Ketooxime / aldeoxime-phosphonate / phosphonic acid compounds, their preparation methods and applications

Abstract

This invention provides ketoxime / aldeoxime-phosphonate / phosphonoside compounds, their preparation methods, and applications. The ketoxime / aldeoxime is generated by a substitution reaction between a haloketoxime / aldeoxime and a trialkyl phosphite; or by an addition reaction between an α,β-unsaturated aldehyde / ketone and a dialkyl phosphite, followed by saponification and acidification to obtain the ketoxime / aldeoxime-phosphonoside compound. Because it simultaneously possesses ketoxime / aldeoxime and phosphonate / phosphonoside functional groups, the ketoxime / aldeoxime group can chelate cobalt ions to form a ring through the oxygen and nitrogen atoms in its structure, while the phosphonate / phosphonoside group is an effective functional group for separating and extracting cobalt and nickel ions. The synergistic chelating ability of the two groups enhances the extraction and recovery of cobalt ions and the separation from nickel ions in the acidic leachate of spent power batteries. The entire extraction and recovery process is simple, efficient, and feasible, meeting the requirements of industrial applications.

Description

Technical Field

[0001] This invention relates to the field of metal ion extraction technology, specifically to ketoxime / aldeoxime-phosphonate / phosphonic acid compounds, their preparation methods, and applications. Background Technology

[0002] Currently, with the rapid development of the new energy industry and strong national support for it, the total volume of retired power batteries, a typical "urban mine," is also growing rapidly. Waste power batteries contain a large amount of valuable metals (such as ~10% Co, 10-15% Ni, and 1-2% Li). The recycling of these valuable metal resources is expected to alleviate the scarcity of domestic non-ferrous metal resources and dependence on foreign resources. Among these, the separation and recycling of cobalt and nickel has always been a key and challenging issue in the recycling of valuable metal resources. Nickel and cobalt have very similar chemical properties, making separation difficult. Solvent extraction is the only method that can obtain high-quality products from mixtures of these two elements and is also the only method that can effectively process them regardless of the metal ion concentration. Therefore, designing and developing efficient extractants for the extraction and separation of low-concentration cobalt and nickel ions in acidic leachates from waste power batteries is of great significance.

[0003] In recent years, several commercial extractants, such as D2EHPA (bis(2-ethylhexyl)phosphoric acid), PC88A (2-ethylhexylphosphonic acid mono-2-ethylhexyl ester), and Cyanex 272 (bis(2,4,4-trimethylpentyl)phosphonic acid), have proven stable under acidic conditions and exhibit high acid resistance, making them commonly used as extractants for cobalt-nickel separation. Cyanex 272, in particular, is an excellent extractant for cobalt-nickel separation. However, the synthesis of Cyanex 272 is complex and requires stringent processes, resulting in high production costs. Summary of the Invention

[0004] The purpose of this invention is to address the above-mentioned shortcomings of the prior art by providing ketoxime / aldehyde oxime-phosphonate / phosphonic acid compounds, their preparation methods, and applications. This extractant can exist stably at high acidity and can form strong complexes with cobalt ions, making it particularly suitable for the efficient extraction and recovery of cobalt and nickel from high-acidity leachates of spent power batteries.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] The first object of the present invention is to provide a ketoxime / aldeoxime-phosphonate / phosphonic acid compound, characterized in that its chemical structure is as shown in formula (I):

[0007]

[0008] Among them, R1 is selected from H, C1-C 16 Alkyl, C6-C10 aryl and C7-C 16 R2 is selected from any of the aralkyl groups; R2 is selected from C1-C2. 16 Alkyl, C6-C 10 aryl, C7-C 16 Aryl groups, C1-C 16 alkoxy groups, C6-C 10 aryloxy groups and C7-C 16 R3 is any one of the arylalkoxy groups; R4 is a C1-C3 hydrocarbon group or arylalkyl group; R5 is H or CH3.

[0009] Furthermore, R1 is selected from any one of hydrogen, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, phenyl, p-tolyl, n-octyl, isooctyl, sec-octyl, 2-ethylhexyl, n-decyl, or isodecyl.

[0010] Furthermore, R2 is selected from any one of ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, phenyl, p-tolyl, n-octyl, isooctyl, sec-octyl, 2-ethylhexyl, n-decyl, isodecyl, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentoxy, isopentoxy, neopentoxy, n-hexoxy, isohexoxy, phenoxy, p-tolyloxy, n-octoxy, isooctoxy, sec-octoxy, 2-ethylhexyloxy, n-decoxy, or isodecoxy.

[0011] Furthermore, R3 is any one of methylene, 1,2-ethylene, ethylene, and benzenemethylene; and R4 is H or CH3.

[0012] A more specific feasible method is: when R4 is hydrogen, R3 is methylene, R1 is ethyl, and R2 is ethoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate diethyl ester;

[0013] When R4 is hydrogen, R3 is methylene, R1 is propyl, and R2 is propoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate dipropyl ester.

[0014] When R4 is hydrogen, R3 is methylene, R1 isopropyl, and R2 isopropoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate diisopropyl ester.

[0015] When R4 is hydrogen, R3 is methylene, R1 is butyl, and R2 is butoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate dibutyl ester.

[0016] When R4 is hydrogen, R3 is methylene, R1 isobutyl, and R2 isobutoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate diisobutyl ester.

[0017] When R4 is hydrogen, R3 is methylene, R1 is sec-butyl, and R2 is sec-butoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate disec-butyl ester.

[0018] When R4 is hydrogen, R3 is methylene, R1 is pentyl, and R2 is pentoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate dipentyl ester.

[0019] When R4 is hydrogen, R3 is methylene, R1 isopentyl, and R2 isopentoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate diisopentyl ester.

[0020] When R4 is hydrogen, R3 is methylene, R1 is neopentyl, and R2 is neopentyloxy, formula (I) is dinepentyl phosphonate (2-(hydroxyimino)ethyl)phosphonate.

