CN102345022B - Rare earth metal agglutinant - Google Patents
Rare earth metal agglutinant Download PDFInfo
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- CN102345022B CN102345022B CN2011102113496A CN201110211349A CN102345022B CN 102345022 B CN102345022 B CN 102345022B CN 2011102113496 A CN2011102113496 A CN 2011102113496A CN 201110211349 A CN201110211349 A CN 201110211349A CN 102345022 B CN102345022 B CN 102345022B
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Abstract
The invention relates to a technology for separating and recycling the terres rares having small ionic radius from the water solution blended with multiple types of terres rares. The invention also relates to an agglutinant used for separating and recycling specified terres rares from the water solution blended with multiple types of terres rares. The agglutinant is characterized by containing water-soluble macromolecules having acid perssad and the water-soluble macromolecules containing amino and with the main chain being a long chain. Further provided are a method and an apparatus for separating and recycling terres rares with the agglutinant.
Description
Technical field
The present invention relates to a kind of method that use is easy and will be mixed in the rare earth metal technology that particularly neodymium (Nd) in coupernick etc. and dysprosium (Dy) separate, specifically, relate to a kind of pharmaceutical chemicals of the separation for rare earth metal and separation method and the tripping device of rare earth metal.
Background technology
Magneticalloy for magnetic recording system or motor vehicle driven by mixed power etc., although main component is iron, but be added with the rare earth metals such as a small amount of neodymium, dysprosium in order to improve coercive force, calling out resource exhaustion now, the activity that the rare earth metals such as these neodymiums, dysprosium are separated, reclaim and recycle is accelerated.
As the existing general method for separating of rare earth metals such as Nd, Dy, can enumerate solvent extration.At first will be dissolved in strong acid containing the alloy of multiple rare earth metal, add extraction agent and the hydrocarbon organic solvent of phosphoric acid system.While being placed after it is stirred, according to the kind of extraction agent, various rare earth metals are distributed in (non-patent literature 1) in water and organic solvent by certain ratio.But, because the different rate variances that distribute of kind of rare earth metal are not bery large, repeatedly carry out the purity that above-mentioned solvent extration improves various metals.Because the distribution rate variance of Nd and Dy is not bery large, in order to make purity, reach more than 99%, allegedly to carry out the solvent extraction of tens of left and right.
The prior art document
Non-patent literature
Non-patent literature 1: resource treatment technology, the 37th volume, 157～164 (1990)
Summary of the invention
Invent problem to be solved
Because solvent extration is used hydrocarbon organic solvent, need to carry out recovery, the processing of solvent, carrying capacity of environment is large.In addition, because distributing rate variance little, need repeatedly tens of times.Due to these reasons, all as price comparison, high metal circulates for Nd and Dy, and circulation is also few.Therefore anticipation, follow the universal of motor vehicle driven by mixed power from now on, and both supplies will become important problem.Therefore, seek easy magnet that the product from scrapping comprises and reclaim efficiently Nd and Dy.
In addition, in addition, because the fluor of the use rare earth metal for cathode tube, PDP etc. be also worldwide huge amount, therefore also seeking from wherein separation, recovering rare earth metalloid.But various physics, the chemical property of rare earth metal are very close.For example, the electronegativity of rare earth metal is approximate, is 0.86～1.14, and particularly the Nd in coupernick is that 1.07, Dy is 1.10, quite approximate.Also approximate because of the ionic radius of rare earth metal, be 0.745～
particularly the Nd in coupernick is
dy is
(being trivalent ion), both are approximate, are difficult to be separated with usual method.In addition, the ionic radius of the rare-earth metal ion in this specification sheets is based on Matsumoto Kazuko's " chemistry of rare earth element ", towards storehouse bookstore, and the radius that August 25, the first edition first version obtained in 2008.
Therefore, the object of the invention is to, be provided for the separation, recovery method and the device that separate, reclaim the pharmaceutical chemicals of multiple rare earth metal and use this pharmaceutical chemicals.
For solving the means of problem
For solving above-mentioned problem, the inventor etc. concentrate on studies, and found that, use the water-soluble polymer that has amino water-soluble polymer and have acidic-group, can separate, reclaim multiple rare earth metal.
That is, the present invention includes following content:
(1) side chain has the water-soluble polymer that amino, main chain are straight chain and has the water-soluble polymer of acidic-group or the Terres rares metal agglutinant that Zeo-karb combines.
(2) Terres rares metal agglutinant as described as (1), it is for optionally reclaiming the rare-earth metal ion of ionic radius minimum from multiple rare-earth metal ion.
(3), as (1) or (2) described Terres rares metal agglutinant, wherein, side chain has the water-soluble polymer that amino, main chain are straight chain and has the structural unit meaned by general formula (I),
[changing 1]
[in formula, R
1for C
1-C
3alkylidene group, R
2and R
3be hydrogen or C independently of each other
1-C
3alkyl], and/or the structural unit meaned by general formula (II),
[changing 2]
[in formula, R
4for hydrogen or C
1-C
3alkyl].
(4) as the described Terres rares metal agglutinant of any one in (1)～(3), wherein, amino is tertiary amino.
(5) a kind of recovery method of rare earth metal, be included in the aqueous solution and mix side chain and have the operation that water-soluble polymer, the water-soluble polymer with acidic-group or Zeo-karb that amino, main chain are straight chain and multiple rare-earth metal ion form agglutinator.
(6) recovery method as described as (5), wherein, for optionally reclaim the rare-earth metal ion of ionic radius minimum from multiple rare-earth metal ion.
(7), as (5) or (6) described recovery method, wherein, amino mole number is 0.1: 1～1.3: 1 with the ratio of the mole number of the rare-earth metal ion of multiple rare-earth metal ion Ionic Radius minimum.
(8), as the described recovery method of any one in (5)～(7), also comprise with acid or alkali and agglutinator is processed and made the operation of its dissolving.
(9), as the described recovery method of any one in (5)～(8), wherein, side chain has the water-soluble polymer that amino, main chain are straight chain and has the structural unit meaned by general formula (I),
[changing 3]
[in formula, R
1for C
1-C
3alkylidene group, R
2and R
3be hydrogen or C independently of each other
1-C
3alkyl], and/or the structural unit meaned by general formula (II),
[changing 4]
[in formula, R
4for hydrogen or C
1-C
3alkyl].
(10) as the described recovery method of any one in (5)～(9), wherein, amino is tertiary amino.
(11) as the described recovery method of any one in (5)～(10), wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
(12) a kind of retrieving arrangement of rare earth metal, have the tempering tank that the described Terres rares metal agglutinant of any one in (1)～(4) is mixed with multiple rare-earth metal ion and form agglutinator, the filter house that reaches the above-mentioned agglutinator of filtration.
The invention effect
According to the present invention, can and only separate in large quantities, reclaim specific rare earth metal from the aqueous solution high speed that contains multiple rare earth metal.Particularly, can be from the aqueous solution high speed that contains Nd and Dy and only separate in large quantities, reclaim Dy.
The accompanying drawing explanation
Fig. 1 is the schematic diagram that metal trapping of the present invention, agglutinator form;
Fig. 2 is the schematic diagram of metal trapping of the present invention;
Fig. 3 is the schematic diagram of metal separation of the present invention;
Fig. 4 is the schematic diagram of metal separation of the present invention, retrieving arrangement;
Fig. 5 is the schematic diagram of metal separating device of the present invention;
Fig. 6 is the schematic diagram of apparatus for recovering metal of the present invention;
Fig. 7 is the schematic diagram of metal separation of the present invention, retrieving arrangement;
Fig. 8 is the schematic diagram of metal separation of the present invention, retrieving arrangement;
Fig. 9 is the schematic diagram of metal separation of the present invention, retrieving arrangement;
Figure 10 is the schematic diagram of metal separating device of the present invention;
Figure 11 is the schematic diagram of apparatus for recovering metal of the present invention.
