCl of about 2M to about 3M.Such as, this stripping solution can comprise the HCl of about 3M to about 4M.

Such as, the method can also comprise employing ion exchange resin pre-treatment or process acidic composition to remove impurity.

Such as, the method can also be included in and from acidic composition, extract at least one rare earth element and optionally before at least one rare metal, adopt this acidic composition of ion exchange resin treatment, therefrom to remove impurity at least in part.

Such as, the method can also comprise using plasma torch to process at least one rare earth element that extracted by the method and optionally at least one rare metal, to be further purified at least one rare earth element and optionally at least one rare metal.

According to another example, the method can comprise:

1-adopts at least one acid (solution of such as HCl or gas HCl) to carry out lixiviate (such as about 0.5 to about 1.5 or the pH of about 0.8 to about 1.2) to argillite.This lixiviate can also be pressurizeed and be carried out;

The ion precipitation that pH value raises as about 10 to about 12 or about 11 to about 12 by adopting by 2-(or adopting extraction agent to extract it) is made a return journey deironing, and filters out all insoluble oxyhydroxide;

3-about 7.5 to about 9.0 or the pH value precipitation of aluminium of about 7.8 to about 8.2, and leaches the aluminium of solid form;

4-optionally uses liquid-liquid extraction, film and at least one be suitable in the aluminum ions extraction agent of complexing to carry out purifying (Al (OH) ₃); With

5-can carry out precipitating, extracting and/or separating at least one rare earth element after at least one in step 1,2,3 and 4.

For more details and the explanation of at least some part about step 1 to 4, can with reference to WO2008141423, it is incorporated herein by reference in their entirety.

According to another example, the method can comprise:

1-adopts acid (the HCl solution of such as 18wt% to 32wt%) to carry out lixiviate to argillite.This lixiviate can also be pressurizeed and be carried out, such as about 4 little of about 7 hours under the pressure of about 350KPag to about 500KPag.

According to another example as shown in Figure 1, the method can relate to following steps (Reference numeral in Fig. 1 corresponds to following steps):

The median size of alumina-bearing material is reduced to about 50 μm to about 80 μm by 1-.

2-adopts spirit of salt process to reduce and the material of classifying, and spirit of salt makes it possible to dissolved aluminum and other elements under predetermined temperature and pressure, as iron, magnesium and other metals comprising rare earth.Silicon-dioxide (with optionally titanium) keeps not dissolving completely.

Then, the mother liquor experience from lixiviate step is separated 3-, cleaning stage is separated with the metal chloride in solution to make pure silicon-dioxide.Then, pure silicon-dioxide can experience the extra leaching stages of a work two (such as the temperature of about 150 DEG C to about 160 DEG C) to bring up to the purity of silicon-dioxide higher than 99.9%.Can by using HCl and MgCl ₂the lixiviate carried out as leaching agent composition makes the TiO comprised in silicon-dioxide ₂be separated with silicon-dioxide.

Then 4-, adopts dry highly enriched gas chlorination hydrogen by being passed in crystallizer, spent acid (filtrate) concentration to be raised.This causes Aluminium chloride hexahydrate (throw out) and other minimum impurity crystallizations.According to the concentration of the iron(ic) chloride in this stage, other crystallisation step may be needed.Then throw out and liquid separation is made.

5-then high-temperature calcination Aluminium chloride hexahydrate (such as adopting rotary kiln, fluidized-bed etc.) to obtain required aluminum oxide.Then, reclaim highly enriched gas chlorination hydrogen, make excessive portion reach possible maximum concentration in form of an aqueous solutions and use to propose (circulation) in step in acidleach.Directly acid can also be delivered to sour purification phase so that HCl concentration is increased to about 95wt% from about 30wt% with gas phase.Such as, this can carry out during drying stage or distillation.

6-is pre-concentration iron(ic) chloride, rare earth element and rare metal (liquid obtained from step 4) then, and considers the Fe from its hydrolysis ₂o ₃(rhombohedral iron ore form) extracts and acid recovery makes it be hydrolyzed at low temperatures.All recovery of heat from other parts of calcining step (step 5), lixiviate partial exothermic reaction (step 1) and the method are all recycled in preconcentrator.

After the removal of 10-at rhombohedral iron ore and the interior recirculation to crystallizer, can process for any one in the method for recovering rare earth element from alumina-bearing material the solution being rich in rare earth element by using described in the disclosure.Such as, the rare earth element of recovery can be various forms of, such as oxide compound, muriate, oxyhydroxide etc.As described in the disclosure before, statement " rare earth element " can also comprise " rare metal ", thus in step 10, also can reclaim rare metal.Such as, rare metal can be rare metal oxide form.Therefore, in fig 1 and 2, such as, step 10 can be the process shown in Fig. 3 or Fig. 4 a and 4b.

Then, the metal chloride (Me-Cl) of other non-hydrolysables, such as MgCl ₂following steps are experienced with other:

Then 7-, adopts dry highly enriched gas chlorination hydrogen to be made to be rich in the strength of solution of non-hydrolysable product under magnesium chloride and other low temperature raise by passing in crystallizer.This causes magnesium chloride sedimentation to be hexahydrate.

Then, (by rotary kiln, fluidized-bed etc.) calcining Magnesium dichloride hexahydrate, bears the spirit of salt of very high density, and makes this spirit of salt get back to lixiviate step 8-thus again.

Other Me-Cl of 9-experience the pyrohydrolysis step of standard, can generate the oxide compound of mixing in this step and regenerate the spirit of salt of azeotropic point (20.2%wt).

Such as, liquid can simmer down to ferric chloride concn be at least 26 % by weight concentrated liquid; Then, iron(ic) chloride can be hydrolyzed at the temperature of about 155 DEG C to about 350 DEG C, maintain simultaneously ferric chloride concn at least 65 % by weight level comprise the composition of the rhombohedral iron ore of liquid and precipitation to generate, and reclaim this rhombohedral iron ore.

Such as, liquid can simmer down to ferric chloride concn be at least 26 % by weight concentrated liquid; Then, iron(ic) chloride can be hydrolyzed at the temperature of about 155 DEG C to about 350 DEG C, maintain simultaneously ferric chloride concn at least 65 % by weight level comprise the composition of the rhombohedral iron ore of liquid and precipitation to generate; Reclaim rhombohedral iron ore; With recovering rare earth from this liquid.Such as, after the recovery of rare earth, the method can also comprise makes liquid and HCl react to make MgCl ₂precipitation, and reclaimed.

As described above, various alumina-bearing material can be used as the parent material of disclosed method in the disclosure.Carry out the example adopting clay and bauxite.But, it will be understood by those skilled in the art that, continuous processing can process the silicon-dioxide (>55%) of high per-cent and the aluminium (being such as low to moderate about 15%) of impurity and quite low per-cent, and still economically and technically feasible.For Al ₂o ₃gratifying productive rate (>93% to 95%) can be obtained, can obtain for rare earth element and rare metal the productive rate being greater than 75%, 85% or 90%.In most of the cases do not need thermal pretreatment.Method disclosed in the disclosure relates to the special technique of lixiviate about very high strength and acid recovery, thus provides the several advantages being better than alkaline process.The solid residue according to alkaline process is not produced by the method benefiting from completely overall HCl recovery circulation.

In step 1, no matter whether thermal treatment, all that mineral are broken, mill and be categorized as the median size with about 50 μm to about 80 μm.

In step 2, introduced in reactor by the raw material ground, it can experience leaching stages.

The lixiviate spirit of salt used in step 2 is the acid from the circulation in step 5,6,8 and 9 or regeneration, and its concentration 15% weight percent changes to 45% weight percent.Use membrane sepn, low temperature and/or high pressure method can obtain higher concentration.Can reduce pressure and carry out acidleach at close to the temperature of its boiling point and carry, thus allow the level of response (90% to 100%) of minimum digestion time and raising.Lixiviate (step 2) can be completed with semi-continuous pattern, the spent acid with remaining free hydrogen chloric acid is replaced with highly enriched acid in this mode in the specified phase of reaction, or allow the acid/mineral ratio of reduction, thus Reaction time shorten and raising reaction kinetics.Such as, kinetic constant k can be: 0.5g/ mole .L to 0.75g/ mole .L, or 0.75g/ mole .L to 1.10g/ mole .L.

As described above, basic metal, iron, magnesium, calcium, potassium, rare earth element and other elements can be also chloride form in different steps.Silicon-dioxide and titanium can remain insoluble, and can experience (step 3) Gu liquid/separation and cleaning stage.Method inclination of the present disclosure in using rake classification, adopt belt filter to filter, muriate in residual ionization spirit of salt that centrifugal etc. technology reclaims maximum and solution reclaims maximize yield to make spirit of salt.Then, not silica containing mother liquor is called as spent acid (various metal chloride and water), and enters crystallisation step (step 4).

In step 4, with to obtain from step 5 or the highly enriched gas chlorination hydrogen of drying of recirculation carries out saturated after the spent acid (or vat liquor) with a large amount of aluminum chloride, this causes the precipitation (AlCl of Aluminium chloride hexahydrate ₃6H ₂o).Then, the precipitation retained to be filtered before calcination stage (step 5) or centrifugal being fed to.Then, by remaining spent acid process from step 4 to acid recovery system (step 6 is to 8), wherein pure secondary product can be obtained.

In steps of 5, directly aluminum oxide (alumina) is obtained by hot conditions.The highly enriched hydrogenchloride of the gas form obtained can be used for expects that step 4 and 7 is for crystallization.Absorb excessive hydrogenchloride and it be used as the regenerating acid of lixiviate step 2 with the form of highly enriched acid, the concentration of the concentration ratio azeotropic point of highly enriched acid is high (>20.2%).Such as, this concentration can be about 25 % by weight to about 45 % by weight, or between 25 % by weight and 36 % by weight.Acid also can in the gas phase directly (>30wt%) to lead again sour purifying.

After step 4, various chloride derivatives (mainly the rare earth element of iron(ic) chloride, magnesium chloride and chloride form) then carries out iron extraction step.This step can such as by using technology disclosed in WO 2009/153321 to carry out, and it is incorporated herein by reference in their entirety.In addition, rhombohedral iron ore can be inoculated for crystal growth.

In step 6, carry out low temperature (155 DEG C to 350 DEG C) hydrolysis, generate pure Fe ₂o ₃(rhombohedral iron ore), and the spirit of salt bearing at least 15% concentration again.Method as described in WO2009/153321 passes through series of steps, as preconcentration steps, wherein iron protochloride are oxidized to the oxidation step of ferric form, with finally by hydrolysing step the solution of iron protochloride and iron(ic) chloride, its possible mixture and free spirit of salt be worked into be called as hydrolyzer (hydrolyser) can in operating unit, wherein ferric chloride concn maintains 65 % by weight to produce rich gas stream, wherein concentratedly guarantees the hydrogen cloride concentration of 15% to 20.2% and will carry out the pure rhombohedral iron ore of physical separation step.By potential condensing units to pre-concentration, and be used as to heat to input together with the excessive heat from calcination stage (step 5).

After iron is removed, in hydrolyzer (step 6), remaining mother liquor is rich in the ortho acid of other non-hydrolysables, and mainly comprises mixture (various muriate) and the rare earth element of magnesium chloride or other possible elements.

The rare earth element high enrichment of chloride form is that hydrolyzer can operating unit (step 6) by precentagewise, and it is extracted (step 10) from mother liquor, the method for recovering rare earth element from alumina-bearing material that the disclosure wherein can be adopted to limit.Such as, various forms of rare earth element can be extracted thus.Such as, it can be oxide compound REO form.Such as, the method for recovering rare earth element of the present disclosure can allow, in hydrolyzer recirculation loop, following rare earth element is concentrated to high density: scandium (Sc), gallium (Ga), yttrium (Y), dysprosium (Dy), cerium (Ce), praseodymium (Pr), neodymium (Nd), europium (Eu), samarium (Sm), gadolinium (Gd), lanthanum (La), erbium (Er).Certainly, at least one rare earth element be recovered will depend on the character of parent material (alumina-bearing material).

By be rich in increment metal, mainly magnesium from step 6 and 10 waste acid liquor process to step 7.Adopt the highly enriched gas chlorination hydrogen from the drying of step 5 to make solution saturated, this causes the precipitation of Magnesium dichloride hexahydrate.The throw out of reservation is fed to calcination stage step 8, obtain pure MgO (>98wt%) in this stage, bear highly enriched spirit of salt (spirit of salt of such as at least 38%) again, and transferred to lixiviate step (step 2).The alternative route of step 7 uses the gaseous hydrochloric acid from the drying of step 8.

In step 9, the metal chloride process do not changed to produce the oxide compound of mixing, wherein can be reclaimed the spirit of salt of 15wt% to 20.2wt% concentration to pyrohydrolysis step (700 DEG C to 900 DEG C).

According to another example as shown in Figure 2, the method similar in appearance to the example shown in Fig. 1, but can comprise some change programmes as described below.

In fact, as shown in Figure 2, the method can comprise the interior recirculation that (after step 6 or only before step 10) gets back to crystallisation step 4.In this case, the mother liquor from hydrolyzer (step 6) completely or partially can be recycled to the crystallization of step 4, and in this step, relative to the non-hydrolysable element comprising rare earth element, concentration can occur increases.

This step may be used for the concentration increasing rare earth element significantly, thus is conducive to its extraction in step 10.

About step 7, as previously mentioned, dry highly enriched gas chlorination hydrogen is adopted to be made to be rich in the strength of solution of non-hydrolysable product under magnesium chloride and other low temperature raise by passing in crystallizer.This can cause magnesium chloride to precipitate (such as after the removal of sodium-chlor and Repone K) with hexahydrated form.

As shown in Figure 2, extra step 11 can be increased.Sodium-chlor can carry out chemical reaction to obtain sodium sulfate and to regenerate the spirit of salt of azeotropic point with sulfuric acid.Repone K can carry out chemical reaction to obtain potassium sulfate and to regenerate the spirit of salt of azeotropic point with sulfuric acid.

Method shown in Fig. 2 A, similar in appearance to the method shown in Fig. 2, is included between stage 12 and stage 2 for using the additional step of obtained purifying acid unlike it.

Method shown in Fig. 2 B, similar in appearance to the method shown in Fig. 2, comprises by from being wherein separated TiO unlike it ₂the SiO carried out ₂the additional step of purifying, and the optional step 5a that wherein can carry out the low-temperature decomposition of aluminum chloride.

Between step 6 in fig. 1 and 2 and 10 and/or between 7 and 10, the composition comprising rare earth element and/or rare metal can be further purified.In fact, ion exchange column can be adopted not to be the impurity of rare earth element and rare metal to process this composition to remove.Such as, pack processing the muriatic this composition of rare earth element and/or rare metal can be contained to remove impurity, such as iron, aluminium or other metals.Then, once complete the process adopting this post, just can as described in method of the present disclosure ground Extraction of rare earth element and/or rare metal.

Be provided for substantially optionally reclaiming with this in the disclosure, precipitate, extract and/or the particular instance of separating at least one rare earth element.Such as, this can complete from vat liquor and/or throw out and any other downstream derivative thing, solution, throw out, composition or solution.