[0021] When R4 is hydrogen, R3 is methylene, R1 is n-hexyl, and R2 is n-hexyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate di-n-hexyl ester.

[0022] When R4 is hydrogen, R3 is methylene, R1 isohexyl, and R2 isohexyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonic acid diisohexyl ester.

[0023] When R4 is hydrogen, R3 is methylene, R1 is phenyl, and R2 is phenoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonic acid diphenyl ester.

[0024] When R4 is hydrogen, R3 is methylene, R1 is p-tolyl, and R2 is p-tolyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonic acid di-p-tolyl ester;

[0025] When R4 is hydrogen, R3 is methylene, R1 is n-octyl, and R2 is n-octyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate di-n-octyl ester;

[0026] When R4 is hydrogen, R3 is methylene, R1 isooctyl, and R2 isooctoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate diisooctyl ester;

[0027] When R4 is hydrogen, R3 is methylene, R1 is 2-octyl, and R2 is 2-octyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate di-2-octyl ester.

[0028] When R4 is hydrogen, R3 is methylene, R1 is 2-ethylhexyl, and R2 is 2-ethylhexyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonic acid bis(2-ethylhexyl) ester;

[0029] When R4 is hydrogen, R3 is methylene, R1 is n-decyl, and R2 is n-decyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate di-n-decyl ester;

[0030] When R4 is hydrogen, R3 is methylene, R1 isodecyl, and R2 isodeoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate diisodecyl ester.

[0031] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is ethoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate hydrogen ethyl ester.

[0032] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is propoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate hydrogen propyl ester.

[0033] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is isopropoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate isopropyl ester.

[0034] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is butoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate hydrogen butyl ester.

[0035] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is isobutoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate isobutyl ester.

[0036] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is sec-butoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate sec-butyl ester.

[0037] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is pentoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate hydropentyl ester.

[0038] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is isopentoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate isopentyl hydrophosphonate.

[0039] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is neopentyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate neopentyl ester.

[0040] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is n-hexyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate n-hexyl ester.

[0041] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is isohexyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate isohexyl ester.

[0042] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is phenoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonic acid phenyl ester.

[0043] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is p-tolyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate p-tolyl ester;

[0044] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is n-octyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate n-octyl ester;

[0045] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is isooctoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate isooctyl ester.

[0046] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is 2-octyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate 2-octyl ester.

[0047] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is 2-ethylhexyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate hydrogen 2-ethylhexyl ester.

[0048] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is n-decyloxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate n-decyl ester;

[0049] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is isodeoxy, formula (I) is (2-(hydroxyimino)ethyl)phosphonate isodeoxy ester.

[0050] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is ethyl, formula (I) is (2-(hydroxyimino)ethyl)(ethyl)phosphonic acid;

[0051] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is propyl, formula (I) is (2-(hydroxyimino)ethyl)(propyl)phosphonic acid;

[0052] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is isopropyl, formula (I) is (2-(hydroxyimino)ethyl)(isopropyl)phosphonic acid;

[0053] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is isobutyl, formula (I) is (2-(hydroxyimino)ethyl)(isobutyl)phosphonic acid;

[0054] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is sec-butyl, formula (I) is (2-(hydroxyimino)ethyl)(sec-butyl)phosphonic acid;

[0055] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is pentyl, formula (I) is (2-(hydroxyimino)ethyl)(pentyl)phosphonic acid;

[0056] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is n-hexyl, formula (I) is (2-(hydroxyimino)ethyl)(n-hexyl)phosphonic acid;

[0057] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is cyclohexyl, formula (I) is (2-(hydroxyimino)ethyl)(cyclohexyl)phosphonic acid;

[0058] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is phenyl, formula (I) is (2-(hydroxyimino)ethyl)(phenyl)phosphonic acid;

[0059] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is p-tolyl, formula (I) is (2-(hydroxyimino)ethyl)(p-tolyl)phosphonic acid;

[0060] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is nonyl, formula (I) is (2-(hydroxyimino)ethyl)(nonyl)phosphonic acid;

[0061] When R4 is hydrogen, R3 is methylene, R1 is hydrogen, and R2 is n-decyl, formula (I) is (2-(hydroxyimino)ethyl)(n-decyl)phosphonic acid;

[0062] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is isopropyl, and R2 isopropoxy, formula (I) is (3-(hydroxyimino)propyl)phosphonate diisopropyl ester.

[0063] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is butyl, and R2 is butoxy, formula (I) is (3-(hydroxyimino)propyl)phosphonate dibutyl ester.

[0064] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is isobutyl, and R2 isobutoxy, formula (I) is (3-(hydroxyimino)propyl)phosphonate diisobutyl ester.

[0065] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is phenyl, and R2 is phenoxy, formula (I) is (3-(hydroxyimino)propyl)phosphonic acid diphenyl ester.

[0066] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is isopropoxy, formula (I) is (3-(hydroxyimino)propyl)phosphonate isopropyl ester.

[0067] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is butoxy, formula (I) is (3-(hydroxyimino)propyl)phosphonate hydrogen butyl ester.

[0068] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is isobutoxy, formula (I) is (3-(hydroxyimino)propyl)phosphonate isobutyl ester.

[0069] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is phenoxy, formula (I) is (3-(hydroxyimino)propyl)phosphonic acid phenyl ester.