Nomenclature
1...Nd ion
2...Dy ion
3... amino
4... contain amino water-soluble polymer
5... acidic-group
6... the water-soluble polymer that contains acidic-group
7... ionic linkage
8... trapped the agglutinator of Dy ion
9... the rare earth class ion of small ion radius
10... the rare earth class ion of heavy ion radius
11... Zeo-karb
12... the acidic-group of Zeo-karb
13... ionic linkage
14... tempering tank
15... pump
16... pipe arrangement
17... the first container
18... pump
19... pipe arrangement
20... second container
21... pump
22... pipe arrangement
23... stirring blade
24... overhead type stirrer
25... the agglutinator that comprises the water-soluble polymer that contains amino water-soluble polymer and contain acidic-group
26... shutter
27... strainer
28... the 3rd container
29... pump
30... pipe arrangement
31... metal recovery groove
32... valve
33... the 4th container
34... pump
35... pipe arrangement
36... the oxyhydroxide of rare earth metal
37... shutter
38... strainer
39... pharmaceutical chemicals accumulator tank
40... the first cylinder
41... second tin roller
42... the 3rd cylinder
43... the 4th cylinder
44... belt
45... agglutinator accumulator tank
46... shutter
47... strainer
48... container
49... passage
50... Zeo-karb
51... valve
52... pump
53... pipe arrangement
54... screen cloth
55... post
56... pressing mechanism
57... electrode
58... power supply
Embodiment
Below, just the present invention is elaborated.
1, ultimate principle
The aqueous solution that use contains Nd ion that ionic radius is large and the little Dy ion of ionic radius illustrates ultimate principle of the present invention.Because Nd and Dy are contained in the coupernick that various electric motor use, as representational example, describe, in addition, such as the lanthanum used in fluor (La), cerium (Ce), europium (Eu), terbium (Tb) etc. also can implement according to identical principle.
(1) use the method for the water-soluble polymer with acidic-group
About reclaiming the method for Dy the aqueous solution from being mixed with Nd ion and Dy ion, utilize Fig. 1 to describe.In addition, when being dissolved in acid by coupernick, Nd, Dy become the form of 3 valency ions, and in the present invention, Nd ion, Dy ion all refer to 3 valency ions.
At first add the straight chain water-soluble polymer 4 with amino 3 in the aqueous solution that is mixed with Nd ion 1, Dy ion 2.So preferentially being had amino straight chain water-soluble polymer, the Dy ion encases.
Secondly, the solution that adds the water-soluble polymer 6 with acidic-group 5.So, just formed the ionic linkage 7 formed by the amino with amino straight chain water-soluble polymer and the acidic-group with water-soluble polymer of acidic-group.By the formation of this ionic linkage, the water-soluble polymer with acidic-group is with to have amino water-soluble polymer crosslinked.So this cross-linking agent becomes water insoluble, as trapping, the agglutinator 8 of Dy ion is arranged and separate out.Can make this agglutinator be separated by filter vat, consequently, can the recovering rare earth metalloid.
While adding sodium hydroxide etc. to become alkalescence in the agglutinator reclaimed, dissolve, if improve alkalinely, the oxyhydroxide of rare earth class will separate out.By it is reclaimed, just can access to contain at high proportion the rare earth class oxyhydroxide of Dy.
Acidic-group with water-soluble polymer of acidic-group forms the salt structure with the alkali added.The ammonium salt structure that the acidic-group of the amino that in addition, has an amino straight chain water-soluble polymer and the water-soluble polymer with acidic-group forms is disintegrated and becomes free structure.Like this, by the disintegration of the ionic linkage between the polymer that forms agglutinator, agglutinator dissolves.
Even adding hydrochloric acid etc. to make it become acidity in agglutinator also can dissolve.Amino with amino straight chain water-soluble polymer forms the salt structure with the acid added.In addition, the acidic-group that has a water-soluble polymer of acidic-group disintegrates and becomes free structure with the ammonium salt structure that the amino with amino straight chain water-soluble polymer forms.Like this, by the disintegration of the ionic linkage between the polymer that forms agglutinator, agglutinator dissolves.
On the other hand, now rare earth class forms the salt structure with the acid added.During because of the salt of the acid that adds to be hydrochloric acid etc. form water miscible rare earth class sour, will become the state simultaneously dissolved with polymer for aggegation, therefore be necessary they are separated.In separation at this moment, use dialysis membrane or use gel-filtration etc., can be separated into the water-soluble polymer of low-molecular-weight rare earth class salt and high molecular.In addition, at this, illustrate the water-soluble polymer with carboxyl as acidic-group, but when sulfo group too.
But, after being mixed with the aqueous solution aggegation of Nd ion, Dy ion, because the Dy ion reduces, relatively the ratio of Nd ion uprises.Therefore, can, when by agglutinator, reclaiming Dy, by raffinate, reclaim Nd.
Think that compare the principle that optionally traps Dy with Nd as follows.At first, the ionic radius of Nd ion is about
the ionic radius of Dy ion is about
the ionic radius that is the Dy ion is little.Can infer and there is amino straight chain water-soluble polymer when trap ions, as shown in Figure 2, become straight chain and become ring and trap the form of a plurality of ions.
But, because of the impact of amino etc., the ring that straight chain forms not is circle, thinks irregularly shaped.Now, the ion that ionic radius is little, even ring also can trap in the mode plugged the gap in a large number for irregularly shaped, and the large ion of ionic radius is because of being difficult to enter space, so be difficult to trap.
In thering is amino water-soluble polymer, for example, as polymine during main chain branching, because main chain can not become the ring of trapping Dy ion, therefore become the form with coordinate bond or ionic linkage trapping Dy ion.
That is, the amino water-soluble polymer that has that is straight chain with main chain is compared, the main chain branching such as polymine there is amino water-soluble polymer, low for the selectivity trapping ability of Dy ion.Think that this is to compare the reason that optionally traps Dy with Nd.
In addition, from the foregoing, present technique is not limited to Nd and Dy, but goes out by aggegation the aqueous solution that has multiple rare-earth metal ion from mixing the technology that rare-earth metal ion that ionic radius is little is trapped.Use this technology, except Nd, Dy, also can seek to extend to for example Separation and Recovery rare earth class from fluor.In fluor, the ionic radius of lanthanum (La) used, cerium (Ce), europium (Eu), terbium (Tb) is respectively
the technology of the application of the invention, the easy order that these elements are trapped by agglutinator is followed successively by Tb, Eu, Ce, La.
(2) use the method for Zeo-karb
In the present invention, there is the water-soluble polymer of acidic-group by interpolation, and there is amino water-soluble polymer and form agglutinator.But, also can replace thering is the water-soluble polymer of acidic-group and use Zeo-karb.Below, utilize Fig. 3 to describe.
