A liquid organic composition for lithium extraction and a low-cost green preparation method thereof

Abstract

The present invention provides a liquid organic composition for extracting lithium, which comprises: component a) a lithium extractant, component b) a synergist, and component c) a diluent, wherein component a) comprises component a1) and component a2), component a1) is 2-hydroxy-4-C 7‑16 Alkoxy-acetophenone and / or 2-hydroxy-4-C 7‑16 Alkoxy-benzophenone, the C 7‑16 The alkoxy group is optionally substituted, and the component a2) is the nitration product of the component a1). Also provided is a method for preparing a liquid organic composition for extracting lithium.

Description

Technical Field

[0001] The present invention relates to the field of lithium extraction technology, and in particular to a method for preparing a novel liquid organic composition for lithium extraction. More specifically, the present invention relates to a liquid organic composition for lithium extraction comprising a phenolic ketone compound, a synergist, and a diluent, and a method for preparing the composition. Background Art

[0002] Lithium is a critical energy metal. The explosive growth of electric vehicles, which utilize lithium batteries as their core component, has led to a growing demand for lithium salts. Lithium salts are primarily derived from lithium-containing ores and brines. The development of both inevitably involves extracting lithium from aqueous solutions containing alkali and alkaline earth metals. Therefore, the development of compounds and combinations with exceptional selectivity for lithium is key to efficient lithium extraction.

[0003] Patent application 202210918111.5 discloses a new type of phenol-ketone lithium extractant that can achieve highly selective separation of lithium from elements such as sodium, potassium, and magnesium in brine. However, how to achieve low-cost and green industrial preparation of such extractants and their organic phases for lithium extraction remains to be studied. In addition, it is also necessary to optimize the specific groups and their combinations in its general structure to obtain better lithium extraction effects. The examples in patent application 202210918111.5 disclose that the preferred lithium extractant structure is 2-hydroxy-4-alkoxy-5-nitroacetophenone or / and 2-hydroxy-4-alkoxy-5-nitrobenzophenone. Among them, 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone intermediates are used as raw materials, and a lithium extractant with excellent performance is prepared by nitration reaction. It uses a vacuum distillation method to remove the acetic acid solvent used in the reaction to obtain a solid extractant. This leads to several problems: 1) the solid extractant is difficult to completely separate from the acetic acid; 2) the solid extractant containing volatile acetic acid is difficult to handle and remove from the reactor; and 3) the distilled aqueous acetic acid waste liquid is difficult to reuse. This lithium extractant preparation process consumes a large amount of acetic acid solvent, resulting in high production costs, and the large amount of impure acetic acid aqueous solution produced as a byproduct is difficult to handle.

[0004] Therefore, further improving the novel phenolic ketone lithium extractant and the preparation method of the liquid organic phase thereof for lithium extraction to reduce the manufacturing cost and environmental load of such extractants is of great significance for industrial application. Summary of the Invention

[0005] To address these issues, the inventors have proposed a method and process for directly preparing a liquid organic composition for lithium extraction, bypassing the synthesis of a pure phenolic-ketone lithium extractant. The disclosed method avoids: 1) the cumbersome process of first preparing the pure phenolic-ketone lithium extractant and then mixing it with a trialkylphosphine oxide co-extractant and a diluent to prepare the liquid organic composition for lithium extraction; and 2) the difficulty of recycling the acetic acid solvent during the preparation of the pure phenolic-ketone lithium extractant.

[0006] The present invention proposes a method for preparing the aforementioned liquid organic composition for lithium extraction, comprising:

[0007] Provide component a1), component a1) is 2-hydroxy-4-C 7-16 Alkoxy-acetophenone or / and 2-hydroxy-4-C 7-16 Alkoxy-benzophenone, the C 7-16 Alkoxy groups are optionally substituted;

[0008] nitrating component a1) in acetic acid solvent to obtain a mixture of component a1) and component a2); and

[0009] Sodium hydroxide, a synergist and a diluent are added to the mixture of component a1) and component a2) to separate the extractant from the nitration solvent, and finally obtain a liquid organic composition for lithium extraction.

[0010] By the method provided by the present invention, a liquid organic composition for lithium extraction is obtained, which comprises: component a) a lithium extractant, component b) a synergist and component c) a diluent, wherein component a) comprises component a1) and component a2), component a1) is 2-hydroxy-4-C 7-16 Alkoxy-acetophenone or / and 2-hydroxy-4-C 7-16 Alkoxy-benzophenone, the C 7-16 The alkoxy group is optionally substituted and the component a2) is the nitration product of component a1).

[0011] The process disclosed herein omits the purification of the solid 2-hydroxy-4-alkoxy-5-nitroacetophenone and / or 2-hydroxy-4-alkoxy-5-nitrobenzophenone, significantly reducing the energy consumption required for distillation of the acetic acid solvent. This effectively avoids potential explosion hazards and other issues encountered during the production of nitro-containing solid materials, while also directly obtaining a liquid organic mixture for lithium extraction. This reduces the complexity and cost of the production process while also ensuring the safety of the extractant preparation and the effectiveness of its use.