[0070] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is ethyl, formula (I) is (3-(hydroxyimino)propyl)(ethyl)phosphonic acid;

[0071] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is propyl, formula (I) is (3-(hydroxyimino)propyl)(propyl)phosphonic acid;

[0072] When R4 is hydrogen, R3 is 1,2-ethylene, R1 is hydrogen, and R2 is isopropyl, formula (I) is (3-(hydroxyimino)propyl)(isopropyl)phosphonic acid;

[0073] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is isobutyl, formula (I) is (3-(hydroxyimino)propyl)(isobutyl)phosphonic acid;

[0074] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is sec-butyl, formula (I) is (3-(hydroxyimino)propyl)(sec-butyl)phosphonic acid;

[0075] When R4 is hydrogen, R3 is 1,2-ethylene, R1 is hydrogen, and R2 is pentyl, formula (I) is (3-(hydroxyimino)propyl)(pentyl)phosphonic acid;

[0076] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is n-hexyl, formula (I) is (3-(hydroxyimino)propyl)(n-hexyl)phosphonic acid;

[0077] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is cyclohexyl, formula (I) is (3-(hydroxyimino)propyl)(cyclohexyl)phosphonic acid;

[0078] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is phenyl, formula (I) is (3--(hydroxyimino)propyl)(phenyl)phosphinoic acid;

[0079] When R4 is hydrogen, R3 is 1,2-ethylidene, R1 is hydrogen, and R2 is p-tolyl, formula (I) is (3-(hydroxyimino)propyl)(p-tolyl)phosphonic acid;

[0080] When R4 is hydrogen, R3 is 1,2-ethylene, R1 is hydrogen, and R2 is nonyl, formula (I) is (3-(hydroxyimino)propyl)(nonyl)phosphonic acid;

[0081] When R4 is hydrogen, R3 is 1,2-ethylene, R1 is hydrogen, and R2 is n-decyl, formula (I) is (3-(hydroxyimino)propyl)(n-decyl)phosphonic acid;

[0082] When R4 is hydrogen, R3 is benzenemethyl, R1 isopropyl, and R2 isopropoxy, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)phosphonate diisopropyl ester.

[0083] When R4 is hydrogen, R3 is benzenemethyl, R1 is butyl, and R2 is butoxy, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)phosphonate dibutyl ester;

[0084] When R4 is hydrogen, R3 is benzenemethyl, R1 isobutyl, and R2 isobutoxy, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)phosphonate diisobutyl ester;

[0085] When R4 is hydrogen, R3 is benzenemethyl, R1 is phenyl, and R2 is phenoxy, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)phosphonic acid diphenyl ester;

[0086] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is isopropoxy, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)phosphonate isopropyl ester.

[0087] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is butoxy, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)phosphonate hydrogen butyl ester;

[0088] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is isobutoxy, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)phosphonate isobutyl hydrochloride.

[0089] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is phenoxy, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)phosphonic acid phenyl ester;

[0090] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is ethyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(ethyl)phosphonic acid;

[0091] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is propyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(propyl)phosphonic acid;

[0092] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is isopropyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(isopropyl)phosphonic acid;

[0093] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is isobutyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(isobutyl)phosphonic acid;

[0094] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is sec-butyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(sec-butyl)phosphonic acid;

[0095] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is pentyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(pentyl)phosphonic acid;

[0096] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is n-hexyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(n-hexyl)phosphonic acid;

[0097] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is cyclohexyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(cyclohexyl)phosphonic acid;

[0098] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is phenyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(phenyl)phosphine;

[0099] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is p-tolyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(p-tolyl)phosphinoic acid;

[0100] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is nonyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(nonyl)phosphonic acid;

[0101] When R4 is hydrogen, R3 is benzenemethyl, R1 is hydrogen, and R2 is n-decyl, formula (I) is (3-(hydroxyimino)-1-phenylpropyl)(n-decyl)phosphonic acid;

[0102] When R4 is methyl, R3 is ethylidene, R1 is ethyl, and R2 is ethoxy, formula (I) is diethyl (3-(hydroxyimino)but-2-yl)phosphonate;

[0103] When R4 is methyl, R3 is ethylidene, R1 is propyl, and R2 is propoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate dipropyl ester;

[0104] When R4 is methyl, R3 is ethylidene, R1 isopropyl, and R2 isopropoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate diisopropyl ester.

[0105] When R4 is methyl, R3 is ethylidene, R1 is butyl, and R2 is butoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate dibutyl ester;

[0106] When R4 is methyl, R3 is ethylidene, R1 isobutyl, and R2 isobutoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate diisobutyl ester;

[0107] When R4 is methyl, R3 is ethylidene, R1 is sec-butyl, and R2 is sec-butoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate disec-butyl ester.

[0108] When R4 is methyl, R3 is ethylidene, R1 is pentyl, and R2 is pentoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate dipentyl ester;

[0109] When R4 is methyl, R3 is ethylidene, R1 isopentyl, and R2 isopentoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate diisoamyl ester.

[0110] When R4 is methyl, R3 is ethylidene, R1 is neopentyl, and R2 is neopentyloxy, formula (I) is dinepentyl phosphonate (3-(hydroxyimino)but-2-yl)phosphonate;

[0111] When R4 is methyl, R3 is ethylidene, R1 is n-hexyl, and R2 is n-hexyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate di-n-hexyl ester;

[0112] When R4 is methyl, R3 is ethylidene, R1 isohexyl, and R2 isohexyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate diisohexyl ester;

[0113] When R4 is methyl, R3 is ethylidene, R1 is phenyl, and R2 is phenoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonic acid diphenyl ester;

[0114] When R4 is methyl, R3 is ethylidene, R1 is p-tolyl, and R2 is p-tolyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonic acid di-p-toluene ester;

[0115] When R4 is methyl, R3 is ethylidene, R1 is n-octyl, and R2 is n-octyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate di-n-octyl ester;

[0116] When R4 is methyl, R3 is ethylidene, R1 isooctyl, and R2 isooctoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate diisooctyl ester;

[0117] When R4 is methyl, R3 is ethylidene, R1 is 2-octyl, and R2 is 2-octyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate di-2-octyl ester;

[0118] When R4 is methyl, R3 is ethylidene, R1 is 2-ethylhexyl, and R2 is 2-ethylhexyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonic acid bis(2-ethylhexyl) ester;

[0119] When R4 is methyl, R3 is ethylidene, R1 is n-decyl, and R2 is n-decyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate di-n-decyl ester;

[0120] When R4 is methyl, R3 is ethylidene, R1 isodecyl, and R2 isodeoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate diisodecyl ester;

[0121] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is ethoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate ethyl hydrogen;

[0122] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is propoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate hydrogen propyl ester;

[0123] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is isopropoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate isopropyl hydrophosphonate.