Such as, can by carrying out removing below, precipitating, extract and/or separating at least one rare earth element:

-precipitation at least one rare earth element (such as about 6 to about 8,7 to the pH value of about 8 or 7 to about 7.5);

-make spent ion exchange resin (such as, as US 4, described in 816,233 (being incorporated herein by reference in their entirety));

-adopt the extraction of solvent (such as, two-(2-ethylhexyl) phosphoric acid (HDEHP (also referred to as DEHPA)) can be used, single (2-ethylhexyl) 2-ethylhexyl phosphonic acid ester (HEP/EHP), octylphenylphosphoric acid ester (OPAP), 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester (PC88A) and optionally toluene carry out liquid-liquid and extract (such as, as Kao etc., ChemicalEngineering Journal, 119th volume, the 2-3 phase, on June 15th, 2006, described in 167-174 page (being incorporated herein by reference in their entirety)), or adopt and use alkyl phosphate to carry out extracting (such as, as US 3, 013, described in 859 (being incorporated herein by reference in their entirety))),

-use extraction agent (such as using two (2,4,4-tri-methyl-amyl) hypophosphorous acid or derivatives thereof);

-absorption (charcoal absorption) on optionally ester modified with Tributyl phosphate gac, or absorption on polyurethane polyethers foam (PUF) (such as, as Zhou etc., RAREMETALS, 27th volume, 3rd phase, 2008, described in 223-227 page (being incorporated herein by reference in their entirety));

The extraction of-employing hollow-fibre membrane; With

-use electrolytic deposition technology (such as, as described in US 2004/0042945 (being incorporated herein by reference in their entirety)).

Such as, from the surplus solution produced during the method, (optionally HNO can be used ₃) precipitation scandium (such as when having precipitated iron and/or when having precipitated aluminium).

Such as, when substantially optionally precipitate from vat liquor and/or throw out and any other downstream derivative thing, extract and/or separating at least one rare earth element time, various order can be performed, namely according to the character of the rare earth element of starting raw material and existence, another kind of given rare earth element can more easily be extracted before or after a kind of given rare earth element.

Such as, as shown in Figure 3, in the mixture of rare elements comprising HCl, water and chloride form or solution, extraction agent process mixture can be adopted therefrom to extract GaCl ₃, thus obtain not containing the solution of Ga.Such as, this extraction agent can be octylphenylphosphoric acid ester (OPAP) or 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester (PC88A) and toluene.Then, GaCl can be precipitated ₃, then changed into Ga by heating ₂o ₃, optionally reclaim HCl.

Then, extraction agent (such as SME 529 can be adopted ^tM, Tributyl phosphate ester or two-isopentyl methylphosphonate, two-(2-ethylhexyl) phosphoric acid, 7-(4-ethyl-1-Methyl Octyl)-oxine (Kelex 100 that with the addition of in the normal heptane of 10% nonylcarbinol ^tM)) process containing the solution of Ga, for substantially optionally therefrom extracting muriate to obtain containing the solution of cerium.Finally, can by CeCl ₃change Ce into ₂o ₃, optionally reclaim HCl simultaneously.

Then, can adopt extraction agent, such as two-(2-ethylhexyl) phosphoric acid or two-(2-ethylhexyl) phospho acid process do not contain the solution of Ce, substantially optionally to extract Sc and to provide not containing the solution of Sc.Oxygenant (such as NaOH) can be adopted to process the Sc of extraction to provide Sc ₂o ₃.

Then, may sequentially can extract not containing various remaining rare earth element (Pr, Nd, Sm, Eu, La, Gd, Y, Dy, Er etc.) in the solution of Sc with different.

Such as, have been noted that the method shown in Fig. 3 can be used as various additive method, a part for such as, method shown in Fig. 1 or Fig. 2.Such as, the step 10 in Fig. 1 and 2 can be the process shown in Fig. 3.

Method shown in Fig. 3 A, similar in appearance to the method shown in Fig. 3, comprises unlike it extra purification step using ion exchange column.

Such as, as shown in Figure 4A and 4B, the method for Extraction of rare earth element can comprise:

Iron is used to be ferrous iron by ferric iron back;

Separating gallium from solution of ferrous chloride;

Precipitation also pre-concentration rare earth element from raffinate;

By rare earth element lixiviate be classified as heavy (HRE) group of light (LRE) combination again;

Separating yttrium from scandium and heavy rare earth element;

Separation of Scandium and heavy rare earth element; With

Lower concentration acid is under atmospheric pressure adopted to carry out lixiviate.

Method shown in Fig. 4 C and 4D, similar in appearance to the method shown in Fig. 4 A and 4B, can comprise the extra purification steps using ion exchange column, optional plasma body purification step, extra acid recovery step and extra calcining step unlike it.

Reductive agent (such as metallic iron, starch) is adopted to be that ferrous iron may be used for preventing iron from extracting altogether or iron precipitation by ferric iron back.Reaction times can be very short, and it can produce heat.The reaction being generally used for reduced iron (III) is as follows:

2Fe ³⁺+Fe ⁰+HCl->3Fe ²+H ₂

As long as under feed solution maintains reductive condition, iron would not be had to be present in this liquor.As shown in figs 4 a and 4b, iron(ic) chloride feed solution 101 can be fed to the retort of stirring, reductive agent (such as metallic iron 102) can be added to allow iron(ic) chloride to be changed into iron protochloride (see " iron removal ").After solid-liquid separation (s/l separation), can extract at gallium the filtrate 103 processing further in loop and obtain.The filter cake comprising solid material and iron can be dewatered, then can prepare to dispose the slurry obtained.

Then, the organic solution comprising extraction agent (being such as dissolved in the Tributyl phosphate ester (TBP) of kerosene) can be adopted to extract gallium (see " gallium recovery ").Therefore, rare earth element and iron can be stayed in raffinate.Extraction can be changed according to chloride ion concentration.Such as, chloride ion concentration is higher, and the trend that gallium complex is formed is stronger, and it is better to extract.

Such as, the reagent of such as Tributyl phosphate ester or tertiary amine (such as Alamine 336) can be used for gallium (reclaiming from hydrochloric acid solution).Such as, when increasing spirit of salt (HCl) concentration, gallium extraction can be raised to maximum value, then can again reduce.Such as, extract for gallium, HCl concentration can be increased to about 4M HCl at most.Under these conditions, gallium can with HGaCl ₄complex compound and as three solvate (HGaCl ₄* 3TBP) TBP extract gallium (such as when extraction agent is TBP) form exist.

The rising that extracting increases with acidity is due to HGaCl ₄extra formation.Below chemical reaction is shown.

GaCl ₄ ^-+H++n TBP->HGaCl ₄*(TBP) _n

For Low acid or neutral solution, the material of extraction is the GaCl of the solvate forms of hydration ₃.

GaCl ₃+m H ₂0+n TBP->GaCl ₃*(H ₂0)m*(TBP)n

The iron of the common extraction accumulated in organic phase can adopt spirit of salt to carry out washing (see " gallium strip liquor ").The organic solution comprising gallium obtained is fed to wherein with the reextraction loop that water 104 pairs of galliums are stripped.Then the raffinate 106 comprising iron protochloride and rare earth element can be fed to rare-earth precipitation part.Final strip liquor 105 comprises gallium.

Such as, the oxalate precipitation of rare earth element causes compound low-down solubleness in aqueous.The precipitation of rare-earth oxalate can realize by adding precipitation agent 107.Such as, oxalic acid 107 may be used for precipitation.Such as, can use precipitation trivalent rare earth element precipitation agent (such as oxalate (deriving from oxalic acid)) effectively.Such as, this kind of precipitation agent can provide low-down solubleness in aqueous to the throw out formed thus.

Following equation is observed in trivalent rare earth element precipitin reaction in aqueous:

2REE ³++3H ₂C ₂O ₄+x H ₂O->[REE ₂(C ₂0 ₄) ₃*x H ₂0] _s+6H+

Overspill from elementary rare earth element precipitation 109 can be fed to ferrous treatment loop.After filtration, the filter cake comprising rare earth element can be fed to cleaning and remove water unit.Then, the slurry 108 obtained can prepare for lixiviate again (see " REE is lixiviate again ").Spirit of salt 110 can be used to carry out the lixiviate again of rare earth filter cake.

((PC88A in kerosene is (also referred to as lonquest for such as two-(2-ethylhexyl) phosphoric acid (D2EHPA) or 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester to adopt extraction agent ^tM801))) Extraction of rare earth Yt, scandium and heavy rare earths (HRE) (see " elementary REE reclaims ") from the chloride soln 111 that the pre-concentration and pH value that comprise such as about 150g/L to about 250g/L regulate.Scandium, other HRE and yttrium can be extracted and light rare earths (LRE) is stayed in raffinate 113.

Then, spirit of salt (2M HCl) can be optionally adopted to wash to remove the LRE of common extraction to load organic phases.Secondary washing part can remove europium by using weak spirit of salt (1M to 1.5M HCl).Then strong acid (3.5M HCl) 112 can be adopted to strip to the extract comprising yttrium, scandium and HRE.

Pack processing can contain the HRE strip liquor 114 of yttrium and scandium to obtain the Y more than 90% in the first loop of duo-sol extraction purification process further ₂o ₃and Sc ₂o ₃.In a first step, ((PC88A in kerosene is (also referred to as lonquest for such as two-(2-ethylhexyl) phosphoric acid or 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester can to make the aqueous solution of the HCl comprising about 25g/L (rare earth element of oxide form) and 0.4M and extraction agent ^tM801))) (see " secondary REE reclaims ") is contacted.Then the spirit of salt of dilution is adopted to wash load organic phases.Can extract scandium, yttrium and HRE by reagent, and the strong spirit of salt 115 of last employing is stripped with high oxide compound/sour ratio.Final strip liquor can have the rare earth oxide concentration of about 40g/L and the HCl of about 1M.This solution is partially neutralized.

Extraction agent (the Tributyl phosphate ester (TBP) in such as kerosene) can be adopted further to extract this pretreated strip liquor 116.Process can be completed with multistage process, carry out reextraction as end finally to adopt water 117 pairs of load organic phases.All HRE and scandium can be extracted thus, yttrium be stayed in raffinate 119.The final strip liquor 118 comprising HRE is formed for the further source that be separated of scandium with heavy rare earths.For this reason, various possible extraction agent can be used, such as two-(2-ethylhexyl) phosphoric acid.

Yttrium can also be removed from by the strip liquor obtained primary extraction step.Such as, can be separated in pH value 3 after interpolation ammonium thiocyanate is as complexing agent.When employing Tributyl phosphate ester, Alamine 336 or Aliquat 336 extract heavy rare earth element, this process can obtain the raffinate being rich in yttrium.

The other solvent extraction purifying loop similar with the Isolation and purification method of aforementioned yttrium can be used to carry out being separated of scandium and other HRE (such as dysprosium and erbium).Therefore, extraction agent can be identical or different extraction agent (such as two-(2-ethylhexyl) phosphoric acid (D2EHPA); (PC88A in kerosene is (also referred to as lonquest for 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester ^tM801)) or two (2,4,4-tri-methyl-amyl) phosphonic acids (lonquest ^tM290), washing soln 120 can be identical with 177, thus provide scandium raffinate 121 and the strip liquor 122 comprising europium and erbium.

As an alternative, as US 3, described in 751,553 (being incorporated herein by reference in their entirety), yttrium can be extracted.In fact, yttrium can be extracted from xenotime enriched material.This can come by using three solvent extraction loops.In a first step, DEHPA can be used to carry out separating yttrium.In the second step, three (octyl methyl) ammonium nitrate (Aliquat 336) can be used to carry out Extraction and separation cerium, and yttrium is stayed in raffinate.In third step, three (octyl methyl) ammonium thiocyanate can be adopted to extract Tm, Yb and Lu.In this extraction circulation, yttrium performance is as Ce elements.From this step, highly purified yttrium oxide can be obtained.

According to another replacement scheme, yttrium oxide can be extracted with two steps, three (octyl methyl) ammonium nitrate namely can be used to carry out separating mixture La-Er/Y-Lu, then use versatic acid to carry out the purifying of yttrium.

Solvent extraction is for the selective separation process by means of the valuable element of organic solution isolation and identification from the aqueous solution.In this process, make to comprise usual lower concentration and the aqueous solution of coherent element together with other dissolved substances (pollutent) mixes with the organic solvent comprising reagent.Relevant element and reagent react are to be formed in organic solution than compound more easily molten in aqueous.Therefore, relevant element transfers to organic solution.

Afterwards, in order to reclaim the material of extraction, the aqueous solution (adopting the aqueous solution to strip to organic solution) making organic solution and its composition that the compound between element with reagent is separated, reclaims element with pure form thus in " newly " aqueous solution.In " newly " aqueous solution, the concentration of element can be raised by regulates liquid flow velocity, is generally 10 to 100 times of concentration in the initial aqueous solution.Organic solution poor for the element of extraction is turned back to other extraction, directly, or after the part of its cleaned impurity.

Such as, the important factor controlling this solvent extraction process can be the concentrated and thinner of the quantity, washing and reextraction stage, the organic solvent that extract.

In typical solvent extraction process, the aqueous phase comprising rare earth element can be such as chloride or nitrogenous acid solution.Organic phase is included in organic solvent, as the extraction agent as described in this disclosure in fatty thinner or surrogate.

Solvent extraction techniques can be used as the abstraction and purification process of rare earth element.Some in following performance are especially relevant when selective extraction agent or chemical extraction agent:

The highly selective of other unwanted metals and acid is exceeded in extracting method,

The high transfer ability of extraction agent,

Good chemical stability,

Kinetics fast.

Such as, precipitation expression removes rare earth element with (solid) compound forming new indissoluble by adding chemical reagent from solution.Such as, can come to precipitate completely by oxalate, Strong oxdiative thing or other compounds.

Also precipitation of hydroxide and bis sulfonate can be used.For large-scale operation, ammonia may be used for carrying out the precipitation of hydroxide from nitrate or chloride soln.Bis sulfonate RE can be precipitated by sodium sulfate being added to the solution comprising rare earth element ₂(SO ₄) ₃* Na ₂sO ₄* nH ₂o.Following equation is observed in trivalent rare earth element precipitin reaction in aqueous:

REE ³⁺+3H ₂O→REE(OH) ₃+3H ⁺

Such as, the solvent extraction that the Tributyl phosphate ester (TBP) in kerosene carries out from the iron (III) chloride soln can be adopted, because the iron in this liquid environment is with chloride complex (FeCl ₄ ^-) form exist:

FeCl ₄ ^-+H++n TBP->HFeCl ₄*(TBP)n

Extraction highly can depend on chloride ion concentration.In fact, chloride ion concentration is higher, and the trend that iron (III) complex compound is formed is stronger, and it is better to extract.Iron (II) also forms similar chloride complex (FeCl ₄ ^-2), but, FeCl ₄ ^-2organic complex is less inclined to and extracts under prevailing conditions.

In order to extract (reextraction) iron from organic solvent again, organic solvent can be cleaned with pure water (such as nanometer water purity).Then, according to following formula, iron (III) can be transferred to water (stripping solution):

HFeCl ₄*(TBP)n->FeCl ₃+HCl+n TBP

Iron back extraction can be taken as iron(ic) chloride.The spirit of salt of identical amount can also be washed out.Chloride concentration increases, and the reextraction of iron stops.Therefore, the concentrated restriction by aluminum ion simultaneously shifted of iron in stripping solution.

The embodiment below illustrated is nonrestrictive, and proves method of the present disclosure for illustrating better.

