Method for promoting ion extraction based on molecular steric configuration

Abstract

The invention provides a method for promoting ion extraction based on molecular spatial configuration. Compared with a monomer extraction agent molecule or a trans-steric configuration molecule, the cis-steric configuration molecule with the pre-organizing structure has the advantage that the extraction capacity of a homeopathic structure on metal ions is obviously improved. And through change of connected monomer molecules, efficient extraction and recovery of different valuable metals can be realized. The method has a good application prospect in the field of hydrometallurgy.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrometallurgy, and specifically relates to a method for promoting ion extraction based on molecular spatial configuration, and more particularly to the design and preparation of extractant molecules with a unique three-dimensional configuration of a reagent and their application in the extraction of metal ions. Background Art

[0002] Solvent extraction is a mature hydrometallurgical technology that is efficient and can be continuously produced on a large scale. Its core lies in the design and preparation of extractant molecules. Relevant scholars have carried out a lot of research work around the development of functional extractants. Most of them are designed based on the principles of molecule-metal coordination thermodynamics, such as the compatibility of coordinating atoms, the bonding and conjugation between coordinating atoms and metals. Although there are hundreds of extractants that have been publicly reported to date, only a small part of them can really play an effective extraction / separation role. Due to the limitations of molecular design concepts, a large amount of R&D investment has not been matched with technological innovation.

[0003] Compared with the optimization of coordination thermodynamic properties, there are few reports on the design / improvement of functional ligands from the perspective of molecular spatial configuration and their use in the extraction / separation of target metal ions. Summary of the invention

[0004] The inventors of the present invention have found that molecules with pre-organized structures essentially have a spatial structure ( Figure 1 ). Based on this special structure, designing / preparing three-dimensional molecules that are conducive to extraction from the perspective of spatial configuration will have the opportunity to show considerable potential in the selective extraction and separation of metal ions.

[0005] One of the purposes of the present invention is to provide a cis-stereo-configuration molecule with a pre-organized structure. Compared with a monomer extractant molecule or a trans-stereo-configuration molecule, the cis-structure has a significantly improved extraction capacity for metal ions.

[0006] The cis stereogenic molecule with a pre-organized structure provided by the present invention has a structural formula as shown in Formula I:

[0007]

[0008] In the above formula I, A represents a pre-organization platform, which can be C3-C 14 The cycloalkyl group may be at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl and cyclotetradecyl;

[0009] The two branches in Formula I are substituents on adjacent carbon atoms of the cycloalkyl group;

[0010] X and Y are the same or different and are independently selected from: Where D represents a C6-C containing a coordinating atom (O, N, S, P). 14 Aryl, biaryl containing coordinating atoms (O, N, S, P), C3-C8 cycloalkyl containing coordinating atoms (O, N, S, P), ether ( wherein m and n are each independently an integer of 1 to 6), at least one of -C1-C6 alkylene;

[0011] R1 and R2 are the same or different and are independently selected from: C1-C 10 Straight or branched alkyl, C3-C8 cycloalkyl, substituted or unsubstituted C6-C 14 The aryl group, or R1, R2 and the N connected thereto form a saturated or unsaturated five-membered or six-membered ring, wherein the saturated or unsaturated five-membered or six-membered ring may be substituted by a coordinating atom (O, N, S, or P), or the H on the carbon atom of the saturated or unsaturated five-membered or six-membered ring may be replaced by a C6-C 14 Aryl or C1-C6 straight chain or branched alkyl substitution;

[0012] R3 and R4 are the same or different and are independently selected from: C1-C 10 Straight or branched alkyl, C3-C8 cycloalkyl, substituted or unsubstituted C6-C 14 The aromatic group, or R3, R4 and the N connected thereto form a saturated or unsaturated five-membered or six-membered ring containing or not containing a coordinating atom (O, N, S, P), wherein the H on the carbon atom of the saturated or unsaturated five-membered or six-membered ring can be replaced by a C6-C 14 Aryl or C1-C6 straight chain or branched alkyl substitution;

[0013] Wherein, the C6-C containing coordination atoms (O, N, S, P) 14 The aryl group may specifically be: furyl, pyridyl, naphthalene, anthracene, phenanthryl containing a nitrogen atom;

[0014] The C6-C 14 The aryl group may specifically be: phenyl;

[0015] The biaryl group containing a coordinating atom (O, N, S, P) may specifically be: a bipyridyl group;

[0016] Substituted C6-C 14 The substituents in the aromatic group can be: nitro, cyano, halogen, C1-C 10 Straight or branched alkyl, C1-C 10 Any of alkoxy and halogen-substituted C1-C6 alkyl.