[0124] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is butoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate hydrogen butyl ester;

[0125] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is isobutoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate isobutyl hydrophosphonate.

[0126] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is sec-butoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate sec-butyl ester.

[0127] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is pentoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate hydropentyl ester;

[0128] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is isopentoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate isopentyl hydrophosphonate.

[0129] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is neopentyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate neopentyl ester;

[0130] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is n-hexyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate n-hexyl ester;

[0131] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is isohexyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate isohexyl ester;

[0132] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is phenoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonic acid phenyl ester;

[0133] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is p-tolyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate p-toluene ester;

[0134] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is n-octyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate n-octyl ester;

[0135] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is isooctoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate hydroisooctyl ester;

[0136] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is 2-octyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate 2-octyl ester;

[0137] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is 2-ethylhexyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate hydrogen 2-ethylhexyl ester;

[0138] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is n-decyloxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate n-decyl ester;

[0139] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is isodeoxy, formula (I) is (3-(hydroxyimino)but-2-yl)phosphonate isodecanyl hydrophosphonate.

[0140] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is ethyl, formula (I) is (3-(hydroxyimino)but-2-yl)(ethyl)phosphonic acid;

[0141] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is propyl, formula (I) is (3-(hydroxyimino)but-2-yl)(propyl)phosphonic acid;

[0142] When R4 is methyl, R3 is ethylene, R1 is hydrogen, and R2 is isopropyl, formula (I) is (3-(hydroxyimino)but-2-yl)(isopropyl)phosphonic acid;

[0143] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is isobutyl, formula (I) is (3-(hydroxyimino)but-2-yl)(isobutyl)phosphonic acid;

[0144] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is sec-butyl, formula (I) is (3-(hydroxyimino)but-2-yl)(sec-butyl)phosphonic acid;

[0145] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is pentyl, formula (I) is (3-(hydroxyimino)but-2-yl)(pentyl)phosphonic acid;

[0146] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is n-hexyl, formula (I) is (3-(hydroxyimino)but-2-yl)(n-hexyl)phosphonic acid;

[0147] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is cyclohexyl, formula (I) is (3-(hydroxyimino)but-2-yl)(cyclohexyl)phosphonic acid;

[0148] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is phenyl, formula (I) is (3-(hydroxyimino)but-2-yl)(phenyl)phosphonic acid;

[0149] When R4 is methyl, R3 is ethylidene, R1 is hydrogen, and R2 is p-tolyl, formula (I) is (3-(hydroxyimino)but-2-yl)(p-tolyl)phosphonic acid;

[0150] When R4 is methyl, R3 is ethylene, R1 is hydrogen, and R2 is nonyl, formula (I) is (3-(hydroxyimino)but-2-yl)(nonyl)phosphonic acid;

[0151] When R4 is methyl, R3 is ethylene, R1 is hydrogen, and R2 is n-decyl, formula (I) is (3-(hydroxyimino)but-2-yl)(n-decyl)phosphonic acid;

[0152] When R4 is methyl, R3 is benzenemethyl, R1 isopropyl, and R2 isopropoxy, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)phosphonate diisopropyl ester.

[0153] When R4 is methyl, R3 is benzenemethyl, R1 is butyl, and R2 is butoxy, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)phosphonate dibutyl ester;

[0154] When R4 is methyl, R3 is benzenemethyl, R1 isobutyl, and R2 isobutoxy, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)phosphonate diisobutyl ester;

[0155] When R4 is methyl, R3 is benzenemethyl, R1 is phenyl, and R2 is phenoxy, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)phosphonic acid diphenyl ester;

[0156] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is isopropoxy, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)phosphonate isopropyl hydrophosphonate.

[0157] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is butoxy, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)phosphonate hydrogen butyl ester;

[0158] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is isobutoxy, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)phosphonate isobutyl hydrochloride.

[0159] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is phenoxy, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)phosphonic acid phenyl ester;

[0160] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is ethyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(ethyl)phosphonic acid;

[0161] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is propyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(propyl)phosphonic acid;

[0162] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is isopropyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(isopropyl)phosphonic acid;

[0163] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is isobutyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(isobutyl)phosphonic acid;

[0164] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is sec-butyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(sec-butyl)phosphonic acid;

[0165] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is pentyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(pentyl)phosphonic acid;

[0166] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is n-hexyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(n-hexyl)phosphonic acid;

[0167] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is cyclohexyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(cyclohexyl)phosphonic acid;

[0168] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is phenyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(phenyl)phosphine;

[0169] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is p-tolyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(p-tolyl)phosphinoic acid;

[0170] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is nonyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(nonyl)phosphonic acid;

[0171] When R4 is methyl, R3 is benzenemethyl, R1 is hydrogen, and R2 is n-decyl, formula (I) is (3-(hydroxyimino)-1-phenylbutyl)(n-decyl)phosphonic acid.

[0172] A second objective of this invention is to provide a method for preparing the above-mentioned ketoxime / aldeoxime-phosphonate / phosphonoside compound, wherein a haloketoxime / aldeoxime is subjected to a substitution reaction with a trialkyl phosphite, the molar ratio of the haloketoxime / aldeoxime to the trialkyl phosphite is 1:(0.8-10), the reaction temperature is 140-170°C, and the reaction time is 2-10 hours, to generate a ketoxime / aldeoxime-phosphonate compound with the structure of Formula I. The ketoxime / aldeoxime-phosphonate compound with the structure of Formula I undergoes a saponification reaction with sodium hydroxide solution in 1,4-dioxane, followed by acidification, extraction, and vacuum distillation to obtain the ketoxime / aldeoxime-phosphonoside compound. The structure of the haloketoxime / aldeoxime is shown in Formula (II), and the structure of the trialkyl phosphite is shown in Formula (III).