In the aqueous solution that contains 10 two kinds of rare earth class ions of rare earth class ion that rare earth class ion 9, ionic radius that ionic radius is little are large, add the straight chain water-soluble polymer 4 with amino 3, make the rare earth class ion that its trap ions radius is little.Then, when adding Zeo-karb 11, acidic-group 12 with the amino of amino straight chain water-soluble polymer and Zeo-karb forms ionic linkages 13, forms the agglutinator that has trapped the rare earth class ion that ionic radius is little on the surface of Zeo-karb.Filtration by the Zeo-karb under this state etc., make the rare earth class ion isolation that rare earth class ion that ionic radius is little and ionic radius are large.
When the agglutinator on the Zeo-karb surface of reclaiming becomes alkalescence adding sodium hydroxide etc., dissolve, while improving alkalescence, the oxyhydroxide of rare earth class will be separated out.By it is reclaimed, can access to contain at high proportion the rare earth class oxyhydroxide of the rare earth class ion that ionic radius is little.
Having the ammonium salt structure that the acidic-group of the amino of amino straight chain water-soluble polymer and Zeo-karb forms disintegrates and becomes free.Like this, by the ionic linkage between the polymer that makes to be formed with agglutinator, disintegrate, agglutinator dissolves.Can reclaim and there is amino straight chain water-soluble polymer, again for the Separation and Recovery of rare earth class.
Even adding hydrochloric acid etc. and become acidity, agglutinator also can dissolve.Amino with amino straight chain water-soluble polymer forms the salt structure with the acid added.Like this, by the ionic linkage between the polymer that makes to be formed with agglutinator, disintegrate, agglutinator dissolves.
On the other hand, now rare earth class forms the salt structure with the acid added.During because of the salt of the acid that adds to be hydrochloric acid etc. form water-solubility rare-earth class sour, will become the state simultaneously dissolved with polymer for aggegation, therefore be necessary they are separated.In separation at this moment, use dialysis membrane or gel-filtration etc., can be separated into the water-soluble polymer of low-molecular-weight rare earth class salt and high molecular.
2, Terres rares metal agglutinant
The present invention relates to a kind ofly by side chain, there is the Terres rares metal agglutinant that the water-soluble polymer that amino, main chain are straight chain (following also referred to as " containing amino water-soluble polymer ") and the water-soluble polymer with acidic-group (following also referred to as " containing the water-soluble polymer of acidic-group ") or Zeo-karb combine.At this, so-called " combining " refer to and comprise with separate stage and contain amino water-soluble polymer and containing the water-soluble polymer of acidic-group or the Terres rares metal agglutinant of Zeo-karb, and contain amino water-soluble polymer and contain the water-soluble polymer of acidic-group or any one of the Terres rares metal agglutinant of Zeo-karb with admixture.
The Terres rares metal agglutinant of the application of the invention, can be from the aqueous solution that contains multiple rare-earth metal ion the specific rare-earth metal ion of Separation and Recovery optionally, the rare-earth metal ion of the rare-earth metal ion Ionic Radius minimum existed in the aqueous solution.
(1) containing amino water-soluble polymer
In the present invention, use containing amino water-soluble polymer, there is for side chain the water-soluble polymer that amino, main chain are straight chain as mentioned above.As long as can trap rare-earth metal ion, main chain just is not particularly limited, but preferably comprises the main chain of hydrocarbon, or comprises hydrocarbon and SO
2main chain.As long as have amino, side chain just is not particularly limited, but preferably-R
1-NR
2r
3(at this, R
1for C
1-C
3alkylidene group, preferred methylene radical, R
2and R
3be hydrogen or C independently of each other
1-C
3alkyl, preferably be methyl) or with the nitrogenous ester ring type heterocycle of 5～7 yuan formed together with the carbon atom of main chain (for example,, with the tetramethyleneimine formed together with two adjacent carbon atoms of main chain).
In addition, in the present invention, use containing amino water-soluble polymer, preferably there is the structural unit meaned by general formula (I),
[changing 5]
[in formula, R
1for C
1-C
3alkylidene group, be preferably methylene radical or ethylidene, more preferably methylene radical; R
2and R
3be hydrogen or C independently of each other
1-C
3alkyl, preferably be hydrogen, and more preferably a side is that hydrogen the opposing party is methyl, is all particularly preferably methyl], and/or the structural unit meaned by general formula (II),
[changing 6]
[in formula, R
4for hydrogen or C
1-C
3alkyl, be preferably hydrogen or methyl, more preferably methyl].
Further, the compound 1～8 containing the preferred following chemical formulation of amino water-soluble polymer used in the present invention:
[changing 7]
Compound 1
[in formula, m is positive integer, and being preferably the number-average molecular weight made containing amino water-soluble polymer becomes 200～1,000,000 such integer, more preferably it is to make to become 500～200 containing the number-average molecular weight of amino water-soluble polymer, 000 such integer];
[changing 8]
[in formula, m and n are positive integer, and being preferably the number-average molecular weight made containing amino water-soluble polymer becomes 200～1,000,000 such integer, more preferably it is to make to become 500～200 containing the number-average molecular weight of amino water-soluble polymer, 000 such integer];
[changing 9]
[in formula, n is positive integer, and being preferably the number-average molecular weight made containing amino water-soluble polymer becomes 200～1,000,000 such integer, more preferably it is to make to become 500～200 containing the number-average molecular weight of amino water-soluble polymer, 000 such integer];
[changing 10]
[in formula, n is positive integer, and being preferably the number-average molecular weight made containing amino water-soluble polymer becomes 200～1,000,000 such integer, more preferably it is to make to become 500～200 containing the number-average molecular weight of amino water-soluble polymer, 000 such integer];
[changing 11]
Compound 5
[in formula, m and n are positive integer, and being preferably the number-average molecular weight made containing amino water-soluble polymer becomes 200～1,000,000 such integer, more preferably it is to make to become 500～200 containing the number-average molecular weight of amino water-soluble polymer, 000 such integer];
[changing 12]
Compound 6
[in formula, m and n are positive integer, and being preferably the number-average molecular weight made containing amino water-soluble polymer becomes 200～1,000,000 such integer, more preferably it is to make to become 500～200 containing the number-average molecular weight of amino water-soluble polymer, 000 such integer];
[changing 13]
Compound 7
[in formula, n is positive integer, and being preferably the number-average molecular weight made containing amino water-soluble polymer becomes 200～1,000,000 such integer, more preferably it is to make to become 500～200 containing the number-average molecular weight of amino water-soluble polymer, 000 such integer]; Or
[changing 14]
Compound 8
[in formula, n is positive integer, and being preferably the number-average molecular weight made containing amino water-soluble polymer becomes 200～1,000,000 such integer, more preferably it is to make to become 500～200 containing the number-average molecular weight of amino water-soluble polymer, 000 such integer].
Even, although amino is the also rare-earth metal ion of trap ions radius minimum optionally of any one amino in primary, secondary, uncle, by using tertiary amino, can be had more the optionally Separation and Recovery of rare earth metal.Its experimental result and calculational chemistry by the reality shown in following confirms.
Synthetic above-claimed cpd 1, by a hydrogen in the amino of compound 1 change to methyl compound (compound 1 '), two hydrogen in the amino of compound 1 are changed to the compound (compound 1 ") of methyl.The amino of compound 1 is primary amino, and the amino of compound 1 ' is secondary amino group, compound 1 " amino be tertiary amino.Use these compounds to carry out the aggegation experiment.So, when optionally the ratio of aggegation Dy is arranged by order from high to low, be: compound 1 ", the order of compound 1 ', compound 1.That is, the ratio that optionally traps Dy amino for uncle when amino for the highest, next coming in order are secondary amino group, primary amino.
