CN104862504A - Synergic extraction agent for heavy rare earth elements and extraction separation method of synergic extraction agent - Google Patents
Synergic extraction agent for heavy rare earth elements and extraction separation method of synergic extraction agent Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 65
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 59
- 238000000926 separation method Methods 0.000 title claims abstract description 15
- 230000002195 synergetic effect Effects 0.000 title abstract description 24
- 239000012074 organic phase Substances 0.000 claims abstract description 31
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 29
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
- 239000012071 phase Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- -1 2-ethylhexyl Chemical group 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000007522 mineralic acids Chemical class 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 125000005496 phosphonium group Chemical group 0.000 claims description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 20
- 238000007127 saponification reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000002600 positron emission tomography Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- JCQGIZYNVAZYOH-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC JCQGIZYNVAZYOH-UHFFFAOYSA-M 0.000 description 1
- RNONQEYAHNKSFG-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC RNONQEYAHNKSFG-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention relates to a synergic extraction agent for heavy rare earth elements and an extraction separation method of the synergic extraction agent. The synergic extraction agent comprises a component (a) and a component (b). The synergic extraction agent and thinner are mixed to form an organic phase to extract a heavy rear earth solution. In the extraction process, due to the fact that the two ionic-liquid-based extraction agents have a quite strong synergic extraction effect on heavy rare earth, the extraction capacity for heavy rare earth is obviously improved. Due to the fact that ionic liquid has a special phase shifting effect, a re-extraction agent more easily enters the organic phase, and the re-extraction rate is greatly increased. Multiple times of circulating saponification are not needed for the ionic liquid, and no ammonia-nitrogen waste water is generated in the extraction process.
Description
Technical Field
The invention relates to the field of rare earth extraction and separation, in particular to a synergistic extractant for heavy rare earth elements and an extraction and separation method thereof.
Background
With the development of science and technology, the demand of rare earth materials related to heavy rare earth is more and more increased. Such as scintillation crystals for Positron Emission Tomography (PET), are extremely dependent on the lutetium element. Separation is particularly difficult due to the close similarity of properties between heavy rare earth elements.
In the prior art, the extraction separation method which mainly adopts 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (code number P507) as a main extracting agent is mainly adopted for separating the heavy rare earth. The P507 extraction system has the following problems to be solved: p507 has smaller separation coefficient to partial rare earth elements; ② the heavy rare earth element back extraction acid has high concentration requirement. The invention patent CN 201310043075 discloses an extractant for separating heavy rare earth elements, which is prepared by fully mixing two acidic phosphine extractants C272 and P507 according to the volume ratio of 1: 0.5-1: 2 and then diluting the mixture with kerosene, partially solves the problem of difficult back extraction of thulium, ytterbium and lutetium elements, but the organic phase of the extractant still needs saponification.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an extractant for extracting and separating heavy rare earth elements, which has high extraction rate, is easy to back extract and does not need repeated cyclic saponification.
Another object of the present invention is to provide a method for efficiently extracting and separating heavy rare earth elements.
In view of this, the present invention provides the following technical solutions:
an extractant for heavy rare earth element extraction, characterized in that the extractant comprises (a) at least one of compounds represented by formula (I) and (b) at least one of compounds represented by formula (II):
wherein,
x is P or N;
R1、R2、R3and R4Identical or different, independently of one another, from the group consisting of substituted or unsubstituted, branched or straight-chain alkyl, substituted or unsubstituted aryl; the substituent is branched or straight chain alkyl, halogen or branched or straight chain alkoxy;
R5and R6Identical or different, independently of one another, from branched or straight-chain alkyl groups, preferably C3-C20More preferably branched or straight-chain alkyl, still more preferably C5-C10Most preferably 2-ethylhexyl.
R7And R8Identical or different, independently of one another, from branched or straight-chain alkyl groups, preferably C3-C20More preferably branched or straight-chain alkyl, still more preferably C5-C10Most preferably 2,4, 4-trimethylpentyl.
According to the invention, preferably, the extractant comprises (a) mono-2-ethylhexyl quaternary phosphonium or quaternary ammonium 2-ethylhexyl phosphonate and (b) di (2,4, 4-trimethylpentyl) phosphinic acid quaternary phosphonium or quaternary ammonium, the quaternary phosphonium and quaternary ammonium having the structure shown in formula (III):
wherein X is P or N;
R1、R2、R3and R4Identical or different, independently of one another, from the group consisting of substituted or unsubstituted, branched or straight-chain alkyl, substituted or unsubstituted aryl; the substituent is branched or straight chain alkyl, halogen or branched or straight chain alkoxy.