[0012] The disclosed process for preparing a liquid organic mixture for lithium extraction produces virtually no waste organic solvents or wastewater, with the only byproduct being a sodium acetate solution. The resulting byproduct sodium acetate solution can be converted into a commercially viable industrial product through concentration and / or crystallization. DETAILED DESCRIPTION

[0013] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the embodiments of the present invention are clearly and completely described below. The embodiments described below are exemplary and are only used to explain the present invention, and are not to be understood as limiting the present invention. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0014] The present invention may be implemented in other specific forms without departing from the essential attributes of the present invention. It should be understood that, without conflict, any and all embodiments of the present invention may be combined with the technical features of any other embodiment or multiple other embodiments to produce additional embodiments. The present invention includes additional embodiments resulting from such combinations.

[0015] All publications and patents mentioned in this disclosure are hereby incorporated into the present disclosure in their entirety by reference. If the purposes or terms used in any publications and patents incorporated by reference conflict with the purposes or terms used in this disclosure, then the purposes and terms of this disclosure shall prevail.

[0016] The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described.

[0017] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as those commonly used in the art to which the claimed subject matter belongs. If there are multiple definitions for a term, the definition herein shall prevail.

[0018] Except in the working examples or otherwise indicated, all numbers stating quantitative properties such as dosage in the specification and claims should be understood to be modified by the term "about" in all cases. It should also be understood that any numerical range recited herein is intended to include all subranges within the range and any combination of the various endpoints of the range or subrange.

[0019] As used in this disclosure, words such as “include”, “contain” or “comprise” and the like mean that the elements preceding the word include the elements listed after the word and their equivalents, without excluding unrecorded elements. The terms “contain” or “include (comprising)” used herein may be open, semi-closed and closed. In other words, the terms also include “essentially consisting of” or “consisting of”. Therefore, the liquid organic composition for extracting lithium comprises component a) a lithium extractant, component b) a synergist and component c) a diluent, which means that the liquid organic composition for extracting lithium may contain other components in addition to components a), b) and c), or may not contain other components in addition to components a), b) and c). For example, the liquid organic composition for extracting lithium may further contain an antioxidant such as ascorbic acid.

[0020] In one embodiment, the liquid organic composition for lithium extraction consists of component a) a lithium extractant, component b) a synergist, and component c) a diluent.

[0021] In another embodiment, the liquid organic composition for lithium extraction consists essentially of component a) a lithium extractant, component b) a synergist, and component c) a diluent, wherein component a) a lithium extractant, component b) a synergist, and component c) a diluent account for 97 weight %, 98 weight %, 99 weight % or more of the liquid organic composition for lithium extraction.

[0022] In another embodiment, the liquid organic composition for lithium extraction comprises component a) a lithium extractant, component b) a synergist, and component c) a diluent, wherein the content of component a) a lithium extractant, component b) a synergist, and component c) a diluent in the liquid organic composition for lithium extraction is less than 97% by weight. The liquid organic composition for lithium extraction may comprise other components, as long as the other components do not negatively affect the lithium extraction performance of the organic composition.

[0023] The term "optional" in this disclosure means that the described situation may or may not be present. For example, a composition including an optional diluent means that the composition may or may not include the diluent. Therefore, C 7-16 Alkoxy is optionally substituted including unsubstituted C 7-16 Alkoxy and substituted C 7-16 Alkoxy, for example, the substituent may be C1-3 alkyl, C1-3 alkoxy, C5-6 cycloalkyl, halogen, nitro, benzyloxy, hydroxyl, etc.

[0024] The term "extractant" as used herein refers to a substance that reacts with the metal being extracted (e.g., lithium, sodium, potassium, etc.) through a coordination chemical reaction to form an extractant that is extracted into the organic phase. The substance can then be extracted from the organic phase into the aqueous phase through a chemical reaction, thereby purifying or enriching the metal. Extractant and extractant are used interchangeably in this disclosure. For example, a lithium extractant or lithium extractant is used to purify or enrich lithium through extraction.

[0025] The term "alkyl" as used herein refers to a branched or straight-chain monovalent hydrocarbon radical having n carbon atoms and 2n+1 hydrogen atoms. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, isoheptyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, dodecyl, hexadecyl, and the like.

[0026] The term "alkoxy" in the present disclosure refers to an alkyl group as defined above connected to the parent structure via an oxygen, and therefore also includes straight-chain alkoxy and branched-chain alkoxy groups. Typical alkyl groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, heptyloxy, isoheptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, isononyloxy, decyloxy, isodecyloxy, dodecyloxy, hexadecyloxy, etc. Therefore, the "alkoxy" in 2-hydroxy-4-alkoxy-5-nitroacetophenone and 2-hydroxy-4-alkoxy-5-nitrobenzophenone in the present application includes straight-chain alkoxy and branched-chain alkoxy.