[0017] The cis stereogenic molecule having a pre-organized structure shown in the above formula I may specifically be any one of the following compounds:

[0018]

[0019] The cis stereogenic molecule with a pre-organized structure shown in the above formula I used as an extractant for metal ions also falls within the protection scope of the present invention.

[0020] Specifically, the cis-stereoconfiguration molecule with a pre-organized structure shown in Formula I is used as an extractant for metal ions in the field of hydrometallurgy.

[0021] In the application, the metal ions include alkali metals, alkaline earth metals, noble metals, rare earth metals and actinide metal ions, and specifically may include Cs, Tc, Sr, Am, Ru, Nd, Lu, U and Pu.

[0022] The second object of the present invention is to provide a method for extracting metal ions using cis stereogenic molecules with a pre-organized structure.

[0023] The method for extracting metal ions provided by the present invention comprises the following steps:

[0024] The cis stereo configuration molecules with the pre-organized structure are dissolved in an organic solvent to obtain an organic phase; the organic phase is directly mixed with an acidic aqueous solution containing specific metal ions, and after the two phases are balanced, the phases are separated by centrifugation to achieve extraction of the metal ions.

[0025] In the above method, the organic solvent includes any one or a mixture of cycloalkanes, fatty alcohols, ketones, and aromatic compounds, and specifically can be any one or a mixture of n-octanol, dodecane, benzene, toluene, cyclohexane, cyclohexanone, and m-nitrotrifluorotoluene; wherein the ratio of the mixture of the organic solvents is not specifically limited, and generally any ratio is acceptable;

[0026] The concentration of the molecule in the organic phase may range from 10 -4 -1mol / L;

[0027] The acidic aqueous solution includes a perchloric acid aqueous solution, a nitric acid aqueous solution, a sulfuric acid aqueous solution, a hydrochloric acid aqueous solution, a phosphoric acid aqueous solution, and the like.

[0028] The acidity range of the aqueous solution may be 10 -5 -14mol / L.

[0029] The specific metal ions include alkali metals, alkaline earth metals, noble metals, rare earth metals and actinide metal ions, and specifically may include Cs, Tc, Sr, Am, Ru, Nd, Lu, U and Pu.

[0030] The concentration range of the specific metal ion in the aqueous solution can be 10 -8 -10-3 mol / L;

[0031] The phase ratio (volume ratio) of the above two phases can be any ratio within the range of 1:10-10:1;

[0032] The two-phase mixing time can be 1-360min;

[0033] The centrifugal conditions are: 3000-5000 rpm, 1-5 min.

[0034] Compared with the prior art, the present invention has the following advantages and outstanding technical effects:

[0035] 1) The extraction system provided by the present invention can achieve a qualitative leap in extraction effect by adjusting the pre-organized configuration without changing the essential molecular structure.

[0036] 2) The extraction system provided by the present invention can change the monomer extractant molecules according to the different target metal ions, and has wide universality.

[0037] 3) The extraction system provided by the present invention can cover a wide range of acidity, which greatly enhances the applicability of the method in the field of metal extraction and separation, and shows good application prospects in the field of hydrometallurgy.

[0038] 4) The equipment, materials and reagents involved in the present invention can all be obtained through commercial channels, without the need for targeted customization, design and preparation, thereby fundamentally achieving cost reduction and efficiency improvement. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The molecules with pre-organized structures are (a) cis stereo configuration (wherein the two branches connected to A are located on the same side of the plane where A is located, i.e., above the plane or below the plane), (b) cis planar configuration, (c) trans stereo configuration (wherein the two branches connected to A are located on the opposite sides of the plane where A is located, i.e., one is above the plane and the other is below the plane), and (d) trans planar configuration. Wherein, A represents the pre-organized platform, and B and C represent monomer extractant molecules.