[0173]

[0174] A third objective of this invention is to provide another method for preparing the aforementioned ketoxime / aldehyde oxime-phosphonate / phosphonoside compound. This method involves an addition reaction of an α,β-unsaturated aldehyde / ketone with a dialkyl phosphite in the presence of a catalyst. The molar ratio of the α,β-unsaturated aldehyde oxime / ketoxime to the dialkyl phosphite is 1:(0.6-2), the catalyst dosage is (0.1-100) mol%, the reaction temperature is 20-60°C, and the reaction time is 0.5-72 hours. This yields a ketoxime / aldehyde oxime-phosphonate compound with the structure of Formula I. The ketoxime / aldehyde oxime-phosphonate compound of Formula I undergoes a saponification reaction with sodium hydroxide solution in 1,4-dioxane. Following acidification, extraction, and vacuum distillation, the ketoxime / aldehyde oxime-phosphonoside compound is obtained. The structural formula of the α,β-unsaturated aldehyde oxime / ketoxime is shown in (IV), and the structure of the dialkyl phosphite is shown in Formula (V).

[0175]

[0176] A fourth objective of this invention is to provide the application of the above-mentioned ketoxime / aldeoxime-phosphonate / phosphonic acid compounds in the preparation of cobalt-nickel ion extractants for acidic leachate from spent power batteries.

[0177] The fifth objective of this invention is to provide a method for extracting and separating cobalt and nickel ions from acidic leachate of spent power batteries. The spent power batteries are cobalt-nickel-containing batteries, and the acidic leachate is a concentrated acid-treated and stirred leachate from spent power batteries. In the extraction and separation system, the aforementioned ketoxime / aldehyde oxime-phosphonate / phosphonic acid compound is used as the organic phase. Cobalt ions in the acidic leachate of the spent power batteries enter the organic phase from the aqueous phase, thereby achieving cobalt extraction and cobalt-nickel separation. The method specifically includes the following steps:

[0178] S1. Prepare the organic phase by dissolving the ketoxime / aldeoxime-phosphonate / phosphonic acid compound in a diluent to obtain the organic phase;

[0179] S2. Prepare an aqueous phase by leaching the waste power battery in a solution containing inorganic acid to obtain an aqueous phase-cobalt-nickel acidic leachate.

[0180] S3. The organic phase obtained in step S1 and the aqueous phase obtained in step S2 are mixed at a volume ratio of 1:(0.1-10), and stirred at 25-30°C for 5-60 minutes at a stirring speed of 250-300 r / min. Cobalt ions are then extracted from the aqueous phase into the organic phase.

[0181] Furthermore, in step S1, the concentration of the ketoxime / aldehyde oxime-phosphonate / phosphonic acid compound in the organic phase is 0.1–2 M; the diluent is selected from any one of kerosene, dodecane, xylene, and sulfonated kerosene.

[0182] Furthermore, in step S2, the mass concentration of cobalt and nickel ions in the acidic leachate of the waste power battery ranges from 0.1 to 100 g / L; in step S3, the concentration of inorganic acid in the aqueous phase is 1 to 5 M, and the inorganic acid is selected from any one of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0183] Compared with the prior art, the beneficial effects of the technical solution provided by the present invention are as follows:

[0184] This invention provides ketoxime / aldehyde oxime-phosphonate / phosphonic acid compounds, their preparation methods, and applications. The method involves a substitution reaction between a haloketoxime / aldehyde oxime and a trialkyl phosphite, wherein the molar ratio of the haloketoxime / aldehyde oxime to the trialkyl phosphite is 1:(0.8-10), the reaction temperature is 140-170℃, and the reaction time is 2-10 hours, to generate a ketoxime / aldehyde oxime-phosphonate compound with the structure of Formula I. The ketoxime / aldehyde oxime-phosphonate compound with the structure of Formula I is obtained in the presence of 1,4-dioxane. The ring undergoes a saponification reaction with sodium hydroxide solution, followed by acidification, extraction, and vacuum distillation to obtain a ketoxime / aldehyde oxime-phosphonic acid compound; Secondly, an addition reaction is carried out between α,β-unsaturated aldehydes / ketones and dialkyl phosphites in the presence of a catalyst, with a molar ratio of α,β-unsaturated aldehyde / ketoxime to dialkyl phosphites of 1:(0.6-2), a catalyst dosage of (0.1-100) mol%, a reaction temperature of 20-60℃, and a reaction time of 0.5-72 hours. Ketooxime / aldoxime-phosphonate compounds of Formula I were obtained. These compounds underwent saponification with sodium hydroxide solution in 1,4-dioxane, followed by acidification, extraction, and vacuum distillation to yield ketooxime / aldoxime-phosphonic acid compounds. This marked the first discovery of a cobalt-nickel separation extractant possessing both ketooxime / aldoxime and phosphoryl groups. The ketooxime / aldoxime group is a metal ion... The functional groups commonly used in cobalt-nickel ion extraction and separation can chelate with cobalt ions to form rings through oxygen and nitrogen atoms in the structure. Phosphonate / phosphonocyanate groups are proven effective structural functional groups for cobalt-nickel ion separation extractants. The synergistic chelation ability of these two groups enhances the cobalt ion chelation capacity and improves selectivity, significantly increasing the extraction and recovery of cobalt ions and their separation from nickel ions in acidic leachates from spent power batteries. It is particularly suitable for the extraction, separation, and recovery of low-concentration cobalt-nickel ions in acidic leachates from spent power batteries. It effectively solves the problem of difficult cobalt-nickel separation; the entire extraction and recovery process is simple, efficient, and feasible, meeting the requirements of industrial applications. Attached Figure Description