While with the Density functional counting method, carrying out Molecular Orbital Calculation, compound 1, compound 1 ', compound 1 " bonded energy of Nd is respectively to 6.9kcal/mol, 7.5kcal/mol, 8.4kcal/mol.On the other hand, the bonded energy of Dy is respectively to 10.2kcal/mol, 11.5kcal/mol, 12.9kcal/mol.
Deduct the value with the bonded energy of Nd from the bonded energy with Dy, for compound 1, compound 1 ', compound 1 ", be respectively 3.3kcal/mol, 4.0kcal/mol, 4.5kcal/mol.This result means, the compound 1 of the poor maximum of bonded energy of Dy and Nd ", the possibility of compound selective ground trapping Dy that has tertiary amino is the highest, to be then the compound with secondary amino group, is then the select progressively reduction with compound of primary amino.
This is very consistent with the optionally order in actual experiment.Therefore think, the reason that causes the trapping selection rate of Dy to create a difference because of the difference of amino progression is the difference of the bonded energy of Dy and Nd.
As mentioned above, use the high molecular situation with tertiary amino, although carrying out optionally aspect the Separation and Recovery rare earth metal preferably, use the water-soluble polymer of the amino that there is in combination primary～uncle also can realize high selectivity.In addition, there is the water-soluble polymer of cyclic amino by use, can be had more optionally Separation and Recovery.
Containing the number-average molecular weight hour of amino water-soluble polymer, even also can produce at normal temperatures the distinctive foul smell of amine.Specifically, in the situation that number-average molecular weight less than 200 becomes remarkable.Therefore, preferably contain the number-average molecular weight of amino water-soluble polymer more than 200.In addition, for imperceptible foul smell almost, as may preferred number average molecular weight more than 500.
On the other hand, when number-average molecular weight becomes large, even it is also high to make its viscosity of the aqueous solution, in input amount management, when dropping into operation in metallic water, process the difficulty that becomes.Specifically, when number-average molecular weight surpasses at 1,000,000 o'clock, even make the aqueous solution of 10 % by weight, viscosity is also more than 3,000mPas.Therefore, preferably the number-average molecular weight containing amino water-soluble polymer is 1,000, below 000.In addition, even make the aqueous solution of 10 % by weight, viscosity is also below 1,000mPas, and in order to simplify input amount management or the processing when dropping into operation in metallic water, preferably the number-average molecular weight containing amino water-soluble polymer is below 200,000.In addition, for number-average molecular weight, gel permeation chromatography (GPC) is measured.
(2) contain the water-soluble polymer of acidic-group
The water-soluble polymer containing acidic-group used in the present invention, as mentioned above for having the water-soluble polymer of acidic-group.Because the trapping of the selectivity of rare-earth metal ion mainly depends on containing amino water-soluble polymer, the water-soluble polymer containing acidic-group used in the present invention, just be not particularly limited so long as can react with the water-soluble polymer containing amino the water-soluble polymer that forms agglutinator.In addition, acidic-group, so long as the acidic-group that can react with amino just is not particularly limited, for example, can be enumerated carboxyl, sulfonic group, phosphate etc.
As the water-soluble polymer with carboxyl, for example, cheap and be easy to carry out optimization polypropylene acid aspect ionic bonding with amino.In addition, also can enumerate the multipolymer etc. of polymethyl acrylic acid, polyacrylic acid and polymethyl acrylic acid.They are polymers that bonding has acidic-group on the main chain consisted of straight chain hydrocarbon.
As thering is sulfonic water-soluble polymer, can enumerate polyvinylsulfonic acid or polystyrolsulfon acid etc.Because sulfonic group is larger than carboxyl acidity, the ratio that forms ionic linkage with amino is high, can access on stable agglutinator this point preferably.
In the present invention, preferably use water-soluble polymer and the high molecular multipolymer that does not there is acidic-group containing acidic-group.As the polymer that does not there is acidic-group, for example, can enumerate polymethyl acrylate, polyethyl acrylate, polyacrylic acid propyl ester, butyl polyacrylate, the own ester of polyacrylic acid, polyacrylic acid monooctyl ester, polyacrylic acid ester in the last of the ten Heavenly stems, polyacrylic acid dodecyl ester, polymethylmethacrylate, polyethyl methacrylate, polypropylmethacryla,es, poly-n-butyl methacrylate, the own ester of polymethyl acrylic acid, polymethyl acrylic acid monooctyl ester, polymethyl acrylic acid ester in the last of the ten Heavenly stems, polymethyl acrylic acid dodecyl ester, polystyrene etc.Multipolymer is by obtaining containing the monomer of the water-soluble polymer of acidic-group and the high molecular monomer mixed polymerization that does not have an acidic-group, the monomer that mixture ratio preferably contains the water-soluble polymer of acidic-group is (for example, 50～90 % by mole) more than 50 % by mole.Reason is, if 50 % by mole of less thaies are insoluble in water.
If the number-average molecular weight containing the water-soluble polymer of acidic-group is too low, because the quantity of agglutinator cross-linking part tails off, the stability step-down of agglutinator.In addition, also there is agglutinator to become the aqueous tendency that viscosity is high.If become like this, in filtration, it is difficult that the recovery of agglutinator just becomes.Therefore, the number-average molecular weight that contains the water-soluble polymer of acidic-group wishes to be more than 2,000.
In addition, if the temperature of the aqueous solution that contains rare earth metal is more than 40 ℃, number-average molecular weight is 2,000 o'clock, the agglutinator binding property that will become.After just rare earth class being dissolved in to acid, temperature can be up to 60 ℃ of left and right sometimes.Now, by further increase number-average molecular weight, even high temperature also can make agglutinator solidify.Specifically, by making number-average molecular weight, reach more than 5,000, even the temperature of the aqueous solution of rear earth containing is 40 ℃, also can make agglutinator solidify.Therefore, containing the number-average molecular weight of the water-soluble polymer of acidic-group, be more preferably more than 5,000.And then, by making number-average molecular weight, reach more than 10,000, even being 60 ℃, temperature at discharging condensate also agglutinator can be solidified.Therefore, containing the number-average molecular weight of the water-soluble polymer of acidic-group, be more preferably more than 10,000.
On the other hand, if number-average molecular weight too increases, the water-soluble polymer that contains acidic-group just becomes and is insoluble in water.Will prepare with a large amount of water like this containing the solution of the dilution of the water-soluble polymer of acidic-group with for aggegation.If do like this, because waste liquid amount becomes huge and impracticable.Therefore, the number-average molecular weight that preferably contains the water-soluble polymer of acidic-group is below 200,000, more preferably below 100,000.Thus, waste liquid amount can be reduced to practical level.
(3) Zeo-karb
In the present invention, can replace using Zeo-karb containing the water-soluble polymer of acidic-group.Zeo-karb is the resin particle that surface has the acidic-groups such as a large amount of carboxyls or sulfonic group, in order to increase surface-area, improves ion-exchanging efficiency, is mostly Porous.Zeo-karb can with trapped the rare earth class ion containing after amino water-soluble polymer ionic bonding, by filtering the aqueous solution existed from multiple rare earth class Ar ion mixing, minute get.Afterwards, utilize alkali or aqueous acid, can remove and trap the ionic linkage between amino water-soluble polymer that contains of rare earth class ion.In addition, by common regeneration of ion-exchange resin method (by method sour, that then use distilled water wash), can the cation regenerant exchange resin.