[0040] Figure 2 NMR of compound L4 1 H NMR characterization spectrum.

[0041] Figure 3 NMR of compound L13 1 H NMR spectrum.

[0042] Figure 4 NMR of compound L22 1 H NMR spectrum. DETAILED DESCRIPTION

[0043] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.

[0044] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial channels.

[0045] In the following examples, the concentration of metal ions in the organic phase (C metal ion-org. ) and the concentration in the aqueous phase (C metal ion-aq. ) is defined as the distribution ratio (Distribution ratio of metal ion).

[0046] The structures in the embodiments and comparative examples listed in the present invention are synthesized using the following routes, and the reference materials are as follows:

[0047] 1. Pretsch E., Ammann D., Osswald HF, Giiggi M., Simon W., Ionophore vomTyp der 3-Oxapentandiamide, Helvetica Chimica Acta, 1980, 63, 191-196.

[0048] 2. J. Nash Sharma, Ritesh J. Ruhra, S. Manohar, P. K. Wattar, Ashok Kumar Suri, Dialkyldiaza-tetraalkyloctanediamide derivatives for separation of trivalent actinides from lanthanides and preparation methods thereof, 2014, CN 102712578B.

[0049] The following is explained by taking compounds L4, L13, and L22 as examples.

[0050] dinucleotide Add thionyl chloride SOCl2 in a molar ratio of 1:2 into the reactor and heat under reflux to obtain diglycolic acid chloride. Dibutylamine The molar equivalent of 1:1 was added into the reactor and heated under reflux to obtain N,N-dibutyl-3-oxo-glutaramide.

[0051] For compound L4, N,N-dibutyl-3-oxo-glutaramide and cis-1,2-cyclohexanediamine The reaction mixture was added into a reactor in a molar equivalent of 2:1 and heated under reflux to obtain compound L4.

[0052] For compound L22, N,N-dibutyl-3-oxo-glutaramide and di-n-butylamine were added into a reactor in a molar equivalent of 1:1, and heated under reflux to obtain compound L22.

[0053] For compound L13, N,N-dibutyl-3-oxo-glutaramide and trans-1,2-cyclohexanediamine were reacted. The reaction mixture was added into a reactor in a molar equivalent of 2:1 and heated under reflux to obtain compound L13.

[0054]

[0055] The NMR of the prepared compound L4 1 H NMR characterization spectrum Figure 2 shown.

[0056] The NMR of the prepared compound L13 1 H NMR spectrum Figure 3 shown.

[0057] The prepared compound L22 1 H NMR spectrum Figure 4 shown.

[0058] The preparation of the structures involved in other embodiments and comparative examples can be completed by referring to the above method.

[0059] Example 1

[0060] Compound L1 was dissolved in n-octanol to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Cs was added to a 1 mol / L nitric acid solution to prepare a Cs concentration of 10 -6 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:1 for 60 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Cs was measured to be 73.

[0061] Example 2

[0062] Compound L2 was dissolved in toluene to a concentration of 10 -4 mol / L organic solution as the organic phase. Add an appropriate amount of Tc to 10 -5 mol / L sulfuric acid solution to prepare a Tc concentration of 10 -8mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 10:1 for 360 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Tc was measured to be 103.

[0063] Example 3

[0064] Compound L3 was dissolved in benzene to prepare an organic solution with a concentration of 1 mol / L as the organic phase. An appropriate amount of Sr was added to 10 -2 mol / L hydrochloric acid solution was prepared to a Sr concentration of 10 -7 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 5:1 for 180 min, centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Sr was measured to be 115.

[0065] Example 4

[0066] Compound L4 was dissolved in dodecane to a concentration of 10 -2 mol / L organic solution as the organic phase. Add an appropriate amount of Am to a 3 mol / L perchloric acid solution to prepare an Am concentration of 10 -5 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:1 for 120 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Am was measured to be 372.