According to the invention，R1、R2、R3And R4Said branched or straight chain alkyl group in (1) is preferably C1-C20More preferably methyl, ethyl, n-butyl, n-hexyl, n-decyl, tetradecyl; the aryl group is preferably phenyl.
According to the invention, R1、R2、R3And R4Two or three of the groups are the same, or, alternatively, all four groups are the same. For example R1、R2、R3And R4Three of which are n-hexyl and the other is n-tetradecyl; or R1、R2、R3And R4Are all n-butyl.
According to the invention, the extractant is an ionic liquid-based synergic extractant.
According to the invention, in the extracting agent, the volume ratio of the component (a) to the component (b) is 1-9: 9-1. Also preferably 1.5-5: 5 to 1.5.
The invention also provides the following technical scheme:
a method for extracting and separating heavy rare earth elements comprises the following steps:
(1) mixing the component (a) and the component (b) in the extractant for extracting the heavy rare earth elements in proportion to obtain a mixture A;
(2) mixing the mixture A obtained in the step (1) with a diluent to form an organic phase;
(3) mixing the organic phase obtained in the step (2) with a heavy rare earth solution, and extracting to ensure that rare earth enters an organic phase;
(4) and (4) carrying out back extraction on the organic phase obtained in the step (3) by using inorganic acid to enable the rare earth to enter the water phase.
Preferably, in the step (1), the volume ratio of the component (a) to the component (b) is 1-9: 9-1, and preferably 1.5-5: 5 to 1.5.
Preferably, the volume ratio of the mixture A to the diluent in the step (2) is 1-50: 99 to 50, preferably 2 to 40: 98-60.
Preferably, the diluent is selected from one or more of alkanes or aromatics. Preferably, the alkane is selected from one or more of heptane, octane, hexadecane, aviation kerosene and 260# solvent kerosene, and the aromatic hydrocarbon is selected from one or more of benzene, toluene and xylene.
Preferably, the inorganic acid is selected from one of hydrochloric acid, nitric acid or sulfuric acid. More preferably hydrochloric acid or nitric acid, most preferably hydrochloric acid.
According to the invention, the molar concentration of the mineral acid is between 0.03 and 3.0mol/L, preferably between 0.4 and 1.5mol/L, more preferably between 0.7 and 1.3 mol/L.
According to the invention, the heavy rare earth element is one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
Compared with the prior art, the invention provides the ionic liquid-based synergic extractant for the heavy rare earth and the extraction method thereof, and in the extraction process, the two ionic liquid-based extractants have strong synergic extraction effect on the heavy rare earth, so that the extraction capability of the heavy rare earth is obviously improved. And secondly, due to the specific phase transfer effect of the ionic liquid, the stripping agent can more easily enter an organic phase, and the stripping rate is greatly improved. Furthermore, due to the specific action of the ionic liquid, the concentration of the used stripping agent is far lower than that of 5.5mol/L in the prior art, and the optimal concentration is 1.2mol/L, so that the stripping rate of 100 percent can be realized. The invention adopts ionic liquid saponification, and does not produce ammonia nitrogen wastewater in the extraction process. Thus, the present invention provides an effective method for effectively increasing the extraction capacity of conventional industrial extractants without the need for multiple rounds of saponification.
Drawings
FIG. 1 is a graph showing the results of synergistic extraction provided in examples 5 to 9 of the present invention.
FIG. 2 is a graph showing the back-extraction results provided in examples 10 to 15 of the present invention.
FIG. 3 is a graph showing the stripping results provided in comparative examples 1 to 6.
Detailed Description
As described above, the present invention provides an extractant for extracting heavy rare earth elements and an extraction method thereof, wherein the extraction method comprises the following steps: (1) mixing the component (a) and the component (b) in the extractant for extracting the heavy rare earth elements in proportion to form a mixture A (an ionic liquid-based synergic extractant); (2) mixing the mixture A with a diluent to form an organic phase; (3) mixing the organic phase with the heavy rare earth solution, and extracting to make the rare earth enter the organic phase; (4) the organic phase is back-extracted with mineral acid to bring the rare earths into the aqueous phase.
In the invention, the ionic liquid group comprises quaternary phosphonium group or quaternary ammonium group, the source of the ionic liquid group synergistic extraction agent and the precursor thereof is not limited, and the ionic liquid is preferably synthesized according to an acid-base neutralization method. The volume ratio of the component (a) to the component (b) is preferably 1-9: 9-1. Mixing the mixture A and a diluent to obtain an organic phase. The mixing method of the present invention is not limited, and may be any mixing method known to those skilled in the art.