Embodiment 1

The preparation of alumina-bearing material sample

Alumina-bearing material (such as argillite) can be crushed to contribute to following steps subtly.Such as, microminiaturization can make the reaction times shorten several hours (about 2 to 3 hours).In order to remove most of iron, optionally between destruction step and calcining step, carry out room temperature lixiviate.Such as, adopt spirit of salt HCl (32wt%) to carry out this operation, use the argillite/sour ratio (weight/volume) of 1:5.Experimentally condition (particle size, treatment time, stirring system), then can dissolve the iron of about 65% to about 95%.But this lixiviate step can also bring the aluminium (0 to 5%) of certain percentage.The final step of the precipitation of argillite comprises the argillite of calcining pretreatment.Complete in this time period that can continue about 1 to 2 hour in the calcining temperature being greater than 550 DEG C.Such as, thermal treatment makes it possible to make the amount increase about 30% of the aluminium of extraction to about 40% for same time section.In other words, the amount of the aluminium of extraction doubles.When carrying out room temperature lixiviate, being separated with recovered acid and reducing heating cost before calcining can be completed.

Acidleach is carried

Acidleach carry can comprise at high temperature make pulverizing and calcining argillite and at least one acid solution (such as HCl) react the given time period.Such as, argillite/sour ratio can be about 1:10 (weight/volume), and HCl concentration can be about 6M or about 18wt% to 20wt%, and temperature can be about 100 DEG C to about 110 DEG C, and the reaction times can be about 30 minutes to about 7 hours.Under these conditions, except impurity, can extract and exceed the aluminium of about 90% and the iron of about 100%.Or, the temperature of about 150 DEG C to about 175 DEG C, lixiviate about 4 can be carried out to about 7 hours under the pressure of about 350KPag to about 500Kpag.

In the later half of this process (such as last 2 or 3 hours), the excessive acid of a part can be reclaimed by flash distillation and condensation.Once stop extracting, just can make solid (argillite that metal is poor) and liquid separation by decant or filtration, then clean described solid.Remaining vat liquor and rinse water can fully be evaporated.Corresponding resistates can use water backwash many times afterwards, to reduce alkali (such as NaOH, KOH, Ca (OH) of acidity and the use of minimizing in iron is removed needed for adjust ph ₂, Mg (OH) ₂deng) amount.Recovery can recycle by adding gas HCl or passing through to add after concentrated HCl (12M) regulates titre.After reaction, the titre of acid experimentally condition can be changed to about 6M from about 4M.About solid, it accounts for the initial mass of the argillite of about 65% to about 75%, can limit its price, and it can be used as ion exchange resin or sorbent material again.

Or can pressurize in autoclave (to improve temperature of reaction) carries out HCl lixiviate.

Such as, rare earth element is recovered in and carries out completing in this stage after above-mentioned acidleach is carried.

Such as, the extraction yield of the metal chloride of 96% is provided with the lixiviate of the ratio of 3.1/1.0 at 180 DEG C of employing 23wt%HCl.

The removal of iron

Extract several replacement schemes for carrying out iron removal in the disclosure.Such as, can by certain ph substantially optionally precipitated iron ion carry out iron removal.Or, some extraction agents as described in WO2008141423 can be used.Film can also be used in conjunction with this kind of extraction agent.

Such as, such as the removal of iron can be carried out in the pH value of at least 10 or the pH value of about 11.5 to about 12.5 by the ion precipitation of iron in alkaline medium.PH value can also be about 3 to about 6, or about 3 to about 5, or about 3 to about 4.Can be that the solution of the NaOH of 10M completes this step by adding such as concentration.Other alkali can also be used, such as KOH.Then, required whole be by filtering, decant or the centrifugal solid part that makes be separated with liquid portion, and adopt the alkali of dilution, the solution (such as concentration is the NaOH of 0.01M to 0.02M) of such as NaOH rinses this solid.Then, this solid is cleaned upstream with water.Liquid portion comprises aluminium and alkaline-earth metal.Iron and substantially removing completely of nearly all impurity (other metals) can realize with the form of insolubles and the oxyhydroxide washed off thus.Optionally, the purification step that employing can be used to be extracted by liquid-liquid of hollow-fibre membrane reclaims iron.

Or, can by the removal using extraction agent and hollow-fibre membrane to carry out iron.Optionally chelated iron ion can be used substantially in this step to exceed the various extrectants of complexing aluminum ion (or complexing aluminum ion exceedes chelated iron ion) according to the ratio of Al/Fe.Such as, can by using HDEHP (or DEHPA (di-(2-ethylhexyl)phosphoric acid)) as the extraction agent being suitable for chelated iron ion.Can at organic solvent, such as, in heptane or any varsol, working concentration is the HDEHP of about 1M.This extraction can need the duration of contact (several minutes) of suitable section.Such as, can use magnitude be 2 pH value, the ratio of aqueous phase/organic phase can be about 1:1.Observe the iron that can extract 86% to 98% under these conditions.Can understand, in this case, iron is limited in organic phase.In order to reclaim iron in aqueous phase, then can carry out adopting spirit of salt (2M or 6M) and the ratio of organic phase/sour phase is the reverse extraction of about 1:0.5.In this case, the aqueous phase obtained is rich in Fe ³⁺ion.

Such as, after carrying out above-mentioned iron recovery, complete rare earth element in this stage to reclaim.

Adopt and use the solvent extraction of reverse flow technique, spirit of salt reextraction and contact with MgO solution afterwards, thus with the form precipitating rare earth element of oxyhydroxide, then in roasting assembly, product is changed into its corresponding oxide compound.

Alum recovery

This step also can be carried out in every way.Such as, aluminum ion can about 7 to about 9 or about 7.5 to about 8.5 or about 8 pH value with Al (OH) ₃form (such as Al (OH) ₃hydrated form) precipitation.Or, aluminum ion can be made to react with the extraction agent as described in WO2008141423.

The solution using precipitation or extractive technique to obtain from abovementioned steps is more clean, and mainly comprises aluminium, such as about 90% to about 95%, or even up to about 90% to about 99.8% (not having alkaline-earth metal when precipitating).Can extract by using liquid-liquid, such as, extraction by using identical hollow-fibre membrane and extraction agent to carry out aluminium, described extraction agent is suitable at least substantially optionally complexing aluminium, and exceedes the complexing with other metals or resistates.Such as, two (2,4,4-tri-methyl-amyl) phospho acid are (as with trade(brand)name Cyanex ^tM272 sales) may be used for there is specific extraction agent to aluminium.Such as, this extraction agent can use with organic solvent, concentration as about 20%v/v in heptane.Ratio between aqueous phase and organic phase can be about 1:1 to about 1:3.Such as, Extracting temperature can be about 40 DEG C, and pH value can maintain about 2.5 to about 3.5.Observe the aluminium that this technology makes it possible to extract more than 70% to 90%.After aluminium is limited in organic phase, instead can extract with Al by using ³⁺the form of ion concentration thing is reclaimed.Such as, spirit of salt (such as concentration is 6M) can be adopted oppositely to extract at the temperature of about 40 DEG C.Under this condition, the aluminium more than 90% can be reclaimed.

Such as, rare earth element completes in this stage after being recovered in and carrying out above-mentioned alum recovery.

Then, can by adding alkali, if NaOH is by Al ³⁺change aluminium hydroxide (such as Al (OH) into ₃hydrated form).Finally, can pass through such as at the temperature calcination Al (OH) of about 800 DEG C to 1200 DEG C ₃by Al (OH) ₃change aluminum oxide (aluminium oxide Al into ₂o ₃).

Can also by Al ³⁺change AlCl into ₃6H ₂o, can reclaim HCl after firing, and generate Al ₂o ₃.

Can be further purified by recrystallization.

Rare earth element reclaims

Such as, then rare earth element reclaims and can complete in this stage by using the aforementioned any technology in the disclosure being used for this.Such as, its can by use as Fig. 3,3A, 4A, 4B, 4C, 4D, 5A, 5B, 5C, 5D, 5E, 5F, 5G, 5H and 26 any one defined in technology carry out.

Fig. 5 E, 5F, 5G are similar with the method shown in 5D to Fig. 5 A, 5B, 5C with the method shown in 5H, can comprise make the extra purification steps of spent ion exchange resin, optional plasma body purification step, extra acid recovery step and extra calcining step unlike it.

Such as, at least one rare earth element is included in the residual solution obtained from aforesaid method.Such as, at least one rare earth element can be lower concentration, and the concentration in the vat liquor such as, obtained in method or vat liquor or solution is lower than about 50ppm, about 25,15,10,5,10,5,4,3,2 or 1ppm.Rare earth element can method latter stage in employing solvent extraction before concentrate.Confirm by inner concentration cycles, concentration (such as 100 times to 1000 times) can be improved significantly, thus for substantially optionally precipitating, extracting and/or separating at least one rare earth element provides more effective condition.

Embodiment 2

As parent material, obtain the sample of clay (argillite) from the Grande Vall é e of Quebec, CAN.

These results represent the average of 80 tests undertaken by each about 900kg sample.These tests are carried out by using method as shown in Figures 1 and 2.

The natural clay of new exploitation state has following composition after grinding and classification:

Al ₂O ₃：15％-26％；

SiO ₂：45％-50％；

Fe ₂O ₃：8％-9％；

MgO：1％-2％；

Rare earth element: 0.04%-0.07%;

LOI：5％-10％。

The HCl of 18 % by weight to 32 % by weight is adopted to carry out lixiviate to this material with two benches process at 140 DEG C to 170 DEG C afterwards.Stoichiometric excess with 10% to 20% of the stoichiometric needed for the removal of the theobromine lixiviate composition based on clay uses HCl solution.In the first leaching stages (step 2) of semi continuous operation, clay and aequum or the spirit of salt of specified proportion of total amount contact 2.5 hours.After removal spent acid, clay contacts about 1.5 hour with pressure with the minimum hydrochloric acid solution of 18 % by weight at uniform temp again.

Filter vat liquor, clean solid with water, and use conventional analytical techniques to carry out analyzing (step 3 see Fig. 1).The purity of the silicon-dioxide obtained is 95.4%, and it is not containing any muriate and HCl.

In another example, be 99.67% by the purity of the silicon-dioxide of extra lixiviate step.

After lixiviate and silicon-dioxide are removed, the concentration of various metal chloride is:

AlCl ₃：15-20％；

FeCl ₃：4-6％；

FeCl ₂：0.5-2.0％；

MgCl ₂：0.5-2.0％；

REE-Cl：0.1–2％

Free HCl:5-50g/l

Then, use the pure dry hydrogen chloric acid of in gas phase about 90% to about 98% to carry out recrystallization with two stages to spent acid, there is in the Aluminium chloride hexahydrate of formation the iron lower than 25ppm.In solution (aqueous phase), the concentration of HCl is about 22% to about 32%, reaches the Al of 95.3% ₂o ₃reclaim.Then, (there is the AlCl of the minimum purity of 99.8% at the crystalline material of 930 DEG C or 1250 DEG C calcining recovery ₃hydrate forms), thus obtain the aluminum oxide (1250 DEG C) of alpha-form.δ form is obtained at 930 DEG C.

Low temperature (decomposing and calcining at about 350 DEG C) carries out another example, and the aluminum oxide of alpha-form is lower than 2%.

The HCl concentration left in the gas phase of calcination stage is about 21 % by weight to about 32 % by weight, and (circulation) is for AlCl ₃and MgCl ₂crystallization.Excessive spirit of salt is absorbed with the concentration needed for lixiviate step and aimed concn.

Then, consider that iron(ic) chloride is with pure rhombohedral iron ore form (Fe ₂o ₃) extraction, iron(ic) chloride is delivered to hydrothermal method.This can adopt the total heat recovery from calcining, prehydrolysis and leaching stages by using the low temperature hydrolysis technology described in WO 2009/153321.

Before step 10 (in the method at Fig. 1 and 2), confirm the element (Al, Fe, Mg and rare earth element, as (Sc, Ga, Y, Ce)) having reclaimed find in parent material about 90 % by weight to about 98 % by weight.Can estimate, can rare earth element effectively for reclaiming about 90% for the method for recovering rare earth element from alumina-bearing material disclosed in the disclosure.Therefore, about the example of the method provided in fig 1 and 2, can estimate, the overall yield reclaiming at least one rare earth element from alumina-bearing material is about 80% to about 90%.

After the pre-concentration from crystallization to hydrolyzer, can from the mother liquor of hydrolyzer (wherein having removed silicon-dioxide, aluminium, iron and most water) Extraction of rare earth element.The rare earth element (RECl) of chloride form concentrates significantly and prepares to be extracted.Verified in hydrolyzer itself for once-through on average concentrated 5 times to 10 times.Concentration factor (once-through) for element-specific acquisition in hydrolyzer is as follows:

Ce：>6

La：>9

Nd：>7

Y：>9

Such as, its can by use as Fig. 3,4A, 4B, 4C, 4D, 5A, 5B, 5C, 5D, 5E, 5F, 5G, 5H and 26 any one defined in technology carry out.

Therefore, skilled person in the art will appreciate that this concentrating can increase quite a lot of when carrying out concentration cycles.

Adopt dry highly enriched spirit of salt to spray remaining magnesium chloride, then calcined as MgO, be recovered in the acid of its azeotropic point simultaneously.

Then, the mixed oxide comprising other non-hydrolysable components carries out pyrohydrolysis at 700 DEG C to 800 DEG C, and such as restored acid (15% to 20.2%wt) is imported lixiviate system again.

The overall yield obtained:

Al ₂o ₃: the 93.0%-95.03% rate of recovery;

Fe ₂o ₃: the 92.65%-99.5% rate of recovery;

Rare earth element: the 95% minimum rate of recovery (mixture);

The MgO:92.64%-98.00% rate of recovery;

Discarded material: 0%-5% maximum value;

HCl totally reclaims: 99.75% minimum value;

Be fed to the HCl intensity 15%-32% (aqueous phase) of lixiviate; 95% (gas phase)

Red mud generates: nothing.

Embodiment 3

Similar feed materials (replacing the bauxite of clay) processes leaching stages according to embodiment 2, and can easily lixiviate under demonstrating the condition determined in example 2.It provides the extraction per-cent for iron 100%, aluminium is greater than to the extraction per-cent of 95%.Find that the method is economically viable, and do not generate harmful by product (red mud).The rare earth element observing about 90% to about 95% or about 91% (weight by compared with parent material) reclaims (as mixture).The sample of test has various Al ₂o ₃concentration (maximum 51%), Fe ₂o ₃concentration (maximum 27%) and the concentration (maximum 1.5%) of MgO.The gallium observing 97.0% extracts.Scandium is extracted as 95%.

Embodiment 4

Some tests are completed with the method shown in proof diagram 4A, 4B, 5A, 5B, 5C and 5D.

Use the gallium chloride from the Alfa Aesar GmbH & Co KG of Karlsruhe, Germany and rare earth chloride hydrate in an experiment.Product is chemical pure quality (99.9%).Chemical dissolution in tap water to obtain stock solution.Aluminum chloride and iron(ic) chloride are technical grade.

The precipitation test of gallium and rare earth element

Wingdale, magnesium oxide and/or caustic soda is used to carry out different galliums and the precipitation test of rare earth.Use oxalic acid as precipitation agent.Regulate by the pH value that ammonia (25%) carries out during oxalate precipitation.At the end of experiment, by filtering, throw out is separated with the aqueous solution.Rare-earth hydroxide in 25 DEG C of mensuration chloride medias and the equilibrium solubility of rare-earth oxalate.