[0067] Example 5

[0068] Compound L5 was dissolved in cyclohexane to a concentration of 10 -3 mol / L organic solution as the organic phase. Add an appropriate amount of Ru to a 5 mol / L phosphoric acid solution to prepare a Ru concentration of 10 -4 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:5 for 10 min, centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Ru was measured to be 96.

[0069] Example 6

[0070] Compound L6 was dissolved in cyclohexanone to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Nd was added to a 14 mol / L nitric acid solution to prepare a solution with a Nd concentration of 10 -3mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:10 for 1 min, and centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Nd was measured to be 164.

[0071] Example 7

[0072] Compound L7 was dissolved in toluene to a concentration of 10 -4 mol / L organic solution as the organic phase. Add an appropriate amount of Lu to 10 -5 mol / L sulfuric acid solution to prepare a Lu concentration of 10 -8 The organic phase and the aqueous phase were mixed at a ratio of 10:1 for 360 min, and the phases were separated by centrifugation (3000 rpm, 5 min). The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Lu was measured to be 493.

[0073] Example 8

[0074] Compound L8 was dissolved in benzene to prepare an organic solution with a concentration of 1 mol / L as the organic phase. An appropriate amount of U was added to 10 -2 mol / L hydrochloric acid solution to prepare a U concentration of 10 -7 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 5:1 for 180 min, centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of U was measured to be 268.

[0075] Example 9

[0076] Compound L9 was dissolved in cyclohexanone to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Pu was added to a 14 mol / L nitric acid solution to prepare a Pu concentration of 10 -3 The organic phase and the aqueous phase were mixed at a ratio of 1:10 for 1 min, and centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Pu was measured to be 377.

[0077] Comparative Example 1

[0078] Compound L10 (the difference between L10 and L1 is that L10 has a trans pre-organized structure, while L1 has a cis pre-organized structure) was dissolved in n-octanol to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Cs was added to a 1 mol / L nitric acid solution to prepare a Cs concentration of 10 -6mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:1 for 60 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Cs was measured to be 6.4.

[0079] Comparative Example 2

[0080] Compound L11 was dissolved in toluene to a concentration of 10 -4 mol / L organic solution as the organic phase. Add an appropriate amount of Tc to 10 -5 mol / L sulfuric acid solution to prepare a Tc concentration of 10 -8 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 10:1 for 360 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Tc was measured to be 7.5.

[0081] Comparative Example 3

[0082] Compound L12 was dissolved in benzene to prepare an organic solution with a concentration of 1 mol / L as the organic phase. An appropriate amount of Sr was added to 10 -2 mol / L hydrochloric acid solution was prepared to a Sr concentration of 10 -7 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 5:1 for 180 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Sr was measured to be 10.

[0083] Comparative Example 4

[0084] Compound L13 was dissolved in dodecane to a concentration of 10 -2 mol / L organic solution as the organic phase. Add an appropriate amount of Am to a 3 mol / L perchloric acid solution to prepare an Am concentration of 10 -5 mol / L aqueous solution as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:1 for 120 min, centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Am was measured to be 22.

[0085] Comparative Example 5

[0086] Compound L14 was dissolved in cyclohexane to a concentration of 10 -3 mol / L organic solution as the organic phase. Add an appropriate amount of Ru to a 5 mol / L phosphoric acid solution to prepare a Ru concentration of 10 -4mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:5 for 10 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Ru was measured to be 5.8.

[0087] Comparative Example 6

[0088] Compound L15 was dissolved in cyclohexanone to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Nd was added to a 14 mol / L nitric acid solution to prepare a solution with a Nd concentration of 10 -3 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:10 for 1 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Nd was measured to be 8.4.

[0089] Comparative Example 7

[0090] Compound L16 was dissolved in toluene to a concentration of 10 -4 mol / L organic solution as the organic phase. Add an appropriate amount of Lu to 10 -5 mol / L sulfuric acid solution to prepare a Lu concentration of 10 -8 The organic phase and the aqueous phase were mixed at a ratio of 10:1 for 360 min, and centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Lu was measured to be 16.

[0091] Comparative Example 8

[0092] Compound L17 was dissolved in benzene to prepare an organic solution with a concentration of 1 mol / L as the organic phase. An appropriate amount of U was added to 10 -2 mol / L hydrochloric acid solution to prepare a U concentration of 10 -7 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 5:1 for 180 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of U was measured to be 13.