[0185] Figure 1 The infrared spectrum of dibutyl phosphonate (3-(hydroxyimino)but-2-yl)phosphonate prepared in Example 1;

[0186] Figure 2 The infrared spectrum of butylhydro-(3-(hydroxyimino)-1-phenylpropyl)phosphonate prepared in Example 2;

[0187] Figure 3 The infrared spectrum is shown for the butylhydro-(3-(hydroxyimino)-1-phenylbutyl)phosphonate prepared in Example 3. Detailed Implementation

[0188] To make the objectives, technical solutions, and advantages of this invention clearer, the specific embodiments and accompanying drawings are described in further detail below. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0189] Example 1

[0190] Preparation of (3-(hydroxyimino)but-2-yl)phosphonate dibutyl ester

[0191]

[0192] 6.08 parts of 3-chloro-2-butanone oxime were added to 12.52 parts of tributyl phosphite at 160℃ under stirring. After the addition was complete, the mixture was stirred at 160℃ for 3 hours. The mixture was washed with water, extracted twice with diethyl ether, and distilled under reduced pressure to obtain dibutyl (3-(hydroxyimino)but-2-yl)phosphonate, with the structural formula shown in Formula 1. Its infrared spectrum is shown in... Figure 1 As shown. The yield was 86%.

[0193] Example 2

[0194] Preparation of butylhydro-(3-(hydroxyimino)-1-phenylpropyl)phosphonate

[0195]

[0196] 7.36 parts of cinnamaldehyde oxime were added to a mixture containing 9.71 parts of dibutyl phosphite and 0.51 parts of tributylphosphine under stirring. After the addition was complete, the mixture was stirred at room temperature for 48 hours. The mixture was then distilled under reduced pressure at 100°C until no liquid evaporated, yielding dibutyl (3-(hydroxyimino)-1-phenylpropyl)phosphonate. This dibutyl phosphonate was then reacted with 8 parts of sodium hydroxide solution in 60 parts of 1,4-dioxane for 4 hours to obtain butylhydro-(3-(hydroxyimino)-1-phenylpropyl)phosphonate, with the structural formula shown in Formula 2. Its infrared spectrum is shown in Formula 2. Figure 2 As shown, the yield was 76%.

[0197] Example 3

[0198] Preparation of butylhydro-(3-(hydroxyimino)-1-phenylbutyl)phosphonate

[0199]

[0200] 8.06 parts of benzyl acetone oxime were added to a mixture of 9.71 parts of dibutyl phosphite and 0.51 parts of tributylphosphine under stirring. After the addition was complete, the mixture was stirred at room temperature for 48 hours. The mixture was then distilled under reduced pressure at 100°C until no liquid evaporated, yielding dibutyl (3-(hydroxyimino)-1-phenylbutyl)phosphonate. This dibutyl phosphonate was then reacted with 8 parts of sodium hydroxide solution in 60 parts of 1,4-dioxane for 4 hours to obtain butylhydro-(3-(hydroxyimino)-1-phenylbutyl)phosphonate, with the structural formula shown in Formula 3. Its infrared spectrum is shown in Formula 3. Figure 3 As shown. The yield was 77%.

[0201] Example 4

[0202] Preparation of (3-(hydroxyimino)-1-phenylbutyl)phosphonate dibutyl ester

[0203]

[0204] 8.06 parts of benzylidene acetone oxime were added to a mixture of 9.71 parts of dibutyl phosphite and 0.51 parts of tributylphosphine under stirring. After the addition was complete, the mixture was stirred at room temperature for 48 hours. The mixture was then distilled under reduced pressure at 100°C until no liquid evaporated, yielding dibutyl (3-(hydroxyimino)-1-phenylbutyl)phosphonate, with the structural formula shown in Figure 4. The yield was 83%.

[0205] Example 5

[0206] Preparation of 2-ethylhexyl hydrogen phosphonate (3-(hydroxyimino)but-2-yl)phosphonate

[0207]

[0208] 6.08 parts of 3-chloro-2-butanone oxime were added to 23.26 parts of tris(2-ethylhexyl) phosphite at 160°C under stirring. After the addition was complete, the mixture was stirred at 160°C for 3 hours to obtain bis(2-ethylhexyl) (3-(hydroxyimino)but-2-yl)phosphonate. The bis(2-ethylhexyl) (3-(hydroxyimino)but-2-yl)phosphonate was then reacted with 8 parts of sodium hydroxide solution in 60 parts of 1,4-dioxane for 4 hours to obtain 2-ethylhexyl (3-(hydroxyimino)but-2-yl)phosphonate hydrogen, with the structural formula shown in Figure 5. The yield was 74%.

[0209] Example 6

[0210] Preparation of (2-(hydroxyimino)ethyl)phosphonate dibutyl ester

[0211]

[0212] 4.68 parts of 2-chloroacetaldehyde oxime were added to 12.52 parts of tributyl phosphite at 160°C under stirring. After the addition was complete, the mixture was stirred at 160°C for 3 hours. The mixture was washed with water, extracted twice with diethyl ether, and distilled under reduced pressure to obtain dibutyl (2-(hydroxyimino)ethyl)phosphonate, with the structural formula shown in Formula 6. The yield was 82%.

[0213] Example 7

[0214] Preparation of 2-ethylhexyl hydrogen phosphonate (2-(hydroxyimino)ethyl)phosphonate

[0215]

[0216] 4.68 parts of 2-chloroacetaldehyde oxime were added to 23.26 parts of tris(2-ethylhexyl) phosphite at 160°C under stirring. After the addition was complete, the mixture was stirred at 160°C for 3 hours to obtain bis(2-ethylhexyl) phosphonate (2-(hydroxyimino)ethyl)phosphonate. The bis(2-ethylhexyl) phosphonate was then reacted with 8 parts of sodium hydroxide solution in 60 parts of 1,4-dioxane for 4 hours to obtain 2-ethylhexyl hydrogen (2-(hydroxyimino)ethyl)phosphonate, with the structural formula shown in Figure 7. The yield was 71%.