Adopt Wingdale to carry out gallium and scandium from the precipitation of hydroxide earth solution, described earth solution comprises the Sc of Y and 70mg/L of Ce, 170mg/L of the Fe (II) of Al, 180g/L of 15g/L, Ga, 1.4g/L of 220mg/L.At high temperature and the aqueous solution to precipitate and to remove gallium and rare earth element.Fig. 6 illustrates the precipitation of hydroxide productive rate of gallium and the scandium obtained according to the pH value in the aqueous solution (35g/L HCl, Eh+380mV).

Graphic representation in Fig. 6 illustrates the precipitation productive rate of gallium and rare earth and the dependence of pH value.PH value raises increases potassium and scandium precipitation productive rate, the pH value about 2.0 for gallium and scandium close to 98%.Fig. 6 also illustrates the increase that there is aluminium co-precipitation in the pH value level higher than 2.0.Cerium and yttrium do not precipitate under these conditions.Therefore, indicate when pH value in precipitation process maintain 2.0 or lower than 2.0 time, gallium and scandium precipitate with minimized aluminium, iron (II) and rare earth element co-precipitation.

In order to study the impact of iron (II) concentration on the precipitation of gallium and scandium, the iron protochloride (II) of the Fe magnitude of 100g/L is added to the feed solution of gallium and scandium.Limit following test parameter:

Temperature: 25 DEG C

Stirring velocity: 400rpm

Time: 1h

Precipitation agent: Wingdale

Final ph: 5.3

Fig. 7 illustrates iron (II) (aqueous solution (270mg/L Ga, 90mg/L Sc and 35mg/L HCl, the Eh+380mV)) impact on the precipitation of gallium.Above Fig. 7 illustrates that the precipitation of iron (II) concentration on gallium does not affect.

The curve drawn in Fig. 8 illustrates the impact that the iron (II) precipitated according to the scandium of pH value (aqueous solution (270mg/L Ga, 90mg/LSc and 35mg/L HCl, Eh+380mV)) pollutes.Identical with Fig. 7 of condition.The precipitation pH value of scandium is increased to about pH value 3.5 from about pH value 2, and this may be owing to there is not iron in water feed solution.The ultimate density of the scandium of the pH value about 4 reaches the Sc of 18mg/L, is equal to the precipitation productive rate of 80%.

Be rich in the throw out of gallium and scandium with water cleaning, then carry out drying at 105 DEG C, and analyze with the rare earth element determining co-precipitation.Table 1 illustrates about the co-precipitation of aluminium, iron (II), cerium and yttrium and its concentration in the throw out of the gallium obtained and scandium of reaching at laboratory Leaching tests on period.

Table 1. iron (II), cerium and yttrium are from the co-precipitation gallium hydroxide and scandium hydroxide

Lixiviate parameter	Project	Value
			Aluminum concentration in throw out	g/kg	4-6
Iron (II) concentration in throw out	g/kg	20-30
			The loss of cerium	％	<0.5
Cerium concentration in throw out	g/kg	1-2
			The loss of yttrium	％	<0.5
Yttrium concentration in throw out	g/kg	0.1-0.2

The result of the removal test of gallium and scandium is summarized in table 2.

The general introduction of the removal test of table 2. gallium and scandium

The precipitation of hydroxide of rare earth element

Adopt the precipitation of hydroxide of the rare earth element of magnesium oxide and caustic soda to adopt solution to carry out, described solution comprises the Pr of Nd and 0.5g/L of Er, 2g/L of Y, 1.8g/L of Ce, 2.3g/L of 1.8g/L.Room temperature caustic soda and 65 DEG C with in magnesium oxide and the aqueous solution with precipitation and remove rare earth element.In order to study the impact that pH value precipitates rare earth element hydroxide, limit following test parameter:

Temperature: 25 DEG C and 60 DEG C

Stirring velocity: 400rpm

Time: 1h

Precipitation agent: magnesium oxide and caustic soda

Final ph: 10

Fig. 9 illustrates that the pH value 6 that is deposited in of rare-earth hydroxide starts, and has its maximum value in the pH value of about 8.0.In fig .9, the initial pH value of the aqueous solution is 1, Eh is+340mV.

Oxalate precipitation

The aqueous solution of the pre-neutralization tested from precipitation of hydroxide by the Pr comprising Nd and 0.5g/L of Er, 2g/L of Y, 1.8g/L of Ce, 2.3g/L of 1.8g/L is heated to 50 DEG C to 60 DEG C.Add oxalic acid slurry.Then, adjust ph is carried out with precipitation and removal rare earth element by dropwise adding ammonia solution.In order to study the impact of the amount of precipitation agent, limit following test parameter:

Temperature: 60 DEG C

Stirring velocity: 400rpm

Time: 1h

Precipitation agent: the oxalic acid of dihydrate form

Final ph: 1.2

Following Figure 10 illustrates the solubleness of the rare-earth oxalate along with the concentration of oxalic acid increased in constant acidity (pH value 1.2).Precipitating concentration scope is 0.06mol/L to 1mol/L oxalic acid.(aqueous solution (LRE and HRE, final ph 1.2, Eh+340mV)).

For given acidity, the solubleness of rare-earth oxalate increases along with concentration of oxalic acid and reduces, and when the concentration of oxalic acid added is 0.15mol/L or higher, reaches the precipitation productive rate of the rare earth element being greater than 99% full-fledged research.

In order to study the impact that iron (II) concentration precipitates rare earth element, limit following test parameter:

Temperature: 60 DEG C

Stirring velocity: 400rpm

Time: 1h

Precipitation agent: oxalic acid

Iron (II) concentration: 100g/L

Final ph: 1.2

The curve drawn in fig. 11 illustrates in constant acidity (pH value 1.2) according to the rare earth element of concentration of oxalic acid and the precipitation of iron.This figure shows that the precipitation of rare earth element under height iron (II) pollutes is not carried out.

The result of the removal test of rare earth element is summarized in table 3.

The general introduction of table 3. rare earth element precipitation test

Solvent extraction is tested

Extracting operation to simulate counter current solvent, carrying out metal balance test.All experiments are carried out at 25 DEG C.All research is carried out in the Laboratory Instruments of bed dimension.

Organic solution contacts about 10 minutes to 15 minutes at the funnel of shake or in the beaker stirred under with the mixing quite at a high speed of different organic-aqueous ratios (O/A).

The pH value using soda lye (10%) to carry out during solvent extraction regulates.After separation of the phases, preserve and analyze the aqueous phase and organic phase that obtain.

The solvent extraction result of gallium and scandium

Based on the selectivity to gallium and scandium exceeding yttrium, other trivalent rare earths and aluminium, selective reagents Tributyl phosphate ester (TBP).On the other hand, TBP is adopted to extract iron (III) altogether.Therefore, before recovery gallium and scandium, by solvent extraction or with metallic iron pre-treatment to be made a return journey deironing (III) by reduction removal iron (III).Figure 12 illustrates the equilibrium criterion of iron from the extraction iron(ic) chloride (III) solution.Organic solution is included in the TBP of 90 volume % in aromatic kerosene (Solvesso 150).

Show in table 4 by the gallium of Tributyl phosphate ester from the common extraction iron(ic) chloride (III) solution.

The common extraction of table 4. gallium

The organic solution TBP of 90 volume % (in the kerosene)

The aqueous solution (40%FeCl ₃, the Ga of 270mg/l, Eh 500mV)

Organic solution	The aqueous solution	Water/organic	Organic-Ga	Water-Ga	D _Ga	P _Ga
							ml	ml	-	mg/l	mg/l	C _o/C _a	％
101.5	8.5	0.08	6.9	188	0.037	30.4
							71.5	8.5	0.12	9.5	190	0.050	29.6
51.3	8.7	0.17	12.4	197	0.063	27.0
							41	19	0.46	43.6	176	0.248	34.8
43	38	0.86	124	130	0.952	51.9
							20	60	3.00	453	119	3.807	55.9

Can by comparing the gallium washing with water and partly remove common extraction with height.The gallium that this washing reduces from the organic solution of load loses.Equilibrium criterion from the washing of the gallium of the organic solution of load is shown in Figure 13.(profile of equilibrium, organic solution (TBP of 90 volume %, comprises the Ga of Fe, 0.13g/L of 110g/L), the aqueous solution (water)).

Equilibrium criterion from the reextraction of the iron of the organic solution of load is shown in Figure 14.(organic solution (TBP of 90 volume %, comprises the Ga of Fe, 0.13g/L of 110g/L), the aqueous solution (water)).

By the precipitate dissolves of gallium/scandium to be prepared the feed solution of gallium and scandium in the hydrochloric acid solution of the HCl comprising 10mol/L.The TBP of the 50 volume % that employing is diluted in fatty kerosene (D85) tests.Isodecyl alcohol is used to be formed to prevent third phase as properties-correcting agent in an experiment.The equilibrium criterion of the extraction of gallium and scandium is shown in Figure 15 (organic solution TBP of 50 volume % (in the kerosene); The aqueous solution, 6g/L Ga, 2.2g/L Sc and 10mol/L HCl).

Figure 16 illustrates the common extraction (organic solution TBP of 50 volume % (in the kerosene) of the spirit of salt during the extraction of gallium and scandium; The aqueous solution (6g/L Ga, 2.2g/L Sc and 10mol/L HCl)).Then, organic solvent also load have gallium and scandium to strip test for carrying out scandium washing and gallium.

In order to remove scandium from the organic solution of load, use the HCl solution of 5mol/L, 6mol/L and 7mol/L with the O/A ratio of 1:1.This washing obviously reduces the quality of the scandium of the organic solution from load.The impact of spirit of salt washing soln on scandium detersive efficiency is shown in table 5.

The washing test of table 5. scandium

Organic solution (TBP of 50 volume %, comprises the Sc of Ga, 1.2g/l of 1.3g/l, initial Ga/Sc ratio 1.07)

The aqueous solution (hydrochloric acid solution)

Washing soln	Water/organic	D _Ga	D _Sc	S	Ga/Sc ratio
						mol/l HCl	-	C _o/C _a	C _o/C _a	D _Ga/D _Sc	[C _Ga/C _Sc] _Organic
5	1.0	266	0.034	7704	31.9
						6	1.0	710	1.553	514	1.75
7	1.0	799	5.667	125	1.25

The equilibrium criterion of the scandium washing in load organic solution is shown in Figure 17.(organic solution (50 volume %TBP, 7.3g/L Ga, 1.6g/L Sc); The aqueous solution (water)).

The equilibrium criterion of stripping from the gallium of the organic solution of load be shown in Figure 18 (organic solution (and in kerosene 7.5% TBP, 0.4g/L Ga); The aqueous solution (water)).

Table 6 is summarized at the aqueous phase feed of solvent extraction duration of test and the composition of raffinate.

The composition of table 6. aqueous phase feed and raffinate (the organic solution TBP of 50 volume % (in the kerosene), the aqueous solution (6g/L Ga, 2.2g/L Sc and 10mol/L HCl))

Metal	Aqueous phase feed	Raffinate	Extraction efficiency
					g/l	mg/l	％
Gallium	6	<5	99
				Scandium	2.2	<5	99

First, Scium trichloride solution is obtained with water with the spirit of salt of very high ratio washing scandium and extraction altogether.Washing is optionally for scandium, and is stayed by gallium in the organic solution of washing.Then, with water with the O/A ratio of 2:1 from stripping gallium through the organic solution of washing of obtaining.

The extraction of light rare earths and heavy rare earth element

As previously shown, the extraction of rare earth element can depend on hydrogen ion (H+) concentration.Therefore, organophosphorus extractant is the extraction agent relying on pH value.Can use can business obtain reagent, such as two (ethylhexyl) phosphoric acid (D2EHPA), two (ethylhexyl) phosphonic acids (lonquest 801).Selectivity calculates with the business of the distribution factor of the distribution factor of yttrium and cerium.(the organic solution reagent of 10 volume % (in the kerosene) as shown in following Figure 19; The aqueous solution (6.4g/L Y, 107g/LCe, initial pH value 1.5, Eh+430mV)), the yttrium/cerium selectivity of lonquest 801, raising before pH value 1, then declines.

Based on the selectivity exceeded the selectivity of yttrium cerium, select two (ethylhexyl) phosphonic acids (lonquest 801).The lonquest801 of the 10 volume % that employing is diluted in fatty kerosene (D85) tests.Do not use properties-correcting agent in an experiment.In chloride media, the dependence of extraction to pH value of yttrium and cerium is shown in Figure 20 (extracting cerium in chloride soln and yttrium with two (ethylhexyl) phosphonic acids (lonquest801) and two (ethylhexyl) phosphoric acid (D2EHPA)).

The extraction of yttrium

Selective reagents two (ethylhexyl) phosphonic acids (lonquest 801).The lonquest 801 of the 10 volume % that employing is diluted in fatty kerosene (D85) tests.Do not use properties-correcting agent in an experiment.Remaining constant by making the pH value during yttrium extraction with sodium hydroxide solution (2mol/L NaOH) dropping is pH value 1.4.Comprise equilibrium criterion that yttrium in the aqueous solution of yttrium and cerium extracts and be shown in Figure 21 (organic solution lonquest 801 of 10 volume % (in the kerosene); The aqueous solution (6.4g/L Y, 107g/L Ce, initial pH value 1.5, Eh+430mV)).

The yttrium rate of recovery is greater than 99%.The maximum yttrium load of 10 volume %lonquest 801 reagent is about 10g/L yttrium.

By removing the cerium of the common extraction of small amount with the spirit of salt washing of dilution.This mensuration obviously reduces the quality of the cerium from load organic phases.The equilibrium criterion of washing from the cerium of the organic solution of load is shown in Figure 22 (organic solution (lonquest 801 of 10 volume %, comprises the Ce of 0.1g/L); The aqueous solution, 1mol/l HCl).

The mensuration concentration extracting the aqueous phase feed in testing and raffinate at yttrium is shown in table 7.

The composition of table 7. aqueous phase feed and raffinate

The organic solution lonquest 801 of 10 volume % (in the kerosene)

Feed solution (Ce of the Y of 6.4g/l, 107g/l, initial pH value 1.5, Eh+430mV)

Metal	Aqueous phase feed	Raffinate	Extraction efficiency
					g/l	g/l	％
Yttrium	6.4	0.1	98
				Cerium	107	107	0.2

The equilibrium criterion of stripping from the yttrium of the organic solution of load is shown in Figure 23 (organic solution (in kerosene, the lonquest 801 of 10 volume %, comprises the Ce of 1g/L); The aqueous solution (3.5mol/LHCl).

Dysprosium is separated with erbium

Feed solution is prepared by Dysprosium trichloride, Erbium trichloride and Yttrium trichloride are dissolved in tap water.Employing be diluted in Tributyl phosphate ester (TBP) in fatty kerosene (D85), 336 Hes 336 test.By dropwise adding ammonia solution (25%), pH value is adjusted to pH value 3.Organic solution contacts about 10 minutes to 15 minutes in the beaker stirred.The ratio (O/A) of organic phase and aqueous phase is 1/1.By TBP, 336 Hes the dysprosium of 336 and the abstraction and purification of erbium are shown in table 18.

The separation test of table 8. dysprosium and erbium

TBP, 336 Hes the organic solution of 336

The aqueous solution (the NH of the Y of Er, 6.2g/l of Dy, 7.1g/l of 6.7g/l, 1mol/l ₄initial pH value 3 in SCN)

The selectivity for yttrium is exceeded, selective reagents Tributyl phosphate ester (TBP) based on the selectivity for dysprosium and erbium.The TBP of the 80 volume % that employing is diluted in fatty kerosene (D85) tests.Do not use properties-correcting agent in an experiment.Test the impact that ammonium thiocyanate concentration is separated with yttrium with erbium with dysprosium with the extraction of erbium dysprosium.The equilibrium criterion of the extraction of dysprosium and erbium is shown in table 9.