In the present invention, the diluent is an alkane or an aromatic hydrocarbon. Preferably, the alkane is selected from one or more of heptane, octane, hexadecane, aviation kerosene and 260# solvent kerosene, and the aromatic hydrocarbon is selected from one or more of benzene, toluene and xylene. More preferably one of n-heptane or toluene.
In the invention, the volume ratio of the extracting agent to the diluting agent is preferably 1-50: 99-50.
The heavy rare earth solution used in the present invention may be a nitrate of a rare earth ion or a chloride of a rare earth ion, which is not limited in the present invention.
And extracting the rare earth elements in the organic phase heavy rare earth solution.
The heavy rare earth element is one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
The present invention preferably further comprises: the rare earth elements in the organic phase are back-extracted using an inorganic acid. The inorganic acid is preferably hydrochloric acid, nitric acid and sulfuric acid, more preferably hydrochloric acid and nitric acid, and most preferably hydrochloric acid. The concentration of the inorganic acid is not limited, but is preferably 0.03 to 3mol/L, and more preferably 0.4 to 1.5 mol/L.
The extraction temperature is preferably 20-35 ℃, and more preferably 23-30 ℃; the extraction time is preferably 5-10 min. The back extraction temperature is preferably 20-35 ℃, and more preferably 23-30 ℃; the back extraction time is preferably 5-10 min.
After the extraction separation process is finished, the mixed rare earth elements in the raffinate or the strip solution obtained by the method are preferably determined by an ICP-MS method, and the method specifically refers to the determination of the oxide content of the fifteen rare earth elements in the 8 th part of the GB/T18114.8-2010 rare earth concentrate chemical analysis method.
The single rare earth element is measured by azoarsine (III) colorimetry. The calculation formulas of the distribution ratio (D), the synergy factor (R), the stripping ratio (S) and the separation coefficient (beta) are as follows:
wherein [ M]tAnd [ M]aInitial concentration and equilibrium concentration, [ M ] of aqueous phase rare earth ions, respectively]aq,aAnd [ M]org,tThe concentration of rare earth in the counter acid and the concentration of organic phase rare earth are respectively. Da、Db、DmixThe distribution ratio of the extracting agent (I) for extracting the rare earth, the distribution ratio of the extracting agent (II) for extracting the rare earth and the distribution ratio of the mixture of the extracting agent (I) and the extracting agent (II) for extracting the rare earth are respectively. D1Is an extracting agent pairDistribution ratio of rare earth, D2Is the distribution ratio of the extractant to the other rare earth.
The synergistic extraction of the invention adopts the mixture of two ionic liquids as an extracting agent, which is distributed in both organic phase and aqueous phase, thus strengthening the complexation of the extracting agent and rare earth ions in the extraction process and improving the extraction rate of heavy rare earth. Therefore, the rare earth metal complex has high selectivity for rare earth elements, is combined with inorganic acid and diluent, and is easy to strip.
The present invention will be described in further detail with reference to the following drawings and examples. However, those skilled in the art will appreciate that the scope of the present invention is not limited to the following examples. In light of the present disclosure, those skilled in the art will recognize that many variations and modifications may be made to the embodiments described above without departing from the spirit and scope of the present invention. The materials used in the following examples are commercially available products unless otherwise specified.
Examples 1 to 2
Synthesis of [ P6,6,6,14] [ P507] and [ P6,6,6,14] [ C272]
In a 125ml separatory funnel, 0.008mol of tetradecyltrihexylphosphonium chloride (described as [ P6,6,6,14] Cl) was added to 60ml of methanol, and 75ml of an anion exchange resin was added to prepare a tetradecyltrihexylphosphonium hydroxide (described as [ P6,6,6,14] OH) solution. 0.008mol of 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (code P507) or bis (2,4, 4-trimethylpentyl) phosphinic acid (code C272) is added to the [ P6,6,6,14] OH solution, the mixture is stirred at room temperature for 6h until the solution becomes neutral, methanol and water are spun off at 70 ℃ using a rotary evaporator, and the product is dried in a vacuum drying cabinet at 70 ℃ for 12h to give a viscous liquid [ P6,6,6,14] [ P507] or [ P6,6,6,14] [ C272 ]. The yield reaches 95 percent.
