CN102690954A

CN102690954A - Back extraction and removement method for aluminium

Info

Publication number: CN102690954A
Application number: CN2012100740488A
Authority: CN
Inventors: 荒川淳一
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2011-03-23
Filing date: 2012-03-20
Publication date: 2012-09-26

Abstract

The invention provides a method which can extract and remove aluminum from a solution containing aluminium. The characteristic is that an acid solution is added to an organic solvent containing aluminium, the pH value is adjusted to 0 to 0.5, and aluminium is back extracted to the acid solution.

Description

The anti-process for extracting of aluminium and remove method

Technical field

The method of removing that the present invention relates to a kind of anti-process for extracting of aluminium and use the aluminium of this method.

Background technology

Lithium ion battery is expanded rapidly as the purposes of Hybrid Vehicle, and then can infer that the turnout of the large-sized battery of being brought by unitary high capacity increases suddenly.In addition, for the expanded demand of lithium ion battery, require to establish valuable metal recovery method from lithium ion battery.

This lithium ion battery mainly is made up of positive pole, negative pole, distance piece, basket, and the anodal structure is: the static eliminator such as positive active material and carbon black that will comprise manganese, cobalt, nickel, lithium carries out mixing in the tackiness agent of fluorine system etc. and is coated on the current collector of aluminium foil.Positive electrode material is made up of with the binder layer that comprises positive active material the aluminium foil of about 15 microns of thickness, and outward appearance is the positive active material of painting black on aluminium foil.

As the recovery method of lithium ion battery, proposing has following method: burn the pulverizing waste lithium ion battery, carry out after acidleach goes out with the raw material after selecting, through solvent extraction various metals of extraction separation from the leach liquor that obtains.But when in raw material, comprising the aluminium of positive electrode material with the form of impurity, aluminium goes out to be leached through acidleach, can produce detrimentally affect to the extraction separation in the solvent extraction.Therefore, under the aluminiferous situation of bag, need remove aluminium in the leach liquor that obtains raw material being carried out acidleach go out.

As the method for removing of the aluminium in the acidic solution, propose to have neutralisation, Tai-Ace S 150 method, solvent-extraction process etc.As neutralisation, as patent documentation 1 (TOHKEMY 2004-33984) is disclosed, propose adds neutralizing agent such as sodium hydroxide and pH is neutralized to the method for 6～8 scope.In addition, as the Tai-Ace S 150 method, as patent documentation 2 (japanese kokai publication hei 1-153517) is put down in writing, propose with SO ₄/ Al mol ratio is 3/2～9/2 to carry out the method that concentrating under reduced pressure, cooling are separated out Tai-Ace S 150.

As use the process for extracting of the aluminium of solvent extraction is arranged, as patent documentation 3 (japanese kokai publication sho 63-25217) is disclosed, reported the extraction separation of the aluminium that utilizes acid phosphoric acid ester, can extract more than 99% of aluminium in the inorganic acid solution.

Patent documentation

Patent documentation 1: TOHKEMY 2004-33984 communique

Patent documentation 2: japanese kokai publication hei 1-153517 communique

Patent documentation 3: japanese kokai publication sho 63-25217 communique

Summary of the invention

, waste and old lithium ion battery has the high raw material of aluminium content in reclaiming.When leaching the high raw material of aluminium content, exist sometimes and comprise the such problem of high concentration of aluminium in the leach liquor.Recycle object metal during lithium ion battery reclaims is manganese, cobalt, nickel, lithium, and aluminium need separate as impurity.

But, in

patent documentation

1 or 2 in the neutralisation of record, the white lake generation gelation of separating out and make the filterableness variation, in addition, also exist because of in and the time co-precipitation make cobalt or nickel in the liquid also precipitate such problem.Also there is a large amount of vitriolic problem of needs in the Tai-Ace S 150 method.

On the other hand, in patent documentation 3 in the solvent-extraction process of record, though can reclaim aluminium,, do not report the separation method of aluminium and other metal.