The separation test of table 9. dysprosium and erbium

The organic solution TBP of 80 volume % (in the kerosene)

NH ₄SCN	S	S
			mol/l	(D _Dy/D _Y)	(D _Er/D _Y)
0	7.9	24
			0.3	2.9	2.3
0.5	2.6	2.4
			0.75	2.5	2.4
1.0	2.5	2.3

By removing the yttrium of common extraction with the washing of high O/A ratio with water.The yttrium that this washing obviously reduces from the organic solution of TBP load loses.The equilibrium criterion of washing from the yttrium of the organic solution of load is shown in Figure 24 (organic solution (in kerosene the TBP of 80 volume %, 1.2g/L Y); The aqueous solution (water)).

Finally, Figure 25 (organic solution (in kerosene the TBP of 80 volume %, 8.4g/L Y) is shown in by the equilibrium criterion that the dysprosium of water washs; The aqueous solution (water))

The summary of solvent extraction test

Test obtains the following instance (table 10) of the extraction conditions being applicable to iron (III) water feed solution.

The selected condition that table 10. iron (III) is removed

Iron is removed		Selected condition
			TBP concentration	％	90
Properties-correcting agent (isodecyl alcohol) concentration	％	-
			Aromatic kerosene (Solvesso 150)	％	10
Area load, continuous aqueous phase (35 DEG C)	m/h	2-3
			Iron load	g/l	100
Iron extraction efficiency	％	90
			Iron raffinate concentration	g/l	20
Gallium load altogether	mg/l	100-130

Test obtains the following instance (table 11) of the extraction conditions of the aqueous solution being applicable to gallium and scandium.

The selected condition of the extraction of table 11. gallium and scandium

The recovery of gallium and scandium		Selected condition
			TBP concentration	％	50
Properties-correcting agent (isodecyl alcohol) concentration	％	15-20
			Fat kerosene	％	30-35
Area load, continuous aqueous phase (25 DEG C)	m/h	2-3
			Gallium load	g/l	30-35

Gallium extraction efficiency	％	>99
			Gallium raffinate concentration	mg/h	<1
Scandium load	g/l	10-15
			Scandium extraction efficiency	％	99
Scandium raffinate concentration	mg/l	10-20

Calcining gallium, the Ga of acquisition ₂o ₃purity be 99.99+%.Impurity is the Al of Cl and 1.1ppm of 8.9ppm.

Also calcine scandium, the Sc of acquisition ₂o ₃purity be greater than 99.9%.Major impurity is the Zr of S and 390ppm of 260ppm.

Test obtains the following instance (table 12) of the extraction conditions being applicable to rare earth aqueous solution.

The selected condition of the extraction of table 12. rare earth (yttrium)

Yttrium reclaims		Selected condition
			Lonquest 801 concentration	％	10
Fat kerosene (D85)	％	90
			Area load, aqueous phase continuously (25 DEG C)	m/h	2-3
Yttrium load	g/l	10
			Yttrium extraction efficiency	％	>98
Yttrium raffinate concentration	mg/l	10-20

Test obtains being applicable to the extraction conditions (table 13) proposed below be separated of heavy rare earths and yttrium strip liquor.

The selected condition of the extraction of table 13. heavy rare earths (Dy, Er)

HRE (Dy, Er) removes		Selected condition
			TBP concentration	％	80
Fat kerosene (D85)	％	20
			Area load, aqueous phase continuously (25 DEG C)	m/h	3-4
HRE load	g/l	10
			HRE extraction efficiency	％	99
HRE raffinate concentration	mg/l	5-10

It is the removal process that iron (III) reclaimed, was afterwards the gallium of the neutralization of gallium and scandium and precipitation, yttrium and scandium before verified.In order to prevent and/or reduce iron co-precipitation, (reduction) remaining iron (III) can be processed further by using ferrous metal.

Have studied following six main method parts:

Part 1: iron (III) is removed by using the solvent extraction of the Tributyl phosphate ester (TBP) in kerosene to remove iron (III) from feed solution;

Part 2: final iron is removed by using the reduction of metallic iron to remove iron;

Part 3: the precipitation of gallium and scandium uses Wingdale or magnesium oxide to remove gallium and scandium;

Part 4: the separation of gallium and scandium be separated from comprising 10mol/L spirit of salt and based on being separated in the extracting solution again of the solvent extraction of the Tributyl phosphate ester (TBP) used kerosene and reclaiming gallium and scandium;

Part 5: the precipitation of yttrium and other rare earths is by using neutralization and the precipitation of Wingdale, and then lixiviate removes yttrium and other rare earth elements again in the spirit of salt of dilution;

Part 6: yttrium reclaims in the solution by using the solvent extraction of two (ethylhexyl) phosphonic acids (lonquest 801) to obtain from part 5 and is separated and reclaims yttrium; With

Part 7: yttrium and HRE are separated by using the solvent extraction of the Tributyl phosphate ester (TBP) in kerosene be separated from heavy rare earths, mainly dysprosium and erbium and reclaim yttrium.

Iron (III) is removed

Iron (III) solvent extraction

The feed solution comprising the gallium (201) of 40% iron(ic) chloride (III) and 270mg/L of preparation is fed to iron and removes loop.Employing comprises organic solution (202) the countercurrent extraction iron of the 90%TBP be dissolved in aromatic kerosene (Solvesso150).The iron extraction efficiency obtained is 90%.The gallium extracted altogether gathers to 0.13g/L gallium in organic phase.The organic solution (203) comprising iron and a small amount of gallium obtained is fed to washing loop.Herein, countercurrent washing gallium is compared with the aqueous solution (204) with height.Then, organic solvent is delivered to reextraction loop.Herein, before organic solution (205) being turned back to extraction loop, iron (206) is got with water (207) countercurrent reextraction.

Iron (III) reduces

The common extraction of iron (III) can be prevented and/or pass through to use iron (0) to be reduced in advance the common extraction that iron (II) prevents iron (III).The raffinate (209) of iron (III) comprising aluminium, gallium, scandium, rare earth element and extraction adopting the process of the iron powder (210) of stoichiometric quantity to obtain, to eliminate iron (III) ion.Starch can also be used reduce.

The recovery of gallium and scandium

The precipitation of gallium and scandium

Introduce gallium and scandium precipitation and reclaim to make gallium and scandium and other rare earths separations and pre-concentration gallium and scandium for further process.Then, filtrate (211) poor for the iron obtained (III) is fed to the removal step of elementary gallium and scandium.Herein, Wingdale (212) is added as neutralization reagent.In this step, solution maintains constant pH value 15 minutes to 30 minutes, and under low ph value horizontal dimension is held in controlled Redox Condition.Reach the gallium of 99% and the precipitation productive rate of scandium.The rare earth element of very lower concentration is detected in the throw out of gallium and scandium.Filtration product (225) is fed to water scavenging system.Then, the slurry (213) preparing to obtain for carrying out lixiviate again in concentrated hydrochloric acid solution (214).

The solvent extraction of gallium and scandium

The filtrate obtained in lixiviate step again from gallium and scandium (215) is fed to the separating circuit of gallium and scandium.Employing comprises organic solution (216) countercurrent extraction gallium and the scandium of the 50 volume %TBP be dissolved in fatty kerosene (D85).The gallium reached and the extraction efficiency of scandium are greater than 99%.

The iron extracted altogether gathers the Fe to 0.2g/L in organic phase.The organic solution (218) comprising gallium and scandium and a small amount of iron obtained is fed to washing loop.Herein, countercurrent washing scandium is compared to provide product (221) with the aqueous solution (219) with height.Then, organic solvent (220) is delivered to stripping cells, in this unit, before organic solution (223) turns back to extraction loop and reclaims gallium, get gallium with water (222) countercurrent reextraction.Also reclaim the raffinate of (217) spirit of salt.

Yttrium reclaims

Rare-earth hydroxide precipitates

The filtrate (225) of the settling step from gallium and scandium is fed to other in and loop.Herein, Wingdale (226) is adopted to carry out precipitating rare earth element by pH value being risen to 8 in 60 minutes under controlled redox-potential and under high temperature (60 DEG C).Reach the precipitation of the rare earth element of the research being greater than 99%.All the other iron (II) meeting and rare earth element coprecipitation.Then, throw out (227) is prepared for carrying out lixiviate again in concentrated hydrochloric acid solution (228).

Elementary yttrium solvent extraction

The product (229) obtained of the settling step from gallium and scandium can be fed to the extraction loop of yttrium.Employing comprises organic solution (230) the countercurrent extraction yttrium of the lonquest 801 of the 10 volume % be dissolved in fatty kerosene (D85).The extraction efficiency of the yttrium reached is greater than 99%.The cerium extracted altogether gathers the Ce to 0.1g/L in organic phase.

Due to cerium concentration high in the aqueous solution, can be carried secretly by the water of extracting solution and cerium is transferred to strip liquor.Therefore, extra single wash step can be comprised pollute to avoid cerium.Such as, can with washing soln (233), if 1N HCl process organic phase (232) is to remove cerium and to obtain composition (234).Finally, the raffinate (231) that can process LRE (Ce, Nd, Eu, Pr) with make it separated from one another and optionally purifying they (see Fig. 5 G).

The organic solution (235) comprising yttrium obtained is fed to reextraction loop.Herein, the solution countercurrent reextraction comprising the spirit of salt (236) of 3.5mol/L is adopted to get yttrium.Finally, before organic solution being turned back to the extraction of elementary yttrium, in the mixing tank-settler stage must removed for organic phase regeneration and scandium at, clean the part of organic reagent with the soda lye of dilution.

Final yttrium solvent extraction

In the second solvent extraction process, from yttrium strip liquor (237), remove dysprosium and erbium after the neutralization.Employing comprises organic solution (238) countercurrent extraction dysprosium and the erbium of 80 volume % Tributyl phosphates ester (TBP) be dissolved in fatty kerosene (D85), thus generates the raffinate (239) of yttrium.The heavy rare earths extraction efficiency more than 99% is issued in controlled pH value condition.The organic solution (240) comprising heavy rare earths and a small amount of yttrium obtained is fed to washing function.Herein, in multistage mixing tank settling vessel instrument, countercurrent washing yttrium (242) is compared with water (241) with height.Washings (242) turns back to feed solution.With the organic solvent (243) that water (244) washing yttrium is poor, and return it to extraction circulation.Dysprosium is for the feed solution that be separated of dysprosium with erbium with the strip liquor (245) of erbium.

The yttrium obtained is calcined as Y ₂o ₃, obtain the purity of 99.9+%.Impurity is the Al of Dy and 6.2ppm of Si, 51ppm of 26ppm.

Embodiment 5

By using method as shown in Figure 26 to complete other tests.Spirit of salt (328) is used to carry out the lixiviate of rare-earth hydroxide filter cake (327).The method shown in Figure 26 that those of skill in the art will recognize that may be used for processing the various compositions of the throw out (227) comprising Fig. 5 c.Such as, the throw out (327) of Figure 26 can be identical with the throw out of Fig. 5 c (227).

(pregnant) extracting solution (329) (after the fine filtering) that be rich in is the feed solution to Rare Earth Separation step.This water feed solution comprises cerium, praseodymium, neodymium, europium, dysprosium, erbium and yttrium, and contacts with D2EHPA or lonquest 801 in kerosene.Alkali adjust ph is used in leaching process.Extract dysprosium, erbium and yttrium (HRE), and cerium, praseodymium, neodymium and europium (LRE) are stayed in raffinate (331).

Then, spirit of salt (HCl of 1M to 2M) is optionally adopted to wash to remove the LRE of common extraction to load organic phases.Then, spirit of salt (HCl of 3M to 4M) (336) is adopted to strip to the extract comprising dysprosium, erbium and yttrium.

Being separated of yttrium and strip liquor (337) can be completed by adopting the Tributyl phosphate ester (TBP) in kerosene extract yttrium.Process can be completed with multistage process, finally to adopt water (344), reextraction be carried out as end to load organic phases.Substantially optionally extract all HRE, yttrium is stayed in raffinate (339).The strip liquor (345) comprising HRE forms the source of the further separation being used for heavy rare earth element (HRE).

Erbium is from the separation of dysprosium

By using the solvent extraction process of D2EHPA or lonquest 801 in kerosene from the final strip liquor comprising dysprosium and erbium of yttrium sepn process (234), dysprosium is stayed in raffinate (347).Alkali is used for adjust ph in extraction loop.Then, spirit of salt (HCl of 2M to 3M) is adopted to wash to load organic phases the dysprosium removing common extraction.Then, spirit of salt (HCl of 3M to 4M) (346) is adopted to strip to the extract comprising erbium the strip liquor (348) generating erbium.

The dysprosium that calcining obtains is to generate the Dy that purity is 99.9+% ₂o ₃.Other impurity are mainly the Ca of Yb and 100ppm of 440ppm.

The erbium that calcining obtains is to generate the Er that purity is 99.9+% ₂o ₃.Other impurity are mainly the Al of Y and 140ppm of 390ppm.

The separation of logical snperoxiaized cerium and cerium precipitation

Raffinate (331A) from primary separation is fed to oxidation and cerium precipitation unit.The oxidation of cerium is realized by adding oxygenant.Such as, clorox (349) can be used.Can pH value in about 0.5 to about 1.5 after adding alkali (350) or about 1 pH value carry out the precipitation of cerous hydroxide.The effluent be oxidized from cerium (352) is fed to europium separating circuit.Comprise the filter cake (351) of cerous hydroxide with sour water cleaning, it is dewatered, and stored and be used for further process.

Obtained cerium is calcined as Ce ₂o ₃, obtain the purity of 99.5+%.Impurity is the Y of Pr and 50ppm of K, 280ppm of 330ppm.

The separation of europium

The filtrate (352) obtained from cerium recycling step is separated with neodymium with praseodymium for making erbium.Water feed solution is contacted with D2EHPA or lonquest 801 in kerosene.Extract europium, and praseodymium, neodymium are stayed in raffinate (354).Alkali is used for adjust ph in extraction loop.Praseodymium and neodymium that washing part is extracted altogether by using weak spirit of salt (HCl of 0.5M to 1.5M) to remove.Then, spirit of salt (HCl of 2M to 3M) (353) is adopted to strip to the extract comprising europium.

The reduction of europium and precipitation

The reduction of europium (III) is realized by adding reductive agent.Such as, europium (355) can be reduced by zinc powder or surrogate (361).The precipitation of europium sulfate can be carried out after adding sodium sulfate (362).Effluent from europium reduction loop is fed to wastewater treatment.Comprise the filter cake (363) of europium sulfate with sour water cleaning, it is dewatered, and stored and be used for further process.

Neodymium is from the separation of praseodymium

The raffinate (354) be separated from europium mainly comprises praseodymium and neodymium.D2EHPA or lonquest 801 in kerosene is adopted to carry out being separated of praseodymium and neodymium.Extract neodymium, and praseodymium is stayed in raffinate (357).Alkali is used for adjust ph in extraction loop.Then, spirit of salt (HCl of 2M to 3M) (356) is adopted to wash to load organic phases the praseodymium removing common extraction.Then, spirit of salt (HCl of 3M to 4M) (359) is adopted to strip to obtain the strip liquor (360) of neodymium to the organic extraction (358) comprising neodymium at present.