[0093] Comparative Example 9

[0094] Compound L18 was dissolved in cyclohexanone to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Pu was added to a 14 mol / L nitric acid solution to prepare a Pu concentration of 10 -3mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:10 for 1 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Pu was measured to be 24.

[0095]

[0096] Comparative Example 10

[0097] Compound L19 was dissolved in n-octanol to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Cs was added to a 1 mol / L nitric acid solution to prepare a Cs concentration of 10 -6 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:1 for 60 min, centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Cs was measured to be 0.52.

[0098] Comparative Example 11

[0099] Compound L20 was dissolved in toluene to a concentration of 10 -4 mol / L organic solution as the organic phase. Add an appropriate amount of Tc to 10 -5 mol / L sulfuric acid solution to prepare a Tc concentration of 10 -8 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 10:1 for 360 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Tc was measured to be 0.45.

[0100] Comparative Example 12

[0101] Compound L21 was dissolved in benzene to prepare an organic solution with a concentration of 1 mol / L as the organic phase. An appropriate amount of Sr was added to 10 -2 mol / L hydrochloric acid solution was prepared to a Sr concentration of 10 -7 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 5:1 for 180 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Sr was measured to be 1.3.

[0102] Comparative Example 13

[0103] Compound L22 was dissolved in dodecane to a concentration of 10 -2 mol / L organic solution as the organic phase. Add an appropriate amount of Am to a 3 mol / L perchloric acid solution to prepare an Am concentration of 10-5 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:1 for 120 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Am was measured to be 1.7.

[0104] Comparative Example 14

[0105] Compound L23 was dissolved in cyclohexane to a concentration of 10 -3 mol / L organic solution as the organic phase. Add an appropriate amount of Ru to a 5 mol / L phosphoric acid solution to prepare a Ru concentration of 10 -4 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:5 for 10 min, and centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Ru was measured to be 0.25.

[0106] Comparative Example 15

[0107] Compound L24 was dissolved in cyclohexanone to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Nd was added to a 14 mol / L nitric acid solution to prepare a solution with a Nd concentration of 10 -3 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:10 for 1 min, and centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Nd was measured to be 0.57.

[0108] Comparative Example 16

[0109] Compound L25 was dissolved in toluene to a concentration of 10 -4 mol / L organic solution as the organic phase. Add an appropriate amount of Lu to 10 -5 mol / L sulfuric acid solution to prepare a Lu concentration of 10 -8 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 10:1 for 360 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of Lu was measured to be 0.09.

[0110] Comparative Example 17

[0111] Compound L26 was dissolved in benzene to prepare an organic solution with a concentration of 1 mol / L as the organic phase. An appropriate amount of U was added to 10 -2 mol / L hydrochloric acid solution to prepare a U concentration of 10 -7mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 5:1 for 180 min, and centrifuged (3000 rpm, 5 min) to separate the phases. The organic phase and the aqueous phase were collected separately, and the extraction distribution ratio of U was measured to be 0.89.

[0112] Comparative Example 18

[0113] Compound L27 was dissolved in cyclohexanone to prepare an organic solution with a concentration of 0.1 mol / L as the organic phase. An appropriate amount of Pu was added to a 14 mol / L nitric acid solution to prepare a Pu concentration of 10 -3 mol / L aqueous solution was used as the aqueous phase. The organic phase and the aqueous phase were mixed at a ratio of 1:10 for 1 min, and centrifuged (3000 rpm, 5 min), and the organic phase and the aqueous phase were collected separately. The extraction distribution ratio of Pu was measured to be 1.7.

[0114]

[0115] Table 1. Extraction results summary comparison table

[0116]

[0117] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, and without the need to carry out unnecessary experimental conditions, the present invention can be implemented in a wide range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principles of the present invention, the application is intended to include any changes, uses or improvements to the present invention, including departure from the disclosed scope in the application, and changes made with conventional techniques known in the art.