Therefore, problem of the present invention is, a kind of anti-process for extracting that can from wrap aluminiferous solution, extract, remove the aluminium of aluminium with high-level efficiency is provided.

Concentrate on studies in order to solve said problem, the result finds, through adding anti-extraction of pH that acidic solution is adjusted to regulation to wrapping aluminiferous organic solvent, can extract, remove aluminium with high-level efficiency.

In this manual, " anti-extract " is meant the operation of from the organic solvent that is dissolved with aluminium, taking out aluminium, and has the operation of extracting aluminium in the solution of having no way of comprising aluminium irrelevant with its last stage.

With above opinion is the anti-process for extracting that one aspect of the invention is a kind of aluminium accomplished of basis, it is characterized in that, in wrapping aluminiferous organic solvent, adds acidic solution, and adjustment pH is 0～0.5 scope, makes that aluminium is counter to be extracted in the acidic solution.

In an embodiment of the anti-process for extracting of aluminium of the present invention, the aluminiferous organic solvent of said bag obtains through from wrap aluminiferous sulfuric acid solution at least, carrying out solvent extraction.

In another embodiment of the anti-process for extracting of aluminium of the present invention, organic solvent is the organic solvent that comprises 2-ethylhexyl phosphonic acid list-2-ethylhexyl.

In another embodiment of the anti-process for extracting of aluminium of the present invention, acidic solution is a sulphuric acid soln.

In another embodiment of the anti-process for extracting of aluminium of the present invention, the metal beyond the said aluminium is to be selected from least a in manganese, cobalt, nickel, the lithium.

Another aspect of the present invention is a kind of method of removing of aluminium, and it comprises following operation: abstraction process, and in wrapping aluminiferous sulfuric acid solution at least, the scope of adjustment pH to 1～3 is carried out solvent extraction to aluminium; Anti-abstraction process adds acidic solution in the aluminiferous organic solvent of the bag that said abstraction process obtains, the scope of adjustment pH to 0～0.5 makes that aluminium is counter to be extracted in the acidic solution.

According to the present invention, a kind of anti-process for extracting that can from wrap aluminiferous solution, extract, remove the aluminium of aluminium with high-level efficiency can be provided.

Description of drawings

Fig. 1 is illustrated in the removing in the method for aluminium of embodiment of the present invention, is that extraction agent carries out manganese, cobalt, nickel, the lithium under the situation of solvent extraction, the pH-extraction yield curve of aluminium with 2-ethylhexyl phosphonic acid list-2-ethylhexyl.

Fig. 2 is illustrated in removing in the anti-process for extracting in the method for the aluminium that is applied to embodiment of the present invention, from the solvent that has extracted aluminium, the aluminium that has used sulphuric acid soln is carried out the anti-extraction yield curve of pH-under the anti-extraction situation.

Embodiment

The method of removing of the aluminium of embodiment of the present invention can be preferred for from the waste and old lithium ion battery body, reclaiming the method for valuable metal; In more detail, can be preferred for extracting in the solution that produces when the positive electrode material that comprises the lithium ion battery is handled with high-level efficiency and remove method as the aluminium of impurity through solvent extraction and anti-.Below; To the aluminium in the leach liquor in through solvent extraction lithium ion battery being reclaimed carry out extraction separation and extract after the anti-situation about extracting of solvent describe; But the present invention does not receive the restriction of following Example, can be used for the various uses that is used for separation and Extraction or removes aluminium beyond it certainly yet.

The leach liquor that contains aluminium that the method for removing of the aluminium of embodiment of the present invention obtains in can lithium ion battery being reclaimed is as process object.That is, the process object liquid as raw material is the sulphuric acid soln that except that comprising aluminium, also comprises manganese, cobalt, nickel, lithium or other metal as the recycle object metal.This process object liquid comprises the sulfuric acid of 0.001～300g/L for example, the aluminium of 0.001～20g/L, the manganese of 0.001～30g/L, the cobalt of 0.001～30g/L, the nickel of 0.001～30g/L, the lithium of 0.001～30g/L.