As the Zeo-karb used in the present invention, needn't use special resin, can use the resin of general grade.
In addition, when magnetic powder is contained in resin inside, or contain while thering is ferromagnetic metal-powder, do not filtered and isolate Zeo-karb the aqueous solution that utilizes the magneticseparation method also can exist from multiple rare earth class Ar ion mixing.
3, the recovery method of rare earth metal
The recovery method of rare earth metal of the present invention, be included in the aqueous solution and mix side chain and have the operation that water-soluble polymer, the water-soluble polymer with acidic-group or Zeo-karb that amino, main chain are straight chain and multiple rare-earth metal ion form agglutinator.More particularly, comprise by containing amino water-soluble polymer, form the operation of agglutinator containing the water-soluble polymer of acidic-group or Zeo-karb add in the aqueous solution that contains multiple rare-earth metal ion.
Recovery method of the present invention is based on following principle,, with optionally trap the rare-earth metal ion of the ionic radius minimum be present in the aqueous solution that contains multiple rare-earth metal ion containing amino water-soluble polymer, then make to have trapped reacting containing amino water-soluble polymer and water-soluble polymer or Zeo-karb containing acidic-group of this rare-earth metal ion, form agglutinator.
Containing the speed of amino water-soluble polymer trapping rare-earth metal ion, faster than the speed of the water-soluble polymer with containing acidic-group or Zeo-karb formation agglutinator.Therefore, add containing amino water-soluble polymer and unimportant containing the order of the water-soluble polymer of acidic-group or Zeo-karb, first add any one water-soluble polymer and all can.In addition, also can add various water-soluble polymers simultaneously.
Contain the optionally rare-earth metal ion of trap ions radius minimum of amino water-soluble polymer, when the whole separated recovery of minimum rare-earth metal ion, optionally trap secondly little rare-earth metal ion.Therefore, the amount containing amino water-soluble polymer of adding by appropriate regulation, and, by repeatedly carrying out recovery method of the present invention, can optionally in each time, reclaim different rare-earth metal ions.
On the other hand, if, when the quantity of the amino of water-soluble polymer, acidic-group is more than the quantity of the rare-earth metal ion of ionic radius minimum, form coordinate bond, ionic linkage etc. between above-mentioned functional group and rare-earth metal ion.Because these keys less affect ionic size, the rare earth class ion that not only ionic radius is little, even the large rare earth class ion of ionic radius is also almost similarly trapped by agglutinator.Therefore, it is desirable to, is to make the mole number same degree of rare earth class ion of amino mole number and ionic radius minimum or the amount below it containing the addition of amino water-soluble polymer.Specifically, the mole number of the rare-earth metal ion of ionic radius minimum (M) is set as at 1 o'clock, the mole number (PB) that contains the amino of amino water-soluble polymer is preferably below 1.3.More particularly, preferably PB: M is 0.1: 1～1.3: 1, more preferably 0.5: 1～1.2: 1, and particularly preferably 0.8: 1～1: 1.At this, " amino mole number " do not refer to the amino number had containing amino water-soluble polymer of 1 molecule, and refers to by adding in the aqueous solution containing amino water-soluble polymer the number of all amino that exist in the aqueous solution.
Be and form ionic linkage containing the amino of amino water-soluble polymer containing the effect of the water-soluble polymer of acidic-group, thereby form insoluble agglutinator in water.If when larger than the rare earth class number of ions of ionic radius minimum containing the acidic-group number of the water-soluble polymer of acidic-group, acidic-group just with the rare earth class ion of ionic radius minimum and the bigger rare earth class ion generation ionic bonding of ionic radius, this key compound further with amino ionic bonding containing amino water-soluble polymer, form insoluble agglutinator in water.Therefore, be difficult to cause the selectivity aggegation of the rare earth class ion little to ionic radius.
Therefore, the addition that contains the water-soluble polymer of acidic-group, be preferably the mole number (PA) that makes containing the acidic-group of the water-soluble polymer of acidic-group than the few amount of the mole number of the rare-earth metal ion of ionic radius minimum (M), and preferably making containing the mole number (PA) of the acidic-group of the water-soluble polymer of acidic-group is equal amts or its following (that is, PA≤PB) with the mole number (PB) of the amino of water-soluble polymer containing amino.The effect of Zeo-karb and addition are also the same with the situation of the water-soluble polymer that contains acidic-group.
In the recovery method of rare earth metal of the present invention,, scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) can separate all rare earth metals.
Particularly, in the recovery method of rare earth metal of the present invention, the preferable separation ionic radius is poor is
above multiple rare-earth metal ion, more preferably the isolating ions correction for semi-diameter is
above multiple rare-earth metal ion, particularly preferably the isolating ions correction for semi-diameter is
above multiple rare-earth metal ion.
More particularly, preferably from the aqueous solution that contains Nd and Dy, optionally reclaim Dy, optionally reclaim Y from the aqueous solution that contains Ce and Y, optionally reclaim Tb from the aqueous solution that contains La and Tb, optionally reclaim Tb from the aqueous solution that contains La, Ce and Tb.In addition, more preferably from the aqueous solution that contains 3 valency Nd ions and 3 valency Dy ions, optionally reclaim Dy.
The recovery method of rare earth metal of the present invention can further include with acid or alkali and processes to comprising containing amino water-soluble polymer with containing the water-soluble polymer of acidic-group or the agglutinator of Zeo-karb the operation that makes its dissolving.Be not particularly limited for making agglutinator dissolve the acid of using, but preferably use mineral acid, specifically, preferably use hydrochloric acid, sulfuric acid, nitric acid etc.In addition, be not particularly limited for making agglutinator dissolve the alkali used, but preferably use mineral alkali, specifically, preferably use alkali-metal oxyhydroxide, for example, sodium hydroxide, potassium hydroxide etc.
4, the retrieving arrangement of rare earth metal
(1) scheme 1 of metal separation retrieving arrangement invention
The retrieving arrangement of rare earth metal of the present invention has the tempering tank that above-mentioned Terres rares metal agglutinant and multiple rare-earth metal ion is mixed and form agglutinator, the filter house that reaches the above-mentioned agglutinator of filtration.With Fig. 4, said apparatus is described particularly.
At first, in tempering tank 14 inside, the aqueous solution that will contain multiple rare earth class ion utilizes pump 15 to add tempering tank by pipe arrangement 16.Secondly utilize pump 18, by pipe arrangement 19, will add containing the aqueous solution of amino water-soluble polymer tempering tank 14 from the first container 17.In addition, add containing amino water-soluble polymer, in the aqueous solution that contains multiple rare earth class ion, optionally trapping has the rare earth class ion of minimum ionic radius.
Secondly, utilize pump 21, by pipe arrangement 22, will add tempering tank 14 containing the aqueous solution of the water-soluble polymer of acidic-group from second container 20.After adding the aqueous solution that contains multiple rare earth class ion, with the overhead type stirrer 24 that agitating vane 23 is housed, continue to stir the aqueous solution.Form in tempering tank thus and comprise the agglutinator 25 that contains amino water-soluble polymer and contain the water-soluble polymer of acidic-group.After agglutinator forms, stop stirring.
Then, when opening shutter 26, the liquid beyond agglutinator is discharged from tempering tank by strainer 27.Because agglutinator is tackled by strainer, can not discharge from tempering tank.After the liquid component of tempering tank is discharged from, close shutter.