Obtained neodymium is calcined as Nd ₂o ₃, obtain the purity of 99.9+%.Impurity is the Y of Pr and 50ppm of the K of 330ppm, 280ppm.

In order to the versatility of method disclosed in proved, other tests several are carried out to show that these methods can be suitable for the parent material in various source.

Embodiment 6

Another parent material is for the preparation of the acidic composition comprising various component.In fact, the material of the enriched material for rare earth element and rare metal (being particularly rich in zirconium) has been tested.Table 14 illustrates the result using the method similar to the method described in detail in the method shown in Fig. 1 and 2 and embodiment 1 to 3 this starting raw material to be carried out to lixiviate.Can be inferred by the result shown in Figure 14, extraction be present in rare earth element in the lixiviate composition of acquisition and rare metal finally can by method of the present disclosure, such as, those methods by providing in embodiment 4 and 5, are separated.Obtain result with use H ₂sO ₄the result of the lixiviate carried out is compared and is exceeded at least 20%.

The test that table 14. carries out the zirconia material be rich in.

Embodiment 7

Complete other in the mode similar to mode described in Fig. 6 to test.In the present embodiment, used carbonatite as parent material.(seeing table 15)

The test that table 15. pair carbonatite carries out

Embodiment 8

Use, according to the method for previous embodiment, another battery of tests is carried out to argillite.

The initial composition measured is:

Table 16. raw material initial composition

Element	Composition measuring (wt.)
		Al ₂O ₃	24.00％
Fe ₂O ₃	8.51％
		MgO	1.33％
Na ₂O	1.06％
		K ₂O	2.86％
Ce ₂O ₃	176ppm
		La ₂O ₃	88ppm
Nd ₂O ₃	82ppm
		Pr ₂O ₃	22ppm
Sm ₂O ₃	15ppm
		Dy ₂O ₃	11.5ppm
Er ₂O ₃	6.3ppm
		Ece ₂O ₃	2.9ppm
Gd ₂O ₃	15.0ppm
		Y ₂O ₃	67.0ppm
Ga ₂O ₃	51ppm
		Sc ₂O ₃	28ppm

Adopt the excessive HCl of 18.0wt%+5% in batch mode to carry out lixiviate to sample at about 150 DEG C to about 160 DEG C, continue 6 hours.

Following extraction efficiency is recorded in leaching stages.

The lixiviate extraction efficiency that table 17. detects

Primitive element	The extraction yield (%) detected
		Al ₂O ₃	97.9
Fe ₂O ₃	100
		MgO	96.4
Na ₂O	92.8
		K ₂O	94.0
Comprise the RE-O of Sc and Ga	96.7

After the processing of the key step by successive processes, record following productive rate.

Table 18. totally reclaims productive rate

Element	The overall rate of recovery (%)
		Al ₂O ₃	96.20
Fe ₂O ₃	98.01
		MgO	92.64
Na ₂O	90.77
		K ₂O	93.97
RE/RM-O	90.04

After for the ion-exchange of extraction step and solvent, the rare earth element of mensuration and the independent rate of recovery of rare metal are:

Table 19.

Element	The rate of recovery (%) detected
		Ga ₂O ₃	83.58
Sc ₂O ₃	95.16
		Ce ₂O ₃	93.63
La ₂O ₃	86.81
		Nd ₂O ₃	91.00
Pr ₂O ₃	96.00
		Sm ₂O ₃	87.14
Dy ₂O ₃	93.00
		Er ₂O ₃	91.38
Eu ₂O ₃	93.83
		Gd ₂O ₃	95.89
Y ₂O ₃	82.95

According to the material balance measured, the consumption to the chemical reagent in solvent extraction is:

Iron powder: 0-is by the Fe being hydrolyzed removal ₂o ₃;

HCl (23%wt): as the 0.75Kg/h of stripping solution ion REE 5 × be separated and lixiviate ree oxalate again;

Nanometer water: strip for solution and the 10kg/h of cleaning of precipitation;

Oxalic acid: for the 325g/h of the precipitation of ree oxalate;

DEHPA 5 × solution: several grams per hour;

TBP 5 × organic solution: the 6.5g/h be separated with yttrium for gallium record;

Kerosene: <5g/h.

Can be inferred by the result shown in Figure 15, extraction be present in rare earth element in the lixiviate composition of acquisition and rare metal finally can by method of the present disclosure, those methods such as, provided in embodiment 4 and 5, are separated.

Method of the present disclosure provides the multiple important advantage and difference that exceed currently known methods.

Skilled person in the art will appreciate that the method for Extraction of rare earth element and rare metal described in the disclosure may be used for processing various parent material.Such as, any composition comprising at least one rare earth element and/or at least one rare earth metal can be used as parent material.Such as, any composition comprising at least one iron ion and at least one rare earth element can be used as parent material.

Those skilled in the art can understand thus, and method of the present disclosure can in conjunction with for the treatment of alumina-bearing material and derivative thereof, containing Zinc material and derivative, copper-bearing materials and derivative thereof, nickel-containing material and derivative thereof, use containing the various methods of magnesium material and derivative and titanium-containing materials.

In fact, can to alumina-bearing material and derivative, iron-bearing materials and derivative thereof, containing Zinc material and derivative, copper-bearing materials and derivative thereof, nickel-containing material and derivative thereof, carry out various different process containing magnesium material and titanium-containing materials and derivative thereof.

Therefore represent, method of the present disclosure is effectively for providing Extraction of rare earth element for existing solution.In addition, demonstrate, this replacement scheme provided by the method is cost-benefit replacement scheme and eco-friendly solution.

Although be described in particular with reference to specific embodiment, it should be understood that to its many amendments be obvious to those skilled in the art.Therefore, above explanation and accompanying drawing as specific examples, and should not have limited significance.

Claims

1. reclaim the method for at least one rare earth element, described method comprises:

Adopting extraction agent, ion exchange resin and/or by making described composition and reductive agent react, from described acidic composition, removing described at least one iron ion at least in part, obtain the composition of described at least one iron ion content reduction thus; And

The described composition that described at least one iron ion content is reduced and precipitation agent react, with substantially optionally make the first rare earth element and optionally first rare metal precipitation.

2. the method for claim 1, wherein said acidic composition comprises (i) described at least one rare earth element and optionally described at least one rare metal and (ii) FeCl ₃.

3. method as claimed in claim 1 or 2, wherein said extraction agent is selected from Tributyl phosphate ester, two-2-ethylhexyl phosphoric acids (HDEHP), two (2,4,4-tri-methyl-amyl) phospho acid and 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester.

4. method as claimed in claim 1 or 2, wherein said extraction agent is Tributyl phosphate ester.

5. method as claimed in claim 1 or 2, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

6. the method according to any one of claim 1 to 5, wherein makes described acidic composition and Fe (0) react, obtains Fe thus ³⁺the composition that content reduces.

7. the method according to any one of claim 1 to 6, wherein said first rare earth element is scandium.

8. the method according to any one of claim 1 to 7, wherein said acidic composition comprises at least one rare metal.

9. method as claimed in claim 8, wherein said method comprises described composition that described at least one iron ion content is reduced and described precipitation agent reacts substantially optionally precipitate described first rare earth element and described first rare metal.

10. method as claimed in any one of claims 1-9 wherein, wherein said first rare metal is gallium.

11. methods according to any one of claim 1 to 10, wherein said precipitation agent is selected from oxalic acid, NaOH, MgO, CaCO ₃and composition thereof.

12. methods according to any one of claim 1 to 10, wherein said precipitation agent is CaCO ₃.

13. methods according to any one of claim 1 to 12, wherein by maintain pH value lower than 2 by described first rare earth element and optionally described first rare metal substantially optionally precipitate.

14. methods according to any one of claim 1 to 12, wherein by maintain pH value for about 1 to about 2 by described first rare earth element and optionally described first rare metal substantially optionally precipitate.

15. methods according to any one of claim 1 to 12, wherein by the redox-potential that maintains about+380mV by described first rare earth element and optionally described first rare metal substantially optionally precipitate.

16. methods according to any one of claim 1 to 15, it comprises described composition that described at least one iron ion content is reduced and described precipitation agent and reacts substantially optionally precipitate the first rare earth element in the throw out that is included in and formed thus and the first rare metal, and reclaims described throw out.

17. methods as claimed in claim 16, it also comprises and carries out lixiviate to described throw out and obtain extracting solution.

18. methods as claimed in claim 17, wherein adopt HCl to carry out lixiviate to described throw out.

19. methods as claimed in claim 18, wherein said HCl has the concentration of about 5mol/L to about 15mol/L.

20. methods according to any one of claim 17 to 19, wherein adopt extraction agent to extract further described extracting solution, substantially optionally to extract described first rare earth element and described first rare metal, and obtain load organic phases.

21. methods as claimed in claim 20, wherein said extraction agent is Tributyl phosphate ester.

22. methods as claimed in claim 20, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

23. methods as claimed in claim 20, wherein said extraction agent is under isodecyl alcohol exists and in kerosene Tributyl phosphate ester.

24. methods according to any one of claim 20 to 23, it also comprises and adopts washing soln described load organic phases to be washed to the organic phase through washing reclaiming described first rare earth element and obtain.

25. methods as claimed in claim 24, wherein said washing soln is comprise the acidic aqueous solution that concentration is the HCl of about 2mol/L to about 12mol/L.

26. methods as described in claim 24 or 25, wherein with the washing soln of about 1:1: the ratio of load organic phases uses described washing soln.

27. methods according to any one of claim 24 to 26, it also comprises and adopts stripping solution to strip to reclaim described first rare metal to the described organic phase through washing.

28. methods as claimed in claim 27, wherein said stripping solution is water.

29. methods as described in claim 27 or 28, wherein with the stripping solution of about 1:2: the ratio of load organic phases uses described stripping solution.

30. methods according to any one of claim 13 to 28, the described composition wherein making described at least one iron ion content reduce and described precipitation agent react, comprise the liquid of the other rare earth element of at least one to obtain and comprise the described throw out of described first rare earth element and described first rare metal, described method also comprises and being separated from described throw out by described liquid.

31. methods as claimed in claim 30, it also comprises makes described liquid and another precipitation agent react to obtain another throw out, and reclaims another throw out described.

32. methods as claimed in claim 31, wherein make described liquid and another precipitation agent described react under the pH value of about 7.8 to about 8.2.

33. methods as claimed in claim 31, wherein make described liquid and described another kind of precipitation agent react under the pH value of about 7.9 to about 8.1.

34. methods according to any one of claim 31 to 33, the redox-potential wherein by maintaining about+340mV makes described liquid and described another kind of precipitation agent react.

35. methods according to any one of claim 31 to 33, the redox-potential wherein by maintaining about+380mV makes described liquid and another precipitation agent described react.

36. methods according to any one of claim 31 to 35, the temperature wherein by maintaining about 50 DEG C to about 70 DEG C makes described liquid and another precipitation agent described react.

37. methods according to any one of claim 31 to 36, another precipitation agent wherein said is selected from NaOH, MgO, CaCO ₃and composition thereof.

38. methods according to any one of claim 31 to 36, another precipitation agent wherein said is CaCO ₃.

39. methods according to any one of claim 31 to 38, it also comprises and carries out lixiviate to another throw out described and obtain the extracting solution comprising the second rare earth element.

40. methods as claimed in claim 39, wherein adopt HCl to carry out lixiviate to another throw out described.

41. methods as described in claim 39 or 40, wherein, adopt extraction agent to extract the described extracting solution comprising described second rare earth element, comprise the load organic phases of described second rare earth element substantially optionally to extract described second rare earth element and to obtain and comprise the aqueous phase of at least one light rare earths.

42. methods as claimed in claim 41, wherein said extraction agent is two (ethylhexyl) phosphonic acids.

43. methods as claimed in claim 41, wherein said extraction agent is two in kerosene (ethylhexyl) phosphonic acids.

44. methods according to any one of claim 41 to 43, it also comprises removes the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

45. methods according to any one of claim 41 to 43, it also comprises by adopting load organic phases described in acidic cleaning solution-treated to remove the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

46. methods as claimed in claim 45, wherein said washing soln comprises the HCl of 1N.

47. methods as described in claim 45 or 46, wherein said 3rd rare earth element is cerium.

48. methods according to any one of claim 45 to 47, it also comprises and adopts acidic strip to get solution-treated to comprise the described load organic phases of described second rare earth element to obtain the strip liquor comprising described second rare earth element, and reclaims described strip liquor.

49. methods as claimed in claim 48, wherein said strip liquor comprises the HCl of 3.5N.

50. methods as described in claim 48 or 49, it comprises and adopts extraction agent pack processing containing the described strip liquor of described second rare earth element substantially optionally to extract the 4th rare earth element and optionally the 5th rare earth element from described strip liquor, and acquisition comprises the raffinate of described second rare earth element.

51. methods as claimed in claim 50, wherein said extraction agent is Tributyl phosphate ester.

52. methods as claimed in claim 50, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

53. methods according to any one of claim 50 to 52, wherein said 4th rare earth element is dysprosium.

54. methods according to any one of claim 50 to 53, wherein said 5th rare earth element is erbium.

55. methods according to any one of claim 50 to 54, it also comprises makes to comprise described 4th rare earth element and optionally the organic phase of described 5th rare earth element and stripping solution react, to obtain the strip liquor comprising described 5th rare earth element and optionally described 5th rare earth element.

56. methods as claimed in claim 55, wherein said stripping solution is water.

57. methods according to any one of claim 41 to 56, wherein said second rare earth element is yttrium.

58. methods as described in claim 39 or 40, wherein adopt extraction agent to extract the described extracting solution comprising described second rare earth element, comprise the load organic phases of described second rare earth element substantially optionally to extract described second rare earth element and to obtain and comprise the raffinate of at least one light rare earths.

59. methods as claimed in claim 58, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

60. methods as described in claim 58 or 59, it also comprises removes the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

61. methods according to any one of claim 58 to 60, it also comprises by adopting load organic phases described in acidic cleaning solution-treated to remove the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

62. methods as claimed in claim 61, wherein said washing soln comprises the HCl of about 1N to about 2N.

63. methods as described in claim 61 or 62, it also comprises and adopts stripping solution pack processing containing the described load organic phases of described second rare earth element to obtain the strip liquor comprising described second rare earth element.

64. methods as described in claim 64, wherein said stripping solution comprises the HCl of about 3M to about 4M.

65. methods as described in claim 63 or 64, wherein, adopt extraction agent to extract to remove the 4th rare earth element and optionally the 5th rare earth element to the described strip liquor comprising described second rare earth element, thus obtain the raffinate that comprises described second rare earth element and the load organic phases comprising described 4th rare earth element and optionally described 5th rare earth element.

66. methods as described in claim 65, wherein said extraction agent is Tributyl phosphate ester.

67. methods as described in claim 65, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

68. methods according to any one of claim 65 to 67, it comprises the described raffinate reclaiming and comprise described second rare earth element.

69. methods according to any one of claim 65 to 68, wherein said second rare earth element is yttrium.

70. methods according to any one of claim 65 to 69, wherein said 4th rare earth element is dysprosium.

71. methods according to any one of claim 65 to 70, wherein said 5th rare earth element is erbium.

72. methods according to any one of claim 65 to 71, it also comprises the described load organic phases that makes to comprise described 4th rare earth element and described 5th rare earth element and stripping solution reacts, to obtain the strip liquor comprising described 4th rare earth element and described 5th rare earth element.

73. methods as described in claim 72, wherein said stripping solution is water.