Examples 3 to 4
Synthesis of [ N4444] [ P507] and [ N4444] [ C272]
Tetrabutylammonium bromide (denoted as [ N4444] Br) in an amount of 0.006mol was added to 40ml of methanol in a 125ml separatory funnel, and 75ml of () anion exchange resin was added to prepare a tetrabutylammonium hydroxide (denoted as [ N4444] OH) solution. To this solution was added 0.006mol of P507 or C272, the resulting mixture was stirred at room temperature for 6h until the solution became neutral, methanol and water were spun off at 70 ℃ using a rotary evaporator, and the product was dried in a vacuum oven at 70 ℃ for 12h to give a viscous liquid [ N4444] [ P507] or [ N4444] [ C272 ]. The yield reaches 96 percent.
Examples 5 to 9
Preparing an organic phase: [ P6,6,6,14] [ P507] synthesized according to the procedure described in example 1 and [ P6,6,6,14] [ C272] available from Cyanid, Canada. Different compositions of [ P6,6,6,14] [ P507] and [ P6,6,6,14] [ C272] were mixed with toluene to make up 5ml of organic phase at concentrations of 0.0208 and 0.0052, 0.0156 and 0.0104, 0.013 and 0.013, 0.0104 and 0.0156, 0.0052 and 0.0208mol/L, respectively.
Preparing a raw material liquid: adding dilute hydrochloric acid into 0.0030mol/L Lu (III) solution to prepare Lu (III) with concentration of 4.5 × 10-4mol/L of the starting material solution, NaCl 0.5 mol/L, pH 2.09.
Mixing the organic phase and the raw material liquid according to the volume ratio of 1:1, and extracting at room temperature, wherein the number of extraction stages is 1 stage. And after extraction is finished, calculating a synergistic extraction coefficient R. As shown in fig. 1, the partition ratio of the ionic liquid mixture after mixing is significantly greater than the partition ratio of the individual ionic liquids before mixing. From the synergy factor R values shown in fig. 1, it can be seen that under this condition, the R generated between the two ionic liquids varies from 7.2 to 19.8. When the concentrations of the two ionic liquids were the same, and both were 0.013mol/l, the maximum R value produced was 33.4.
Examples 10 to 15
Will [ P6,6,6,14]][P507](synthesized according to the procedure of example 1) with [ P6,6,6,14][C272](synthesized according to the method of example 2) in a volume ratio of 1:1 to form an ionic liquid-based synergic extractant, and mixing the synergic extractant with n-heptane to prepare an organic phase of 0.026 mol/L. Loading 0.06mol/LLuCl3The organic phase of (2) is mixed with the back extraction liquid with different concentrations in a volume ratio of 1:1, and back extraction is carried out at room temperature. The back extraction liquid is 0.1, 0.2, 0.3, 0.7, 1.0 and 1.2mol/L respectively. After the extraction was completed, the back extraction rate S% was calculated. As a result, as shown in FIG. 2, complete stripping was achieved with 1.2mol/L hydrochloric acid. This example illustrates that the heavy rare earths can be efficiently stripped after loading with an ionic liquid-based co-extractant.
Comparative examples 1 to 6
2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (code P507) and bis (2,4, 4-trimethylpentyl) phosphinic acid (code C272) were mixed in a volume ratio of 1:1, mixing the mixed extractant with n-heptane to prepare a 0.12mol/L organic phase. Loading 0.017mol/L LuCl3The organic phase of (2) is mixed with the back extraction liquid with different concentrations in a volume ratio of 1:1, and back extraction is carried out at room temperature. The back extraction liquid is 0.5, 1.0, 2.0, 3.0, 4.0 and 5.0mol/L respectively. After the extraction was completed, the back extraction rate S% was calculated. The results are shown in FIG. 3, where LuCl in the organic phase was stripped in a single pass with 4mol/L HCl3The back-extraction is still incomplete.
Examples 16 to 20
Is prepared from [ N4444]][P507](synthesized as in example 3) with [ N4444]][C272](synthesized according to the method of example 4) in a volume ratio of 1:1 to form an ionic liquid-based synergic extractant, and mixing the synergic extractant with n-heptane to prepare a 0.05mol/L organic phase. The organic phase was separately mixed with 0.015mol/L HoCl3、ErCl3、TmCl3、YbCl3And LuCl3The solutions were mixed at a volume ratio of 1:1 and extracted at room temperature. And after extraction is finished, calculating the synergistic extraction coefficient R. The results show that the product is represented by [ N4444]][P507]And [ N4444][C272]Mixing the components in a volume ratio of 1:1 composition Ionic liquid-based synergistic extractant pair HoCl3、ErCl3、TmCl3、YbCl3And LuCl3The synergistic extraction coefficients of (A) are 4, 8, 15, 25 and 60 respectively.