Through solvent-extraction process extraction separation aluminium from this leach liquor.Extraction agent uses 2-ethylhexyl phosphonic acid list-2-ethylhexyl.Mix with the hydrocarbon system solvent and this extraction agent is diluted and the solvent and the aluminiferous above-mentioned sulphuric acid soln of bag that are prepared from and carry out the solvent extraction of aluminium.The ratio of mixture of 2-ethylhexyl phosphonic acid list-2-ethylhexyl and solvent is preferably 1: 3.As the hydrocarbon system solvent, fragrant family capable of using, alkane hydrocarbon system, naphthene series solvent etc., wherein preferred naphthene series solvent.

The relation of the balance pH when Fig. 1 representes solvent extraction and the extraction yield of each element.With regard to the balance pH when extracting with regard to aluminium, preferably add neutralizing agent be adjusted to more than 1.8, preferred more than 2, and be adjusted to below 3, preferred below 2.5, further preferred scope below 2.3.As neutralizing agent, can use sodium hydroxide, yellow soda ash etc.Balance pH is more than 13 when following, comprises in the solution under the situation of the metal beyond the aluminium such as cobalt, nickel, lithium, and metal and the aluminium that can suppress beyond these aluminium are extracted together, and the result can be more efficiently and optionally extracted aluminium, therefore preferably.Particularly in solution under the manganiferous situation of bag, through balance pH is made as 2 or more 2.5 below, preferred below 2.3, can suppress manganese and aluminium is extracted together, the result can be more efficiently and is optionally extracted aluminium, so preferably.

For the solvent that has extracted aluminium in the abstraction process, available acidic solution is counter to be extracted.As acidic solution, can use sulphuric acid soln, hydrochloric acid soln etc.The relation of the balance pH when Fig. 2 representes anti-extraction the and the extraction yield of aluminium.Balance pH during anti-the extraction preferably is adjusted to 0～0.5 scope.PH is higher than at 0.5 o'clock, and the anti-extraction of aluminium is not thorough, sometimes can residual aluminum in the solvent.In addition, pH is lower than at 0 o'clock, and acid concentration is high, and processing afterwards becomes difficulty.

Need to prove; In this embodiment; Suppress the example that metal beyond the aluminium carries out the anti-extraction of aluminium after being contained in the organic solvent and describe carry out solvent extraction with specific organic solvent in last stage of anti-abstraction process; Even but if metal, for example manganese, cobalt, nickel, lithium beyond the aluminium be contained in as in the anti-solution that extracts the object of handling, to the anti-extraction of aluminium, remove also almost not influence.

Embodiment

Below, the embodiment of the invention is described, but embodiment is used for example and does not mean that qualification the present invention.

(embodiment 1)

Sulphuric acid soln (H to the various metals that comprise table 1 record ₂SO ₄Concentration 10g/L) and with the naphthene series solvent (Shell Chemicals trade(brand)name: shellsol D70) (big eight commodity chemical names: PC-88A) the dilution solvent that is adjusted to 25vol% mixes stirring with the mode of organic phase/water=1 (volume ratio) with 2-ethylhexyl phosphonic acid list-2-ethylhexyl; Use sodium hydroxide to regulate, carry out the extraction of aluminium simultaneously so that balance pH is 2.3.The extraction yield of each element is shown in table 2.

Table 1

Element	Mn	Co	Ni	Li	Al
						Concentration (g/L)	2.5	2.6	2.6	0.9	0.9

Table 2

Element	Mn	Co	Ni	Li	Al
						Extraction yield (%)	15.7	0.0	0.0	0.0	97.3

(embodiment 2)

Sulphuric acid soln (the H that will comprise the various metals of table 1 record ₂SO ₄Concentration 10g/L) under balance pH is 2.7 condition, likewise carries out the extraction of aluminium with embodiment 1.The extraction yield of each element is shown in table 3.

Table 3

Element	Mn	Co	Ni	Li	Al
						Extraction yield (%)	25.0	0.0	0.0	0.0	99.5

(embodiment 3)

Sulphuric acid soln (the H that will comprise the various metals of table 1 record ₂SO ₄Concentration 10g/L) under balance pH is 1.9 condition, likewise carries out the extraction of aluminium with embodiment 1.The extraction yield of each element is shown in table 4.