[0217] Example 8

[0218] Preparation of (3-(hydroxyimino)propyl)phosphonate dibutyl ester

[0219]

[0220] 3.55 parts of acrolein oxime were added to a mixture of 9.71 parts of dibutyl phosphite and 0.51 parts of tributylphosphine under stirring. After the addition was complete, the mixture was stirred at room temperature for 48 hours. The mixture was then distilled under reduced pressure at 100°C until no liquid evaporated, yielding dibutyl (3-(hydroxyimino)propyl)phosphonate, with the structural formula shown in Figure 8. The yield was 85%.

[0221] Example 9

[0222] Preparation of (3-(hydroxyimino)-1-phenylpropyl)phosphonate dibutyl ester

[0223]

[0224] 7.36 parts of cinnamaldehyde oxime were added to a mixture of 9.71 parts of dibutyl phosphite and 0.51 parts of tributylphosphine under stirring. After the addition was complete, the mixture was stirred at room temperature for 48 hours. The mixture was then distilled under reduced pressure at 100°C until no liquid evaporated, yielding dibutyl (3-(hydroxyimino)-1-phenylpropyl)phosphonate, with the structural formula shown in Formula 9. The yield was 86%.

[0225] Example 10

[0226] Preparation of (3-(hydroxyimino)propyl)(isobutyl)phosphonic acid

[0227]

[0228] 3.55 parts of acrolein oxime were added to a mixture of 9.71 parts of diisobutyl phosphite and 0.51 parts of tributylphosphine under stirring. After the addition was complete, the mixture was stirred at room temperature for 48 hours. The mixture was then distilled under reduced pressure at 100°C until no liquid evaporated, yielding diisobutyl (3-(hydroxyimino)propyl)phosphonate. This diisobutyl phosphonate was then reacted with 8 parts of sodium hydroxide solution in 60 parts of 1,4-dioxane for 4 hours to obtain (3-(hydroxyimino)propyl)(isobutyl)phosphonic acid, with the structural formula shown in Figure 10. The yield was 72%.

[0229] Examples 11-13 illustrate the application of extractants with ketoxime / aldeoxime-phosphonate / phosphonic acid compound structures prepared in Examples 1-3 to the extraction, recovery, and separation of cobalt and nickel ions in a simulated cobalt-nickel ion mixed solution.

[0230] Simulated preparation process of cobalt-nickel ion mixed solution: Accurately weigh analytical grade cobalt sulfate heptahydrate and nickel sulfate hexahydrate, dissolve them in a volumetric flask, and make up to 1L to prepare an initial concentration range of (0.1-10)g / L for cobalt ions and (1-100)g / L for nickel ions, and then acidify with sulfuric acid to pH ~5.

[0231] The determination process and calculation formula for the cobalt ion extraction rate obtained in Examples 11-13 are as follows: The concentrations of cobalt ions and nickel ions in the aqueous phase before and after extraction were measured using a UV spectrophotometer and recorded as follows: and

[0232] Allocation ratio:

[0233]

[0234] Extraction rate:

[0235] Extraction separation coefficient: β Co / Ni = Co / D Ni

[0236] Where R represents comparison.

[0237] Example 11

[0238] Separation and extraction of cobalt and nickel ions by dibutyl phosphonate (3-(hydroxyimino)but-2-yl)phosphonate

[0239] Dibutyl 3-(hydroxyimino)but-2-yl)phosphonate was prepared into an extraction organic phase with a concentration of 0.5 M using kerosene as the diluent. The initial concentrations of cobalt ions and nickel ions in the aqueous phase were 2.67 g / L and 65.21 g / L, respectively, and the solution was acidified with sulfuric acid to pH ~5. The volume ratio of the organic phase to the aqueous phase was 1:1. Extraction was performed at room temperature for 30 min, and the cobalt ion extraction rate reached 97.9%, with a cobalt-nickel separation coefficient of 1095.

[0240] Example 12

[0241] Separation and extraction of cobalt and nickel ions by butylhydro-(3-(hydroxyimino)-1-phenylpropyl)phosphonate

[0242] Butylhydro-(3-(hydroxyimino)-1-phenylpropyl)phosphonate was prepared into an extraction organic phase with a concentration of 0.2 M using dodecane as the diluent. The initial concentrations of cobalt ions and nickel ions in the aqueous phase were 1.89 g / L and 25.23 g / L, respectively, and the solution was acidified with sulfuric acid to pH ~5. The volume ratio of the organic phase to the aqueous phase was 1:5. Extraction was performed at room temperature for 20 min, and the cobalt ion extraction rate reached 99.3%, with a cobalt-nickel separation coefficient of 1206.

[0243] Example 13

[0244] Separation and extraction of cobalt and nickel ions by butylhydro-(3-(hydroxyimino)-1-phenylbutyl)phosphonate

[0245] Butylhydro-(3-(hydroxyimino)-1-phenylbutyl)phosphonate was prepared into an extraction organic phase with a concentration of 0.4 M using kerosene as the diluent. The initial concentrations of cobalt ions and nickel ions in the aqueous phase were 0.34 g / L and 5.20 g / L, respectively, and the solution was acidified with sulfuric acid to pH ~5. The volume ratio of the organic phase to the aqueous phase was 1:3. Extraction was performed at room temperature for 30 min, and the cobalt ion extraction rate reached 98.8%, with a cobalt-nickel separation coefficient of 1101.

[0246] To better illustrate the effect of the ketoxime / aldeoxime-phosphonate / phosphonic acid compound of the present invention on the extraction, separation and recovery of low concentration cobalt and nickel ions in the acidic leachate of waste power batteries, the applicant has also carried out specific applications.