74. methods as described in claim 72 or 73, it also comprises makes described strip liquor and extraction agent react substantially optionally extract described 5th rare earth element from described strip liquor, obtains thus and comprises the raffinate of described 4th rare earth element and comprise the load organic phases of described 5th rare earth element.

75. methods as described in claim 74, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

76. methods as described in claim 74 or 75, it also comprises makes described raffinate be separated from the described load organic phases comprising described 5th rare earth element, adopt load organic phases described in washing soln process therefrom to remove impurity, then adopt load organic phases described in stripping solution process to obtain the strip liquor comprising described 5th rare earth element.

77. methods as described in claim 76, wherein said washing soln comprises the HCl of about 2M to about 4M.

78. methods as described in claim 76 or 77, wherein said stripping solution comprises the HCl of about 3M to about 4M.

79. methods according to any one of claim 58 to 60, wherein, make described raffinate and oxidant reaction to be oxidized by described 3rd rare earth element.

80. methods as described in claim 79, wherein said oxygenant comprises clorox.

81. methods as described in claim 79 or 80, wherein make described raffinate and oxidant reaction under the pH value of about 0.5 to about 1.5.

82. methods according to any one of claim 79 to 81, it also comprises the 3rd rare earth element through oxidation removing precipitated form from described raffinate, obtains the filtrate comprising the 6th rare earth element thus.

83. methods as described in claim 82, it also comprises makes described filtrate and extraction agent react from described filtrate, substantially optionally extract described 6th rare earth element, obtain thus and comprise the load organic phases of described 6th rare earth element and comprise another raffinate of the 7th rare earth element and the 8th rare earth element, and the described load organic phases comprising described 6th rare earth element is separated from described raffinate.

84. methods as described in claim 83, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

85. methods as described in claim 83 or 84, it also comprises and adopts load organic phases described in washing soln process therefrom to remove impurity, then adopts load organic phases described in stripping solution process to obtain the strip liquor comprising described 6th rare earth element.

86. methods as described in claim 85, wherein said washing soln comprises the HCl of about 0.5M to about 1.5M.

87. methods as described in claim 85 or 86, wherein said stripping solution comprises the HCl of about 2M to about 3M.

88. methods according to any one of claim 83 to 87, wherein said 6th rare earth element is europium.

89. methods according to any one of claim 83 to 88, wherein said 7th rare earth element is praseodymium.

90. methods according to any one of claim 83 to 88, wherein said 8th rare earth element is neodymium.

91. methods according to any one of claim 83 to 90, it also comprises and adopts reductive agent to reduce described 6th rare earth element.

92. methods as described in claim 91, wherein said reductive agent is zinc (0).

93. methods according to any one of claim 83 to 92, it also comprises makes described 6th rare earth element and sodium sulfate react its sulfate-derivatives to obtain precipitated form, and reclaims described throw out.

94. methods according to any one of claim 83 to 92, it also comprises the described raffinate that makes to comprise described 7th rare earth element and described 8th rare earth element and extraction agent reacts, substantially optionally to extract described 8th rare earth element from described raffinate, obtain thus and comprise the load organic phases of described 8th rare earth element and comprise the raffinate of described 7th rare earth element, and the described load organic phases comprising described 8th rare earth element is separated from described raffinate.

95. methods as described in claim 94, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

96. methods as described in claim 94 or 95, it also comprises and adopts load organic phases described in washing soln process therefrom to remove impurity, then adopts load organic phases described in stripping solution process to obtain the strip liquor comprising described 8th rare earth element.

97. methods as described in claim 96, wherein said washing soln comprises the HCl of about 2M to about 3M.

98. methods as described in claim 96 or 97, wherein said stripping solution comprises the HCl of about 3M to about 4M.

The method of 99. recovery at least one rare earth elements, described method comprises:

Described composition and precipitation agent are reacted, substantially optionally to precipitate the first rare earth element and optionally the first rare metal.

100. methods as described in claim 99, wherein said first rare earth element is scandium.

101. methods as described in claim 99 or 100, wherein said acidic composition comprises at least one rare metal.

102. methods as described in claim 101, wherein said method comprises makes described composition and described precipitation agent react, substantially optionally to precipitate described first rare earth element and described first rare metal.

103. methods according to any one of claim 99 to 102, wherein said first rare metal is gallium.

104. methods according to any one of claim 99 to 103, wherein said precipitation agent is selected from NaOH, MgO, CaCO ₃and composition thereof.

105. methods according to any one of claim 99 to 103, wherein said precipitation agent is CaCO ₃.

106. methods according to any one of claim 99 to 105, wherein by maintain pH value lower than 2 by described first rare earth element and optionally described first rare metal substantially optionally precipitate.

107. methods according to any one of claim 99 to 105, wherein by maintain pH value about 1 to about 2 by described first rare earth element and optionally described first rare metal substantially optionally precipitate.

108. methods according to any one of claim 99 to 107, wherein by the redox-potential that maintains about+380mV by described first rare earth element and optionally described first rare metal substantially optionally precipitate.

109. methods according to any one of claim 99 to 108, it comprises makes described composition and described precipitation agent react, substantially optionally to precipitate the first rare earth element and the first rare metal that are included in the throw out formed thus, and reclaim described throw out.

110. methods as described in claim 109, it also comprises and carries out lixiviate to described throw out and obtain extracting solution.

111. methods as described in claim 110, wherein, adopt HCl to carry out lixiviate to described throw out.

112. methods as described in claim 111, wherein said HCl has the concentration of about 5mol/L to about 15mol/L.

113. methods according to any one of claim 110 to 112, wherein adopt extraction agent to extract further described extracting solution, substantially optionally to extract described first rare earth element and described first rare metal, and obtain load organic phases.

114. methods as described in claim 113, wherein said extraction agent is Tributyl phosphate ester.

115. methods as described in claim 113, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

116. methods as described in claim 113, wherein said extraction agent is under isodecyl alcohol exists and in kerosene Tributyl phosphate ester.

117. methods according to any one of claim 113 to 116, it also comprises and adopts washing soln described load organic phases to be washed to the organic phase through washing reclaiming described first rare earth element and obtain.

118. methods as described in claim 117, wherein said washing soln is comprise the acidic aqueous solution that concentration is the HCl of about 2mol/L to about 12mol/L.

119. methods as described in claim 117 or 118, wherein with the washing soln of about 1:1: the ratio of load organic phases uses described washing soln.

120. methods according to any one of claim 117 to 119, it also comprises and adopts stripping solution to strip to reclaim described first rare metal to the described organic phase through washing.

121. methods as described in claim 120, wherein said stripping solution is water.

122. methods as described in claim 120 or 121, wherein with the stripping solution of about 1:2: the ratio of load organic phases uses described stripping solution.

123. methods according to any one of claim 110 to 122, described composition and described precipitation agent is wherein made to react, comprise the liquid of the other rare earth element of at least one to obtain and comprise the described throw out of described rare earth element and described first rare metal, described method also comprises makes described liquid be separated from described throw out.

124. methods as described in claim 123, it also comprises makes described liquid and another precipitation agent react to obtain another throw out, and reclaims another throw out described.

125. methods as described in claim 124, wherein make described liquid and another precipitation agent described react under the pH value of about 7.8 to about 8.2.

126. methods as described in claim 124, wherein, make described liquid and another precipitation agent described react under the pH value of about 7.9 to about 8.1.

127. methods according to any one of claim 124 to 126, the redox-potential wherein by maintaining about+340mV makes described liquid and another precipitation agent described react.

128. methods according to any one of claim 124 to 126, the redox-potential wherein by maintaining about+380mV makes described liquid and another precipitation agent described react.

129. methods according to any one of claim 124 to 128, the temperature wherein by maintaining about 50 DEG C to about 70 DEG C makes described liquid and another precipitation agent described react.

130. methods according to any one of claim 124 to 129, another precipitation agent wherein said is selected from NaOH, MgO, CaCO ₃and composition thereof.

131. methods according to any one of claim 124 to 129, another precipitation agent wherein said is CaCO ₃.

132. methods according to any one of claim 124 to 131, it also comprises and carries out lixiviate to another throw out described and obtain the extracting solution comprising the second rare earth element.

133. methods as described in claim 132, wherein adopt HCl to carry out lixiviate to another throw out described.

134. methods as described in claim 132 or 133, wherein, adopt extraction agent to extract the described extracting solution comprising described second rare earth element, comprise the load organic phases of described second rare earth element substantially optionally to extract described second rare earth element and to obtain and comprise the aqueous phase of at least one light rare earths.

135. methods as described in claim 134, wherein said extraction agent is two (ethylhexyl) phosphonic acids.

136. methods as described in claim 134, wherein said extraction agent is two in kerosene (ethylhexyl) phosphonic acids.

137. methods according to any one of claim 134 to 136, it also comprises removes the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

138. methods according to any one of claim 134 to 137, it also comprises by adopting load organic phases described in acidic cleaning solution-treated to remove the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

139. methods as described in claim 138, wherein said washing soln comprises the HCl of 1N.

140. methods as described in claim 138 or 139, wherein said 3rd rare earth element is cerium.

141. methods according to any one of claim 138 to 140, it also comprises adopt acidic strip to get described load organic phases that solution-treated comprises described second rare earth element to obtain the strip liquor comprising described second rare earth element, and reclaims described strip liquor.

142. methods as described in claim 141, wherein said strip liquor comprises the HCl of 3.5N.

143. methods as described in claim 141 or 142, it comprises and adopts extraction agent pack processing containing the described strip liquor of described second rare earth element substantially optionally to extract the 4th rare earth element and optionally the 5th rare earth element from described strip liquor, and acquisition comprises the raffinate of described second rare earth element.

144. methods as described in claim 143, wherein said extraction agent is Tributyl phosphate ester.

145. methods as described in claim 143, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

146. methods according to any one of claim 143 to 145, wherein said 4th rare earth element is dysprosium.

147. methods according to any one of claim 143 to 146, wherein said 5th rare earth element is erbium.

148. methods according to any one of claim 143 to 147, it also comprises makes to comprise described 4th rare earth element and optionally the organic phase of described 5th rare earth element and stripping solution react, to obtain the strip liquor comprising described 5th rare earth element and optionally described 5th rare earth element.

149. methods as described in claim 148, wherein said stripping solution is water.

150. methods according to any one of claim 134 to 149, wherein said second rare earth element is yttrium.

151. methods as described in claim 132 or 133, wherein, adopt extraction agent to extract the described extracting solution comprising described second rare earth element, comprise the load organic phases of described second rare earth element substantially optionally to extract described second rare earth element and to obtain and comprise the raffinate of at least one light rare earths.

152. methods as described in claim 151, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

153. methods as described in claim 151 or 152, it also comprises removes the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

154. methods according to any one of claim 151 to 153, it also comprises by adopting load organic phases described in acidic cleaning solution-treated to remove the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

155. methods as described in claim 154, wherein said washing soln comprises the HCl of about 1N to about 2N.

156. methods as described in claim 154 or 155, it also comprises and adopts stripping solution pack processing containing the described load organic phases of described second rare earth element to obtain the strip liquor comprising described second rare earth element.

157. methods as described in claim 156, wherein said stripping solution comprises the HCl of about 3M to about 4M.

158. methods as described in claim 156 or 157, wherein, adopt extraction agent to extract to remove the 4th rare earth element and optionally the 5th rare earth element to the described strip liquor comprising described second rare earth element, thus obtain the raffinate that comprises described second rare earth element and the load organic phases comprising described 4th rare earth element and optionally described 5th rare earth element.

159. methods as described in claim 158, wherein said extraction agent is Tributyl phosphate ester.

160. methods as described in claim 158, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

161. methods according to any one of claim 158 to 160, it comprises the described raffinate reclaiming and comprise described second rare earth element.

162. methods according to any one of claim 158 to 160, wherein said second rare earth element is yttrium.

163. methods according to any one of claim 158 to 162, wherein said 4th rare earth element is dysprosium.

164. methods according to any one of claim 158 to 162, wherein said 5th rare earth element is erbium.

165. methods according to any one of claim 158 to 164, it also comprises the described load organic phases that makes to comprise described 4th rare earth element and described 5th rare earth element and stripping solution reacts, to obtain the strip liquor comprising described 4th rare earth element and described 5th rare earth element.

166. methods as described in claim 165, wherein said stripping solution is water.

167. methods as described in claim 165 or 166, it also comprises makes described strip liquor and extraction agent react substantially optionally extract described 5th rare earth element from described strip liquor, obtains thus and comprises the raffinate of described 4th rare earth element and comprise the load organic phases of described 5th rare earth element.

168. methods as described in claim 167, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

169. methods as described in claim 167 or 168, it also comprises makes described raffinate be separated from the described load organic phases comprising described 5th rare earth element, adopt load organic phases described in washing soln process therefrom to remove impurity, then adopt load organic phases described in stripping solution process to obtain the strip liquor comprising described 5th rare earth element.

170. methods as described in claim 169, wherein said washing soln comprises the HCl of about 2M to about 4M.

171. methods as described in claim 169 or 170, wherein said stripping solution comprises the HCl of about 3M to about 4M.

Method according to any one of 172. claims 151 to 153, wherein, makes described raffinate and oxidant reaction to be oxidized by described 3rd rare earth element.

Method described in 173. claims 172, wherein said oxygenant comprises clorox.

Method described in 174. claims 172 or 173, wherein, makes described raffinate and oxidant reaction under the pH value of about 0.5 to about 1.5.

Method according to any one of 175. claims 172 to 174, it also comprises the 3rd rare earth element through oxidation removing precipitated form from described raffinate, obtains the filtrate comprising the 6th rare earth element thus.

176. methods as described in claim 175, it also comprises makes described filtrate and extraction agent react from described filtrate, substantially optionally extract described 6th rare earth element, obtain thus and comprise the load organic phases of described 6th rare earth element and comprise another raffinate of the 7th rare earth element and the 8th rare earth element, and the described load organic phases comprising described 6th rare earth element is separated from described raffinate.

177. methods as described in claim 176, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

178. methods as described in claim 176 or 177, it also comprises and adopts load organic phases described in washing soln process therefrom to remove impurity, then adopts load organic phases described in stripping solution process to obtain the strip liquor comprising described 6th rare earth element.

179. methods as described in claim 178, wherein said washing soln comprises the HCl of about 0.5M to about 1.5M.

180. methods as described in claim 178 or 179, wherein said stripping solution comprises the HCl of about 2M to about 3M.

181. methods according to any one of claim 176 to 180, wherein said 6th rare earth element is europium.

182. methods according to any one of claim 176 to 181, wherein said 7th rare earth element is praseodymium.

183. methods according to any one of claim 176 to 182, wherein said 8th rare earth element is neodymium.

184. methods according to any one of claim 176 to 183, it also comprises and adopts reductive agent to reduce described 6th rare earth element.

185. methods as described in claim 184, wherein said reductive agent is zinc (0).

186. methods according to any one of claim 176 to 185, it also comprises makes described 6th rare earth element and sodium sulfate react its sulfate-derivatives to obtain precipitated form, and reclaims described throw out.

187. methods according to any one of claim 176 to 186, it also comprises the described raffinate that makes to comprise described 7th rare earth element and described 8th rare earth element and extraction agent reacts, substantially optionally to extract described 8th rare earth element from described raffinate, obtain thus and comprise the load organic phases of described 8th rare earth element and comprise the raffinate of described 7th rare earth element, and the described load organic phases comprising described 8th rare earth element is separated from described raffinate.