Table 4

Element	Mn	Co	Ni	Li	Al
						Extraction yield (%)	6.0	0.0	0.0	0.0	63.9

(embodiment 4～18)

Sulphuric acid soln (the H that will comprise the various metals of table 1 record ₂SO ₄Concentration 10g/L) likewise carries out the extraction of aluminium with embodiment 1 under below the condition of balance pH,, the relation of the extraction yield of balance pH and each element is shown in Fig. 1 respectively as embodiment 4～18.

Balance pH when the Al among each embodiment of table 5 extracts

Can know that according to embodiment 1～18 with other compared with metal, aluminium is extracted expeditiously.Can know when particularly balance pH is between 1～3, demonstrate according to the metal difference of extracting object and extractability is different, optionally extract aluminium.And then can know balance pH 2～2.5, particularly between 2～2.3 the time, compare with manganese, optionally be extracted aluminium significantly.

(embodiment 19)

In order to extract, use sulphuric acid soln (H to the aluminium that is extracted in the solvent among the embodiment 1 is counter ₂SO ₄Concentration 20g/L), be anti-extraction the under 0.48 the condition at organic phase/water=1 (volume ratio), balance pH.To be shown in table 6 from the anti-extraction yield of the aluminium in the solvent.Can know that by table 6 93% the aluminium that comprises in the solvent is extracted by anti-.

Table 6

Element	Al
		Anti-extraction yield (%)	93.1

(embodiment 20)

In embodiment 19, be instead under 0.06 the condition to extract operation at balance pH, in addition and embodiment 19 operate the anti-aluminium that extracts from solvent equally.The relation of anti-extraction yield and pH is shown in Fig. 2.

(comparative example 1～5)

In embodiment 19, instead under the condition of balance pH below extract operation, in addition and embodiment 19 operate equally, to extracting from the aluminium in the solvent is counter.The relation of anti-extraction yield and pH is shown in Fig. 2.

Balance pH when the Al in each comparative example of table 7 extracts

Comparative example	1	2	3	4	5
						Balance pH	1.74	1.51	1.43	1.01	0.77

Can know according to Fig. 2,, need balance pH be made as below 0.5 in order to extract to the aluminium in the solvent is counter.

Claims

1. the anti-process for extracting of an aluminium is characterized in that, adds acidic solution at bag in the aluminiferous organic solvent, and the scope of adjustment pH to 0～0.5 makes that aluminium is counter to be extracted in the acidic solution.

2. method according to claim 1, wherein, the aluminiferous organic solvent of said bag obtains through from wrap aluminiferous sulfuric acid solution at least, carrying out solvent extraction.

3. method according to claim 1 and 2, wherein, said organic solvent is the organic solvent that comprises 2-ethylhexyl phosphonic acid list-2-ethylhexyl.

4. according to each described method in the claim 1～3, wherein, said acidic solution is a sulphuric acid soln.

5. according to each described method in the claim 1～4, wherein, the metal beyond the said aluminium is to be selected from least a in manganese, cobalt, nickel, the lithium.

6. the method for removing of an aluminium is characterized in that, said method comprises following operation:

Abstraction process, in wrapping aluminiferous sulfuric acid solution at least, the scope of adjustment pH to 1～3, and aluminium carried out solvent extraction;

Anti-abstraction process adds acidic solution in the aluminiferous organic solvent of the bag that said abstraction process obtains, the scope of adjustment pH to 0～0.5 makes that aluminium is counter to be extracted in the acidic solution.

7. method according to claim 6, wherein, said organic solvent is the organic solvent that comprises 2-ethylhexyl phosphonic acid list-2-ethylhexyl.

8. according to claim 6 or 7 described methods, wherein, said acidic solution is a sulphuric acid soln.

9. according to each described method in the claim 6～8, wherein, the metal beyond the said aluminium is to be selected from least a in manganese, cobalt, nickel, the lithium.