[0247] Example 14

[0248] The extractant with a ketoxime / aldeoxime-phosphonate / phosphonic acid compound structure prepared in Example 3 was used to extract and recover low concentrations of cobalt and nickel ions from the acidic leachate of spent power batteries.

[0249] Acidic leachate from spent power batteries: The leaching process was carried out at 80℃. A total of 8.7g of powder was extracted from the positive and negative electrodes and placed in a 500mL flask. 55g of 2M H2SO4 was added, and the mixture was stirred for 3 hours. After leaching, the filtrate and filter residue were separated. The filter residue was washed with water. The resulting solution had a pH of approximately 5, a cobalt ion concentration of 0.72g / L, and a nickel ion concentration of 14.70g / L.

[0250] Extraction, separation and recovery of cobalt and nickel ions by butylhydro-(3-(hydroxyimino)-1-phenylpropyl)phosphonate

[0251] Butylhydro-(3-(hydroxyimino)-1-phenylpropyl)phosphonate was prepared into an extraction organic phase with a concentration of 0.2M using kerosene as the diluent. The cobalt and nickel ion contents in the acidic leachate of waste power batteries were 0.72 g / L and 14.70 g / L, respectively, with a pH of approximately 5. The volume ratio of the organic phase to the aqueous phase was 1:1. Extraction was performed at room temperature for 20 min, and the cobalt ion extraction rate reached 98.5%, with a separation coefficient of 1173.

[0252] Example 15

[0253] Acidic leachate from spent power batteries: Same as in Example 14.

[0254] The extractant is butylhydro-(3-(hydroxyimino)-1-phenylbutyl)phosphonate.

[0255] Extraction, separation, and recovery of cobalt and nickel ions using butylhydro-(3-(hydroxyimino)-1-phenylbutyl)phosphonate:

[0256] Butylhydro-(3-(hydroxyimino)-1-phenylbutyl)phosphonate was prepared into an extraction organic phase with a concentration of 0.3M using dodecane as the diluent. The cobalt and nickel ion contents in the acidic leachate of waste power batteries were 0.72 g / L and 14.70 g / L, respectively, and the pH was approximately 5. The volume ratio of the organic phase to the aqueous phase was 1:1. Extraction was carried out at room temperature for 30 min, and the cobalt ion extraction rate reached 97.4%, with a separation coefficient of 1003.

[0257] Comparative Example 1

[0258] Extraction and separation of cobalt and nickel ions by bis(2,4,4-trimethylpentyl)phosphonic acid

[0259]

[0260] Bis(2,4,4-trimethylpentyl)phosphonic acid was prepared into an extraction organic phase with a concentration of 0.2M using kerosene as the diluent. The cobalt and nickel ion contents in the acidic leachate of waste power batteries were 0.72 g / L and 14.70 g / L, respectively, with a pH of approximately 5. The volume ratio of the organic phase to the aqueous phase was 1:1. Extraction was performed at room temperature for 30 min, and the cobalt ion extraction rate reached 90.4%, with a separation coefficient of 723.

[0261] Where there is no conflict, the above embodiments and features described herein can be combined with each other.

[0262] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A ketoxime / aldoxime-phosphonate compound, characterized in that, Chemical structure The formula is shown in formula (Ⅰ): (Ⅰ) Wherein, equation (I) is selected from .

2. The method for preparing the ketoxime / aldehyde oxime-phosphonate compound according to claim 1, characterized in that: A substitution reaction is carried out between a haloketoxime / aldehyde oxime and a trialkyl phosphite, wherein the molar ratio of the haloketoxime / aldehyde oxime to the trialkyl phosphite is 1:(0.8-10), the reaction temperature is 140-170℃, and the reaction time is 2-10 hours, to generate a ketoxime / aldehyde oxime-phosphonate compound with the structure of Formula I, wherein the structure of the haloketoxime / aldehyde oxime is shown in Formula (II), and the structure of the trialkyl phosphite is shown in Formula (III). (II); (III)。 3. The application of the ketoxime / aldeoxime-phosphonate compound as described in claim 1 in the preparation of cobalt-nickel ion extractant for acidic leachate of spent power batteries.

4. A method for extracting and separating cobalt and nickel ions from acidic leachate of spent power batteries, characterized in that, The spent power battery is a cobalt-nickel battery, and the acidic leachate from the spent power battery is a concentrated acid aging and stirring leachate from the spent power battery. In the extraction and separation system, the ketoxime / aldehyde oxime-phosphonate compound as described in claim 1 is used as the organic phase. Cobalt ions in the acidic leachate from the spent power battery enter the organic phase from the aqueous phase, thereby achieving cobalt extraction and cobalt-nickel separation. Specifically, the system includes the following steps: S1. Prepare the organic phase by dissolving the ketoxime / aldehyde oxime-phosphonate compound in a diluent to obtain the organic phase; S2. Prepare an aqueous phase by leaching the waste power battery in a solution containing inorganic acid to obtain an aqueous phase-cobalt-nickel acidic leachate. S3. The organic phase obtained in step S1 and the aqueous phase obtained in step S2 are mixed at a volume ratio of 1:(0.1~10), and stirred at 25~30 ℃ with a stirring speed of 250~300 r / min for 5~60 min. Cobalt ions enter the organic phase from the aqueous phase, thus extracting cobalt ions.

5. The method as described in claim 4, characterized in that, In step S1, the concentration of the ketoxime / aldehyde oxime-phosphonate compound in the organic phase is 0.1~2 M; the diluent is selected from any one of kerosene, dodecane, xylene and sulfonated kerosene.

6. The method as described in claim 5, characterized in that, In step S2, the mass concentration of cobalt and nickel ions in the acidic leachate of the waste power battery ranges from 0.1 to 100 g / L; in step S3, the concentration of inorganic acid in the aqueous phase is 1 to 5 M, and the inorganic acid is selected from any one of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.

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