188. methods as described in claim 187, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

189. methods as described in claim 187 or 188, it also comprises and adopts load organic phases described in washing soln process therefrom to remove impurity, then adopts load organic phases described in stripping solution process to obtain the strip liquor comprising described 8th rare earth element.

190. methods as described in claim 189, wherein said washing soln comprises the HCl of about 2M to about 3M.

191. methods as described in claim 189 or 190, wherein said stripping solution comprises the HCl of about 3M to about 4M.

192. methods according to any one of claim 1 to 191, wherein said method also comprises and adopts ion exchange resin pre-treatment or process described acidic composition to remove impurity.

193. methods according to any one of claim 1 to 192, wherein said method also comprises, at least one rare earth element is being extracted and optionally before at least one rare metal from described acidic composition, adopt acidic composition described in ion exchange resin treatment, with at least in part from wherein removing impurity.

194. methods according to any one of claim 1 to 192, wherein said method also comprises using plasma torch to process the described at least one rare earth element that extracted by described method and optionally described at least one rare metal, to be further purified described at least one rare earth element and optionally described at least one rare metal.

The method of 195. recovery at least one rare earth elements, described method comprises:

Obtain acidic composition, described acidic composition comprises (i) at least one rare earth element and optionally at least one rare metal; And (ii) at least one metal ion;

Adopting extraction agent, ion exchange resin and/or by making described composition and reductive agent react, from described acidic composition, removing described at least one metal ion at least in part, obtain the composition of described at least one metal ion content reduction thus; And

The described composition that described at least one metal ion content is reduced and precipitation agent react, with substantially optionally make the first rare earth element and optionally first rare metal precipitation.

196. methods as described in claim 195, wherein said acidic composition comprises (i) described at least one rare earth element and described at least one rare metal.

197. methods as described in claim 195 or 196, wherein said extraction agent is selected from Tributyl phosphate ester, two-2-ethylhexyl phosphoric acids (HDEHP), two (2,4,4-tri-methyl-amyl) phospho acid and 2-ethylhexyl phosphonic acid list-2-(ethyl hexyl) ester.

198. methods as described in claim 195 or 196, wherein said extraction agent is Tributyl phosphate ester.

199. methods as described in claim 195 or 196, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

200. methods according to any one of claim 195 to 199, wherein said at least one metal ion comprises at least one aluminum ion, at least one zine ion, at least one cupric ion, at least one nickel ion, at least one magnesium ion, at least one titanium particle and/or at least one iron ion.

201. methods according to any one of claim 195 to 200, wherein said first rare earth element is scandium.

202. methods according to any one of claim 195 to 201, wherein said acidic composition comprises at least one rare metal.

203. methods as described in claim 202, wherein said method comprises described composition that described at least one metal ion content is reduced and described precipitation agent reacts substantially optionally precipitate described first rare earth element and described first rare metal.

204. methods according to any one of claim 195 to 203, wherein said first rare metal is gallium.

205. methods according to any one of claim 195 to 204, wherein said precipitation agent is selected from NaOH, MgO, CaCO ₃and composition thereof.

206. methods according to any one of claim 195 to 204, wherein said precipitation agent is CaCO ₃.

207. methods according to any one of claim 195 to 206, wherein by by maintain pH value lower than 2 by described first rare earth element and optionally described first rare metal substantially optionally precipitate.

208. methods according to any one of claim 195 to 206, wherein by maintain pH value for about 1 to about 2 by described first rare earth element and optionally described first rare metal substantially optionally precipitate.

209. methods according to any one of claim 195 to 206, wherein by the first rare earth element described in the redox-potential that maintains about+380mV and optionally described first rare metal substantially optionally precipitate.

210. methods according to any one of claim 195 to 209, it comprises described composition that described at least one metal ion content is reduced and described precipitation agent reacts, substantially optionally to precipitate the first rare earth element and the first rare metal that are included in the throw out formed thus, and reclaim described throw out.

211. methods as described in claim 210, it also comprises and carries out lixiviate to described throw out and obtain extracting solution.

212. methods as described in claim 211, wherein, adopt HCl to carry out lixiviate to described throw out.

213. methods as described in claim 211 or 212, wherein, adopt extraction agent to extract further described extracting solution, substantially optionally to extract described first rare earth element and described first rare metal, and obtain load organic phases.

214. methods as described in claim 213, wherein said extraction agent is Tributyl phosphate ester.

215. methods as described in claim 213, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

216. methods as described in claim 213, wherein said extraction agent is under isodecyl alcohol exists and in kerosene Tributyl phosphate ester.

217. methods according to any one of claim 214 to 216, it also comprises and adopts washing soln described load organic phases to be washed to the organic phase through washing reclaiming described first rare earth element and obtain.

218. methods as described in claim 217, wherein said washing soln is comprise the acidic aqueous solution that concentration is the HCl of about 2mol/L to about 12mol/L.

219. methods as described in claim 217 or 218, wherein with the washing soln of about 1:1: the ratio of load organic phases uses described washing soln.

220. methods according to any one of claim 217 to 219, it also comprises and adopts stripping solution to strip to reclaim described first rare metal to the described organic phase through washing.

221. methods as described in claim 220, wherein said stripping solution is water.

222. methods as described in claim 220 or 221, wherein with the stripping solution of about 1:2: the ratio of load organic phases uses described stripping solution.

223. methods according to any one of claim 207 to 222, the described composition wherein making described at least one metal ion content reduce and described precipitation agent react, comprise the liquid of the other rare earth element of at least one to obtain and comprise the described throw out of described first rare earth element and described first rare metal, described method also comprises and being separated from described throw out by described liquid.

224. methods as described in claim 223, it also comprises makes described liquid and another precipitation agent react to obtain another throw out, and reclaims another throw out described.

225. methods as described in claim 224, wherein, make described liquid and another precipitation agent described react under the pH value of about 7.8 to about 8.2.

226. methods as described in claim 224, wherein, make described liquid and another precipitation agent described react under the pH value of about 7.9 to about 8.1.

227. methods according to any one of claim 224 to 226, the redox-potential wherein by maintaining about+340mV makes described liquid and another precipitation agent described react.

228. methods according to any one of claim 224 to 226, wherein, make described liquid and another precipitation agent described react by the redox-potential maintaining about+380mV.

229. methods according to any one of claim 224 to 228, the temperature wherein by maintaining about 50 DEG C to about 70 DEG C makes described liquid and another precipitation agent described react.

230. methods according to any one of claim 224 to 229, another precipitation agent wherein said is selected from NaOH, MgO, CaCO ₃and composition thereof.

231. methods according to any one of claim 224 to 229, wherein said precipitation agent is CaCO ₃.

232. methods according to any one of claim 224 to 231, it also comprises and carries out lixiviate to another throw out described and obtain the extracting solution comprising the second rare earth element.

233. methods as described in claim 232, wherein, adopt HCl to carry out lixiviate to another throw out described.

234. methods as described in claim 232 or 233, wherein, adopt extraction agent to extract the described extracting solution comprising described second rare earth element, comprise the load organic phases of described second rare earth element substantially optionally to extract described second rare earth element and to obtain and comprise the aqueous phase of at least one light rare earths.

235. methods as described in claim 234, wherein said extraction agent is two (ethylhexyl) phosphonic acids.

236. methods as described in claim 234, wherein said extraction agent is two in kerosene (ethylhexyl) phosphonic acids.

237. methods according to any one of claim 234 to 236, it also comprises removes the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

238. methods according to any one of claim 234 to 236, it also comprises by adopting load organic phases described in acidic cleaning solution-treated to remove the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

239. methods as described in claim 238, wherein said washing soln comprises the HCl of 1N.

240. methods as described in claim 238 or 239, wherein said 3rd rare earth element is cerium.

241. methods according to any one of claim 238 to 240, it also comprises adopt acidic strip to get described load organic phases that solution-treated comprises described second rare earth element to obtain the strip liquor comprising described second rare earth element, and reclaims described strip liquor.

242. methods as described in claim 241, wherein said strip liquor comprises the HCl of 3.5N.

243. methods as described in claim 241 or 242, it comprises and adopts extraction agent pack processing containing the described strip liquor of described second rare earth element substantially optionally to extract the 4th rare earth element and optionally the 5th rare earth element from described strip liquor, and acquisition comprises the raffinate of described second rare earth element.

244. methods as described in claim 243, wherein said extraction agent is Tributyl phosphate ester.

245. methods as described in claim 243, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

246. methods according to any one of claim 243 to 245, wherein said 4th rare earth element is dysprosium.

247. methods according to any one of claim 243 to 245, wherein said 5th rare earth element is erbium.

248. methods according to any one of claim 243 to 247, it also comprises makes to comprise described 4th rare earth element and optionally the organic phase of described 5th rare earth element and stripping solution react, to obtain the strip liquor comprising described 5th rare earth element and optionally described 5th rare earth element.

249. methods as described in claim 248, wherein said stripping solution is water.

250. methods according to any one of claim 234 to 249, wherein said second rare earth element is yttrium.

251. methods as described in claim 232 or 233, wherein, adopt extraction agent to extract the described extracting solution comprising described second rare earth element, comprise the load organic phases of described second rare earth element substantially optionally to extract described second rare earth element and to obtain and comprise the raffinate of at least one light rare earths.

252. methods as described in claim 251, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

253. methods as described in claim 251 or 252, it also comprises removes the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

254. methods according to any one of claim 251 to 253, it also comprises by adopting load organic phases described in acidic cleaning solution-treated to remove the 3rd rare earth element at least in part from the described load organic phases comprising described second rare earth element.

255. methods as described in claim 254, wherein said washing soln comprises the HCl of about 1N to about 2N.

256. methods as described in claim 254 or 255, it also comprises and adopts stripping solution pack processing containing the described load organic phases of described second rare earth element to obtain the strip liquor comprising described second rare earth element.

257. methods as described in claim 256, wherein said stripping solution comprises the HCl of about 3M to about 4M.

258. methods as described in claim 256 or 257, wherein, adopt extraction agent to extract to remove the 4th rare earth element and optionally the 5th rare earth element to the described strip liquor comprising described second rare earth element, thus obtain the raffinate that comprises described second rare earth element and the load organic phases comprising described 4th rare earth element and optionally described 5th rare earth element.

259. methods as described in claim 258, wherein said extraction agent is Tributyl phosphate ester.

260. methods as described in claim 258, wherein said extraction agent is the Tributyl phosphate ester in kerosene.

261. methods according to any one of claim 258 to 260, it comprises the described raffinate reclaiming and comprise described second rare earth element.

262. methods according to any one of claim 258 to 261, wherein said second rare earth element is yttrium.

263. methods according to any one of claim 258 to 262, wherein said 4th rare earth element is dysprosium.

264. methods according to any one of claim 258 to 263, wherein said 5th rare earth element is erbium.

265. methods according to any one of claim 258 to 264, it also comprises the described load organic phases that makes to comprise described 4th rare earth element and described 5th rare earth element and stripping solution reacts, to obtain the strip liquor comprising described 4th rare earth element and described 5th rare earth element.

266. methods as described in claim 265, wherein said stripping solution is water.

267. methods as described in claim 265 or 266, it also comprises makes described strip liquor and extraction agent react substantially optionally extract described 5th rare earth element from described strip liquor, obtains thus and comprises the raffinate of described 4th rare earth element and comprise the load organic phases of described 5th rare earth element.

268. methods as described in claim 267, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

269. methods as described in claim 267 or 268, it also comprises makes described raffinate be separated with the described load organic phases comprising described 5th rare earth element, adopt load organic phases described in washing soln process therefrom to remove impurity, then adopt load organic phases described in stripping solution process to obtain the strip liquor comprising described 5th rare earth element.

270. methods as described in claim 269, wherein said washing soln comprises the HCl of about 2M to about 4M.

271. methods as described in claim 269 or 270, wherein said stripping solution comprises the HCl of about 3M to about 4M.

272. methods according to any one of claim 251 to 253, wherein, make described raffinate and oxidant reaction to be oxidized by described 3rd rare earth element.

273. methods as described in claim 272, wherein said oxygenant comprises clorox.

274. methods as described in claim 272 or 273, wherein, make described raffinate and oxidant reaction under the pH value of about 0.5 to about 1.5.

275. methods according to any one of claim 272 to 274, it also comprises the 3rd rare earth element through oxidation removing precipitated form from described raffinate, obtains the filtrate comprising the 6th rare earth element thus.

276. methods as described in claim 275, it also comprises makes described filtrate and extraction agent react from described filtrate, substantially optionally extract described 6th rare earth element, obtain thus and comprise the load organic phases of described 6th rare earth element and comprise another raffinate of the 7th rare earth element and the 8th rare earth element, and the described load organic phases comprising described 6th rare earth element is separated from described raffinate.

277. methods as described in claim 276, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

278. methods as described in claim 276 or 277, it also comprises and adopts load organic phases described in washing soln process therefrom to remove impurity, then adopts load organic phases described in stripping solution process to obtain the strip liquor comprising described 6th rare earth element.

279. methods as described in claim 278, wherein said washing soln comprises the HCl of about 0.5M to about 1.5M.

280. methods as described in claim 278 or 279, wherein said stripping solution comprises the HCl of about 2M to about 3M.

281. methods according to any one of claim 276 to 280, wherein said 6th rare earth element is europium.

282. methods according to any one of claim 276 to 281, wherein said 7th rare earth element is praseodymium.

283. methods according to any one of claim 276 to 282, wherein said 8th rare earth element is neodymium.

284. methods according to any one of claim 276 to 283, it also comprises and adopts reductive agent to reduce described 6th rare earth element.

285. methods as described in claim 284, wherein said reductive agent is zinc (0).

286. methods according to any one of claim 276 to 285, it also comprises makes described 6th rare earth element and sodium sulfate react its sulfate-derivatives to obtain precipitated form, and reclaims described throw out.

287. methods according to any one of claim 276 to 285, it also comprises the described raffinate that makes to comprise described 7th rare earth element and described 8th rare earth element and extraction agent reacts, substantially optionally to extract described 8th rare earth element from described raffinate, obtain thus and comprise the load organic phases of described 8th rare earth element and comprise the raffinate of described 7th rare earth element, and the described load organic phases comprising described 8th rare earth element is separated from described raffinate.

288. methods as described in claim 287, wherein said extraction agent is two (ethylhexyl) phosphonic acids or two-(2-ethylhexyl) phosphoric acid.

289. methods as described in claim 287 or 288, it also comprises and adopts load organic phases described in washing soln process therefrom to remove impurity, then adopts load organic phases described in stripping solution process to obtain the strip liquor comprising described 8th rare earth element.

290. methods as described in claim 289, wherein said washing soln comprises the HCl of about 2M to about 3M.

291. methods as described in claim 289 or 290, wherein said stripping solution comprises the HCl of about 3M to about 4M.

292. methods according to any one of claim 195 to 291, wherein said at least one metal ion is the ion of the metal being selected from aluminium, iron, zinc, copper, nickel, magnesium and titanium.

293. methods according to any one of claim 195 to 292, wherein said method also comprises and adopts ion exchange resin pre-treatment or process described acidic composition to remove impurity.

294. methods according to any one of claim 195 to 293, wherein said method also comprises, at least one rare earth element is being extracted and optionally before at least one rare metal from described acidic composition, adopt acidic composition described in ion exchange resin treatment, with at least in part from wherein removing impurity.

295. methods according to any one of claim 195 to 294, wherein said method also comprises using plasma torch to process the described at least one rare earth element that extracted by described method and optionally described at least one rare metal, to be further purified described at least one rare earth element and optionally described at least one rare metal.