Then, when from the 3rd container 28, utilizing pump 29, while by pipe arrangement 30, aqueous hydrochloric acid being added to tempering tank, agglutinator dissolves.While again opening shutter, the liquid after agglutinator dissolves is discharged from tempering tank by strainer, enters metal recovery groove 31.In addition, control whether to the metal recovery groove, add described liquid with valve 32.
Then from the 4th container 33, utilize pump 34, by pipe arrangement 35, aqueous sodium hydroxide solution added to the metal recovery groove.So the ion of rare earth metal is separated out as the oxyhydroxide 36 of the rare earth metal that is insoluble in water.During the shutter 37 of opening metal accumulator tank bottom, liquid enters pharmaceutical chemicals accumulator tank 39 via strainer 38 from accumulator tank.
Taking-up remains in the oxyhydroxide of the rare earth metal in the metal recovery groove, and thus, the recovery of the rare earth class that ionic radius is little finishes.
Although not shown at this, after these EOs, by use washing tempering tank and the accumulator tank such as purify waste water, can remove the hydrochloric acid that is attached to wall etc.In addition, containing the water-soluble polymer of acidic-group and also passable on the contrary containing the addition sequence of amino water-soluble polymer.
(2) scheme 2 of metal separation retrieving arrangement invention
Utilize Fig. 5 and Fig. 6, in rare earth metal separating and reclaiming device of the present invention, the formation of using magnetic separation method to carry out rare earth metal separation, recovery describes.
At first, magnetic powder is mixed with the water-soluble polymer aqueous solution containing amino of second container.From second container by magnetic powder with when adding tempering tank together with the amino water-soluble polymer aqueous solution, form agglutinator, contain magnetic powder in agglutinator.
In this device, have comprise the first cylinder 40, second tin roller 41, the 3rd cylinder 42, the 4th cylinder 43, belt 44 containing magnetic powder agglutinator conveyer.Be the structure with magnetic force from the 4th cylinder to the belt surface between second tin roller through the first cylinder, thereby can make the agglutinator containing magnetic powder in the first tempering tank be attached to belt surface.There is no magnetic force between second tin roller to the four cylinders, so agglutinator comes off from the 3rd cylinder, fall into agglutinator accumulator tank 45.Like this, the agglutinator that has trapped metal ion is collected in the agglutinator accumulator tank.
Below, use Fig. 6 explanation to reclaim the operation of metal from the agglutinator that has trapped metal ion.
At first, utilize pump, by pipe arrangement, aqueous hydrochloric acid added to the agglutinator accumulator tank from the 3rd container.So agglutinator dissolves.While opening shutter 46, liquid and magnetic powder after agglutinator dissolves are added into the metal recovery groove via strainer 47.Then, from the 4th container 33 utilize pump 34, while by pipe arrangement 35, to the metal recovery groove, adding aqueous sodium hydroxide solution, lysed rare earth metal becomes oxyhydroxide, thereby separates out.At this, if open shutter 37, the water-soluble polymer containing acidic-group of dissolving, containing amino water-soluble polymer, by strainer 38, enter pharmaceutical chemicals accumulator tank 39.The oxyhydroxide of the rare earth metal of separating out remains on strainer 38.Like this by using the magneticseparation mode, also recovering rare earth metalloid optionally.
(3) scheme 3 of metal separation retrieving arrangement invention
The basic comprising of the metal separation retrieving arrangement of the present invention while utilizing Fig. 7 to use Zeo-karb to replacing containing the water-soluble polymer of acidic-group describes.
Containing after adding the aqueous solution containing amino water-soluble polymer in the aqueous solution of multiple rare earth class ion, from container 48, by passage 49, add Zeo-karb 50.Add-on is controlled by valve 51.The amino water-soluble polymer that contains that has trapped like this rare earth class ion of small ion radius carries out ionic bonding on the Zeo-karb surface.
From tempering tank will be discharged containing the aqueous solution of multiple rare earth class ion, when adding the aqueous solution of hydrochloric acid, containing amino water-soluble polymer, from Zeo-karb, be removed.Afterwards, Zeo-karb is purified waste water to wash by use and is regenerated, and can again with the water-soluble polymer containing amino, form ionic linkage.
That from Zeo-karb, leaves on the other hand, is stored in the metal recovery groove containing amino water-soluble polymer.At this, when adding aqueous sodium hydroxide solution, the rare earth class ion of small ion radius becomes oxyhydroxide and separates out.Further, by the shutter of opening metal accumulator tank, the aqueous solution that contains amino water-soluble polymer moves to the pharmaceutical chemicals accumulator tank.Recovery remains in the oxyhydroxide of the rare earth metal of the small ion radius in the metal recovery groove, EO thus.
(4) scheme 4 of metal separation retrieving arrangement
Utilize Fig. 8 in metal separation retrieving arrangement of the present invention, Zeo-karb being filled in post and the formation of using describes.
Containing after mixing the aqueous solution containing amino water-soluble polymer in the aqueous solution of multiple rare earth class ion, utilize pump 52 to join and be filled with in the post 55 that Zeo-karb and bottom are screen cloth 54 by pipe arrangement 53 this mixed solution.Post top is provided with the pressing mechanism 56 that uses pressurized air or compressed nitrogen etc.Like this, by Zeo-karb is filled in post and uses, do not need the operation that ion exchange resin is removed from tempering tank.
(5) scheme 5 of metal separation retrieving arrangement
Utilize Fig. 9 to describe in metal separation retrieving arrangement of the present invention, Zeo-karb being filled in post to the formation of using and be provided with electrode in post.
At first, not the hydrogen injecting aqueous solution of sodium oxide in the 4th container, but add sodium chloride aqueous solution.In the above-described embodiment, in the stage after just adding aqueous sodium hydroxide solution (in the present embodiment for after just adding sodium chloride aqueous solution), by 57, electrode, by power supply 58, producing potential differences, sodium-chlor, by electrolysis, generates sodium hydroxide.
Be identified as Hazardous substances containing the parts (also comprising solution) of sodium hydroxide more than 5%, also will note during processing.But, by using device, the method for the present embodiment, even directly be not used as the sodium hydroxide of Hazardous substances, also can carry out the Separation and Recovery of rare earth metal.Due to by power supply is controlled, can produce necessary minimal sodium hydroxide, so have advantages of in liquid waste disposal etc. and also can reduce the heavy burdens.
In addition, in the present embodiment, can replace sodium-chlor and use the basic metal such as Repone K, lithium chloride.In addition interelectrode potential difference is set as making more than alkali metal chloride used becomes the required value of oxyhydroxide.
(6) scheme 6 of metal separation retrieving arrangement
Utilize Figure 10 with Figure 11, the formation of using Zeo-karb in metal separation retrieving arrangement of the present invention and using magnetic to separate to be described.
In this embodiment, Zeo-karb is used the inner material that contains magnetic powder.Zeo-karb with trapped the rare earth class ion containing after amino water-soluble polymer bonding, be recycled to agglutinator accumulator tank 45 by the agglutinator conveyer containing magnetic powder that comprises the first cylinder to the four cylinders, belt 44.
Afterwards, use the device shown in Figure 11, can be with the processing recovering rare earth metalloid same with embodiment 2.
While using this scheme, the sodium hydroxide added when rare earth metal is transformed to oxyhydroxide, the regeneration of the amino containing amino water-soluble polymer of hydrochloride structure, this polymer also is reproduced itself.Further, Zeo-karb also can be regenerated by adding hydrochloric acid.Therefore by implementing this programme, containing amino water-soluble polymer, Zeo-karb, both can regenerate.By regenerating both, the waste in the time of can seeking to reduce the rare earth metal Separation and Recovery also reduces component costs.