Claims

1. A cis stereogenic molecule having a pre-organized structure, the structural formula of which is shown in Formula I: In the above formula I, A represents a pre-organization platform, which can be C3-C 14 The cycloalkyl group may be at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl and cyclotetradecyl; The two branches in Formula I are substituents on adjacent carbon atoms of the cycloalkyl group; X and Y are the same or different and are independently selected from: Where D represents a C6-C 14 Aryl, biaryl containing coordinating atoms (O, N, S, P), C3-C8 cycloalkyl containing coordinating atoms (O, N, S, P), ether ( in, m, n are each independently an integer of 1-6), at least one of -C1-C6 alkylene; R1 and R2 are the same or different and are independently selected from: C1-C 10 Straight or branched alkyl, C3-C8 cycloalkyl, substituted or unsubstituted C6-C 14 The aryl group, or R1, R2 and the N connected thereto form a saturated or unsaturated five-membered or six-membered ring, wherein the saturated or unsaturated five-membered or six-membered ring may be substituted by a coordinating atom (O, N, S, or P), or the H on the carbon atom of the saturated or unsaturated five-membered or six-membered ring may be replaced by a C6-C 14 Aryl or C1-C6 straight chain or branched alkyl substitution; R3 and R4 are the same or different and are independently selected from: C1-C 10 Straight or branched alkyl, C3-C8 cycloalkyl, substituted or unsubstituted C6-C 14 The aromatic group, or R3, R4 and the N connected thereto form a saturated or unsaturated five-membered or six-membered ring containing or not containing a coordinating atom (O, N, S, P), wherein the H on the carbon atom of the saturated or unsaturated five-membered or six-membered ring can be replaced by a C6-C 14 The alkyl group may be substituted with an aryl group or a C1-C6 straight chain or branched alkyl group.

2. The molecule according to claim 1, characterized in that The C6-C containing coordination atoms (O, N, S, P) 14 Aryl is: furanyl, pyridyl, naphthalene, anthracene, phenanthryl containing nitrogen atoms; The C6-C 14 Aryl is: phenyl; The biaryl group containing coordinating atoms (O, N, S, P) is: bipyridyl; Substituted C6-C 14 The substituents in the aromatic group are: nitro, cyano, halogen, C1-C 10 Straight or branched alkyl, C1-C 10 Any of alkoxy and halogen-substituted C1-C6 alkyl.

3. The molecule according to claim 1 or 2, characterized in that The molecule is any one of the following compounds:

4. Use of the cis-stereoconfiguration molecule having a pre-organized structure represented by formula I according to any one of claims 1 to 3 as an extractant for metal ions.

5. The use according to claim 4, characterized in that: The cis stereo-configuration molecule with a pre-organized structure shown in Formula I is used as an extractant for metal ions in the field of hydrometallurgy.

6. The use according to claim 4 or 5, characterized in that: In the application, the metal ions include alkali metals, alkaline earth metals, noble metals, rare earth metals and actinide metal ions.

7. A method for extracting metal ions, comprising the steps of: The cis-stereoconfiguration molecule with a pre-organized structure shown in formula I of any one of claims 1 to 3 is dissolved in an organic solvent to obtain an organic phase; the organic phase is directly mixed with an acidic aqueous solution containing specific metal ions, and after the two phases are balanced, centrifugation is performed to separate the phases to achieve extraction of the metal ions.

8. The method according to claim 7, characterized in that The organic solvent includes any one or a mixture of cycloalkanes, fatty alcohols, ketones, and aromatic compounds; The concentration range of the molecules in the organic phase is 10 -4 -1mol / L.

9. The method according to claim 7, characterized in that: The acidic aqueous solution includes an aqueous perchloric acid solution, an aqueous nitric acid solution, an aqueous sulfuric acid solution, an aqueous hydrochloric acid solution, and an aqueous phosphoric acid solution; The acidity range of the aqueous solution is 10 -5 -14mol / L.

10. The method according to claim 7, characterized in that The concentration range of the specific metal ion in the aqueous solution can be 10 -8 -10 -3 mol / L; The volume ratio of the two phases is any ratio within the range of 1:10-10:1; The two-phase mixing time is 1-360min; The centrifugal conditions are: 3000-5000 rpm, 1-5 min.

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