Claims (10)
1. An extractant for heavy rare earth element extraction, characterized in that the extractant comprises (a) at least one of compounds represented by formula (I) and (b) at least one of compounds represented by formula (II):
wherein,
x is P or N;
R1、R2、R3and R4Identical or different, independently of one another, from the group consisting of substituted or unsubstituted, branched or straight-chain alkyl, substituted or unsubstituted aryl; the substituent is branched or straight chain alkyl, halogen or branched or straight chain alkoxy;
R5and R6Identical or different, independently of one another, from branched or straight-chain alkyl groups, preferably C3-C20More preferably branched or straight-chain alkyl, still more preferably C5-C10Most preferably 2-ethylhexyl.
R7And R8Identical or different, independently of one another, from branched or straight-chain alkyl groups, preferably C3-C20More preferably branched or straight-chain alkyl, still more preferably C5-C10Most preferably 2,4, 4-trimethylpentyl.
2. The extractant of claim 1 comprising (a) mono-2-ethylhexyl 2-ethylhexylphosphonate or quaternary ammonium and (b) bis (2,4, 4-trimethylpentyl) phosphinic acid as quaternary phosphonium or quaternary ammonium, the quaternary phosphonium and quaternary ammonium having the structure of formula (III):
x is P or N;
R1、R2、R3and R4Identical or different, independently of one another, from the group consisting of substituted or unsubstituted, branched or straight-chain alkyl, substituted or unsubstituted aryl; the substituent is branched or straight chain alkyl, halogen or branched or straight chain alkoxy.
Preferably, R1、R2、R3And R4Said branched or straight chain alkyl group in (1) is preferably C1-C20More preferably methyl, ethyl, n-butyl, n-hexyl, n-decyl, tetradecyl; the aryl group is preferably phenyl.
More preferably, R1、R2、R3And R4Two or three of the groups are the same, or, alternatively, all four groups are the same. For example R1、R2、R3And R4Three of which are n-hexyl and the other is n-tetradecyl; or R1、R2、R3And R4Are all n-butyl.
3. The extractant of claim 1 or 2, which is an ionic liquid-based co-extractant.
4. The extractant of any one of claims 1 to 3, wherein the volume ratio of component (a) to component (b) in the extractant is 1-9: 9-1.
The volume ratio is preferably 1.5-5: 5 to 1.5.
5. A method for extracting and separating heavy rare earth elements comprises the following steps:
(1) mixing the component (a) and the component (b) in the extractant of any one of claims 1 to 4 in proportion to obtain a mixture A;
(2) mixing the mixture A obtained in the step (1) with a diluent to form an organic phase;
(3) mixing the organic phase obtained in the step (2) with a heavy rare earth solution, and extracting to ensure that rare earth enters an organic phase;
(4) and (4) carrying out back extraction on the organic phase obtained in the step (3) by using inorganic acid to enable the rare earth to enter the water phase.
6. The extractive separation method according to claim 5, wherein in the step (1), the volume ratio of the component (a) to the component (b) is 1-9: 9-1. The volume ratio is preferably 1.5-5: 5 to 1.5.
7. The extraction separation method according to claim 5 or 6, wherein the volume ratio of the mixture A to the diluent in the step (2) is 1-50: 99 to 50. The volume ratio is preferably 2-40: 98-60.
8. The extractive separation process of any one of claims 5 to 7, wherein the diluent is selected from one or more of an alkane or an aromatic hydrocarbon. Preferably, the alkane is selected from one or more of heptane, octane, hexadecane, aviation kerosene and 260# solvent kerosene, and the aromatic hydrocarbon is selected from one or more of benzene, toluene and xylene.
9. The extractive separation method according to any one of claims 5 to 8, wherein the inorganic acid is one selected from hydrochloric acid, nitric acid, and sulfuric acid. More preferably hydrochloric acid or nitric acid, most preferably hydrochloric acid.
Preferably, the molar concentration of the inorganic acid is between 0.03 and 3.0mol/L, preferably between 0.4 and 1.5mol/L, more preferably between 0.7 and 1.3 mol/L.
10. The extractive separation method according to any one of claims 5 to 9, wherein the heavy rare earth element is one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
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| CN110724161A (en) * | 2019-10-31 | 2020-01-24 | 安阳师范学院 | Functionalized ionic liquid linear primary amine phosphinate homolog and preparation method and application thereof |
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