Below, utilize embodiment to describe in more detail the present invention, but technical scope of the present invention is not limited thereto.
[embodiment 1]
Preparation is by Neodymium trichloride (NdCl
3), Dysprosium trichloride (DyCl
3) be dissolved in the aqueous solution of water.Now, the concentration of Nd, Dy all is modulated to 500ppm.
This aqueous solution 35g (two kinds of rare-earth metal ions add up to 0.916mmol) is injected to container to be stirred, add the aqueous solution 0.067g (number of repeat unit is 0.093mmol) of polyacrylic 10 % by weight that number-average molecular weight is 5,000 in stirring.Further add the aqueous solution of 10 % by weight of the above-claimed cpd 1～8 of appropriate (number of repeat unit is 0.458mmol, and in addition, having two in repeating unit is 0.229mmol when amino).So, produce white agglutinator.After placing a few hours, be deposited in container bottom.By sucking-off solution parts such as transfer pipets, make in container almost to only have agglutinator.
Then washed the operation of agglutinator.Specifically, put into 35g and purify waste water, after stirring with ultrasonic cleaner, with transfer pipet etc., by the sucking-off of solution part, make in container to only have agglutinator.After carrying out 5 these washing operations, splash into the hydrochloric acid of 0.5 mol/L, finish until agglutinator dissolves.Add water, until the liquid weight in container reaches 35g.
Use inductively coupled plasma (ICP) analysis, detect Nd in this solution and the concentration of Dy.At this, detected value is to become trapped in Nd in agglutinator and the concentration of Dy.Show the result in table 1.
Aggegation experimental result when table 1 is used the polymer with various amino
*: during cyclic amine, be zero
Known use compound 1～8 o'clock is all that Dy is high to the capture rate of agglutinator.The backbone structure of these compounds is straight chain.On the other hand, while using the polymine that main chain is branched structure, the capture rate of Nd and Dy is not seen difference.
By above-mentioned, shown, by select main chain be not branching but straight chain there is amino water-soluble polymer, optionally trap the Dy less than Nd ionic radius.
If compare with amino progression, when use has the polymer ( compound 2,4,6,8) of tertiary amine, can find the tendency that the capture rate of Nd is low, the capture rate of Dy is high.Secondly what Dy capture rate was high is the polymer (compound 3,5,7) with secondary amine, only has the Dy capture rate of compound 1 of primary amine minimum.In addition, the polymer (compound 2,5,6) that has the amino of a plurality of progression all approaches the capture rate of the amino that progression is large.
Above-mentioned showing, the amino progression of the water-soluble polymer that to have amino, main chain be straight chain is larger just more optionally traps the Dy less than Nd ionic radius.
If more amino structure, compound 3～8 becomes the cyclic amine structure.Compound 2 and compound 6 have two amino, and one is the non-annularity primary amine.Another is non-cyclic tertiary amines for compound 2, and compound 6 is cyclic tertiary amines.If comparative compound 2 and 6, the Nd capture rate of compound 6 is low.The Dy capture rate of compound 2 is slightly low in addition.
More than show, for having the water-soluble polymer that amino, main chain are straight chain, with the situation that amino is non-annularity amino, compare, cyclic amino more optionally traps the Dy less than Nd ionic radius.
[embodiment 2]
Remove the 28.6 % by weight aqueous solution 0.067g (number of repeat unit is 0.093mmol) of the polystyrolsulfon acid that replacement polyacrylic acid use number-average molecular weight is 200,000 in addition, carry out the experiment identical with embodiment 1.Consequently, the difference of the result of the capture rate of the Nd in agglutinator, Dy with polyacrylic acid the time be ± below 10%.Thus, can show, even use polystyrolsulfon acid, also can optionally trap in agglutinator compare the Dy that ionic radius is little with Nd.
[embodiment 3]
Except replacing polyacrylic acid to use Zeo-karb (surface has sulfonic type, adds the amount that the sulfonic number that makes surface reaches 0.093mmol) in addition, to carry out experiment similarly to Example 1.Consequently, the difference of the result of the capture rate of the Nd in agglutinator, Dy with respect to polyacrylic acid the time be ± below 10%.Show thus, even use Zeo-karb, also can optionally trap in agglutinator compare the Dy that ionic radius is little with Nd.
[embodiment 4]
Except the muriate as rare earth metal, replace being mixed with NdCl
3and DyCl
3the aqueous solution 35g of each 500ppm, used to be mixed with to be all the muriatic Yttrium trichloride (YCl of rare earth metal
3), Cerium II Chloride (CeCl
3) aqueous solution 26.1g (two kinds of rare-earth metal ions add up to 0.916mmol) of each 500ppm in addition, attempted experiment similarly to Example 1.
In addition, the ionic radius of Y and Ce is respectively
therefore the ionic radius of Y is little.Show the result in table 2.
Aggegation experimental result when table 2 is used the polymer with various amino
*: during cyclic amine, be zero
With Ce, compare, the capture rate of the Y-direction agglutinator that ionic radius is little is high.In addition, have amino water-soluble polymer, compared with the situation of main chain branching, when main chain is straight chain, amino progression is larger, in the situation that cyclic amine more optionally traps and compares the Y that ionic radius is little with Ce.
[embodiment 5]
Except the muriate as rare earth metal, replace being mixed with NdCl
3with DyCl
3the aqueous solution 35g of each 500ppm, used to be mixed with to be all the muriatic Lanthanum trichloride (LaCl of rare earth metal
3), terbium chloride (TbCl
3) aqueous solution 34g (two kinds of rare-earth metal ions add up to 0.916mmol) of each 500ppm in addition, attempted experiment similarly to Example 1.
In addition, the ionic radius due to Tb and La is respectively
therefore the ionic radius of Tb is little.Show the result in table 3.
Aggegation experimental result when table 3 is used the polymer with various amino
*: during cyclic amine, be zero
With La, compare, the Tb that ionic radius is little is high to the capture rate of agglutinator.In addition, have amino water-soluble polymer, compared with the situation of main chain branching, when main chain is straight chain, amino progression is larger, in the situation that cyclic amine more optionally traps and compares the Tb that ionic radius is little with La.
[embodiment 6]
Except the muriate as rare earth metal, replace being mixed with NdCl
3and DyCl
3the aqueous solution 35g of each 500ppm, used to be mixed with to be all the muriatic Lanthanum trichloride (LaCl of rare earth metal
3), Cerium II Chloride (CeCl
3), terbium chloride (TbCl
3) aqueous solution 19.6g (three kinds of rare-earth metal ions add up to 0.916mmol) of this three kinds of each 500ppm in addition, attempted experiment similarly to Example 1.
In addition, the ionic radius because of Tb, Ce and La is respectively
in these three kinds, the ionic radius minimum of Tb.Show the result in table 4.
Aggegation experimental result when table 4 is used the polymer with various amino
*: during cyclic amine, be zero
With La, Ce, compare, the Tb that ionic radius is little is high to the capture rate of agglutinator.In addition, have amino water-soluble polymer, compared with the situation of main chain branching, when main chain is straight chain, amino progression is larger, in the situation that cyclic amine, more optionally trapping compares with La, Ce the Tb that ionic radius is little.
By embodiment 1～3 and embodiment 4～6, shown, the technology of the application of the invention, even in the aqueous solution that is mixed with the rare earth metal beyond Nd, Dy, also can optionally by ionic radius, little rare earth metal traps in agglutinator.
[embodiment 7]
Only according to the ratio identical with embodiment 1 use rare earth metal mixed solution, the polyacrylic aqueous solution, there is the aqueous solution of amino water-soluble polymer, while as device, using the device of Fig. 4 to carry out the Separation and Recovery of rare earth metal, Nd, Dy are the result below ± 5% to the capture rate of agglutinator with respect to the result of table 1.
Show thus, use device of the present invention, also can optionally reclaim the rare earth class that ionic radius is little.
Claims (21)
1. a Terres rares metal agglutinant, the water-soluble polymer or the Zeo-karb that are had the water-soluble polymer that amino, main chain are straight chain and had an acidic-group by side chain combine, wherein, side chain has the water-soluble polymer that amino, main chain are straight chain and has the structural unit meaned by general formula (I) and/or the structural unit meaned by general formula (II)
[changing 1]
In formula, R
1for C
1-C
3alkylidene group, R
2and R
3be hydrogen or C independently of each other
1-C
3alkyl,
[changing 2]
In formula, R
4for hydrogen or C
1-C
3alkyl.
2. Terres rares metal agglutinant claimed in claim 1, for optionally reclaiming the rare-earth metal ion of ionic radius minimum from multiple rare-earth metal ion.
3. the described Terres rares metal agglutinant of claim 1 or 2, wherein, amino is tertiary amino.
4. the recovery method of a rare earth metal, be included in the aqueous solution and mix side chain and there is the operation that water-soluble polymer, the water-soluble polymer with acidic-group or Zeo-karb that amino, main chain are straight chain and multiple rare-earth metal ion form agglutinator, wherein, side chain has the water-soluble polymer that amino, main chain are straight chain and has the structural unit meaned by general formula (I) and/or the structural unit meaned by general formula (II)
[changing 3]
In formula, R
1for C
1-C
3alkylidene group, R
2and R
3be hydrogen or C independently of each other
1-C
3alkyl,
[changing 4]
In formula, R
4for hydrogen or C
1-C
3alkyl.
5. recovery method claimed in claim 4 wherein, optionally reclaims the rare-earth metal ion of ionic radius minimum from multiple rare-earth metal ion.
6. the described recovery method of claim 4 or 5, wherein, amino mole number is 0.1: 1～1.3: 1 with the ratio of the mole number of the rare-earth metal ion of multiple rare-earth metal ion Ionic Radius minimum.
7. the described recovery method of claim 4 or 5, also comprise with acid or alkali and agglutinator processed to the operation that makes its dissolving.
8. recovery method claimed in claim 6, also comprise with acid or alkali and agglutinator processed to the operation that makes its dissolving.
9. the described recovery method of claim 4 or 5, wherein, amino is tertiary amino.
10. recovery method claimed in claim 6, wherein, amino is tertiary amino.
11. recovery method claimed in claim 7, wherein, amino is tertiary amino.
12. recovery method claimed in claim 8, wherein, amino is tertiary amino.
13. the described recovery method of claim 4 or 5, wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
14. recovery method claimed in claim 6, wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
15. recovery method claimed in claim 7, wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
16. recovery method claimed in claim 8, wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
17. recovery method claimed in claim 9, wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
18. recovery method claimed in claim 10, wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
19. the described recovery method of claim 11, wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
20. the described recovery method of claim 12, wherein, multiple rare-earth metal ion is 3 valency neodymium ions and 3 valency dysprosium ions.
21. the retrieving arrangement of a rare earth metal, have the tempering tank that the described Terres rares metal agglutinant of any one in claim 1～3 is mixed with multiple rare-earth metal ion and form agglutinator, the filter house that reaches the above-mentioned agglutinator of filtration.
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| JP5677345B2 (en) * | 2012-03-19 | 2015-02-25 | 株式会社日立製作所 | Rare earth separation and recovery method and apparatus using the same |
| JP2014031536A (en) * | 2012-08-02 | 2014-02-20 | Hitachi Ltd | Separation recovery method and separation recovery system of rare earth element |
| WO2014030218A1 (en) * | 2012-08-22 | 2014-02-27 | 株式会社 日立製作所 | Flocculant, transition metal separation method, and transition metal separation device |
| JP2014043634A (en) * | 2012-08-29 | 2014-03-13 | Hitachi Ltd | Method for separating rare earth and apparatus for separating rare earth |
| JP6088386B2 (en) * | 2013-08-22 | 2017-03-01 | 株式会社日立製作所 | Water treatment method and organic acid flocculant |
| JP6032303B2 (en) * | 2015-02-20 | 2016-11-24 | 住友金属鉱山株式会社 | Solvent extraction method, clad generation prevention method |
| CN111268779B (en) * | 2020-03-09 | 2022-03-08 | 常熟理工学院 | Method for quickly converting tributyl phosphate in waste liquid into polymerized iron phosphate flocculant |
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| JPS62275183A (en) * | 1986-05-22 | 1987-11-30 | Nippon Junyaku Kk | Metal trapping method |
| JPH0725542B2 (en) * | 1987-11-12 | 1995-03-22 | 東ソー株式会社 | Method for separating and refining rare earth elements |
| JPH0725543B2 (en) * | 1987-11-17 | 1995-03-22 | 東ソー株式会社 | Rare earth element separation method |
| US5766478A (en) * | 1995-05-30 | 1998-06-16 | The Regents Of The University Of California, Office Of Technology Transfer | Water-soluble polymers for recovery of metal ions from aqueous streams |
| JP3928017B2 (en) * | 1996-06-04 | 2007-06-13 | 株式会社片山化学工業研究所 | Treatment agent for waste liquid containing heavy metal and treatment method thereof |
| JP2000325915A (en) * | 1999-05-20 | 2000-11-28 | Miyoshi Oil & Fat Co Ltd | Method for treating solid waste |
| JP2002263665A (en) * | 2001-03-09 | 2002-09-17 | National Institute Of Advanced Industrial & Technology | Method for removing heavy metal in waste water |
| JP5277997B2 (en) * | 2009-01-29 | 2013-08-28 | 株式会社日立プラントテクノロジー | Water purification method |
| JP5352256B2 (en) * | 2009-01-29 | 2013-11-27 | 株式会社日立製作所 | Waste water purification flocculant, and waste water purification method and waste water purification apparatus using the same |
| JP2011088047A (en) * | 2009-10-21 | 2011-05-06 | Nippon Filcon Co Ltd | Polymer fixed type metal adsorbent and method of manufacturing the same |
| JP2011231366A (en) * | 2010-04-27 | 2011-11-17 | Ibaraki Univ | Valuable metal recovery method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1041183A (en) * | 1988-09-16 | 1990-04-11 | 日本重化学工业株式会社 | The separation method of rare earth element |
| CN1064109A (en) * | 1989-09-13 | 1992-09-02 | 罗纳·布朗克化学公司 | The treatment process of ores containing rare earths |
| JP2006036692A (en) * | 2004-07-27 | 2006-02-09 | National Institute Of Advanced Industrial & Technology | Metal ion-transporting agent |
| JP2011132573A (en) * | 2009-12-25 | 2011-07-07 | Hitachi Ltd | Chemical for recovering metal, method for recovering metal, and apparatus for separation-recovering metal using chemical for recovering metal |
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| JP2012030139A (en) | 2012-02-16 |
| JP5213925B2 (en) | 2013-06-19 |
| CN102345022A (en) | 2012-02-08 |
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