[0027] The term "cycloalkyl" as used herein refers to a monocyclic or polycyclic group containing only carbon and hydrogen, which may be saturated or partially unsaturated. In some embodiments, the cycloalkyl is a C3-C6 cycloalkyl. Illustrative examples of cycloalkyl include, but are not limited to, the following groups: cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. In some preferred embodiments, the cycloalkyl is cyclopentyl or cyclohexyl.

[0028] The term "nitro" in this disclosure refers to a -NO2 group.

[0029] The term "benzyloxy" in the present disclosure refers to a monovalent group PhCH2O- remaining after benzyl alcohol loses a hydrogen atom from the hydroxyl group.

[0030] The term "halo" or "halogen" as used herein refers to fluorine, chlorine, bromine, or iodine. In some embodiments, "halo" or "halogen" is chlorine or bromine. In other embodiments, "halo" or "halogen" is fluorine. The term "halohydrocarbon" as used herein includes straight-chain halogenated hydrocarbons and branched-chain halogenated hydrocarbons.

[0031] In the present disclosure, a synergist refers to a reagent that can increase the distribution ratio after being added to an extractant. Synergist can be used interchangeably with co-extraction agent in the present disclosure.

[0032] Diluents in this disclosure refer to agents that improve the physical properties of the extracted organic phase, such as serving as an organic solvent for the extractant, increasing the solubility of the extractant in the organic phase, reducing the viscosity of the extractant to increase its fluidity, and changing the density of the organic phase.

[0033] In the liquid organic composition for extracting lithium in the present application, component a) lithium extractant includes component a1) and component a2), wherein component a) includes component a1) and component a2), component a1) is 2-hydroxy-4-C 7-16 Alkoxy-acetophenone or / and 2-hydroxy-4-C 7-16 Alkoxy-benzophenone, the C 7-16 The alkoxy group is optionally substituted and the component a2) is the nitration product of component a1).

[0034] In a preferred embodiment, the component a2) is 2-hydroxy-4-C 7-16 Alkoxy-5-nitroacetophenone or / and 2-hydroxy-4-C 7-16 Alkoxy-5-nitrobenzophenone.

[0035] For example, the component a1) is 2-hydroxy-4-heptyloxyacetophenone, 2-hydroxy-4-octyloxyacetophenone, 2-hydroxy-4-nonyloxyacetophenone, 2-hydroxy-4-decyloxyacetophenone, 2-hydroxy-4-undecyloxyacetophenone, 2-hydroxy-4-dodecyloxyacetophenone, 2-hydroxy-4-tridecyloxyacetophenone, 2-hydroxy-4-tetradecyloxyacetophenone, 2-hydroxy-4-pentadecyloxyacetophenone, 2-hydroxy-4-hexadecyloxyacetophenone, 2-hydroxy-4 -heptyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-nonyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4-undedecyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-tridecyloxybenzophenone, 2-hydroxy-4-tetradecyloxybenzophenone, 2-hydroxy-4-pentadecyloxybenzophenone, 2-hydroxy-4-hexadecyloxybenzophenone or a mixture of any of them.

[0036] For example, the component a2) is 2-hydroxy-4-heptyloxy-5-nitroacetophenone, 2-hydroxy-4-octyloxy-5-nitroacetophenone, 2-hydroxy-4-nonyloxy-5-nitroacetophenone, 2-hydroxy-4-decyloxy-5-nitroacetophenone, 2-hydroxy-4-undecyloxy-5-nitroacetophenone, 2-hydroxy-4-dodecyloxy-5-nitroacetophenone, 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone, 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone, 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone, 2-hydroxy-4 2-Heptyloxy-5-nitrobenzophenone, 2-hydroxy-4-octyloxy-5-nitrobenzophenone, 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, 2-hydroxy-4-decyloxy-5-nitrobenzophenone, 2-hydroxy-4-undecyloxy-5-nitrobenzophenone, 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone, 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone, 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone, 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone, 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone or a mixture of any two thereof.

[0037] In the liquid organic composition for lithium extraction of the present application, the component a2) and the component a1) can be in any ratio. Preferably, the molar ratio of the component a1) to the component a2) is 1:1 to 1:1000, more preferably 1:2 to 1:200, and even more preferably 1:10 to 1:100.

[0038] Component a1) and component a2) are both lithium extractants. Generally, component a2) has a better lithium extraction capability than component a1). Therefore, in the liquid organic composition for lithium extraction of the present application, the content of component a2) is preferably higher than that of component a1).

[0039] In the liquid organic composition for lithium extraction of the present application, component a2) is the nitration reaction product of component a1). When x% of component a1) undergoes nitration, the molar ratio of component a1) to component a2) is (100-x):x. For example, when 50% of component a1) undergoes nitration, the molar ratio of component a1) to component a2) is 1:1. For example, when 90% of component a1) undergoes nitration, the molar ratio of component a1) to component a2) is 1:9. For example, when 99% of component a1) undergoes nitration, the molar ratio of component a1) to component a2) is 1:99. Those skilled in the art can control the extent of the nitration reaction by controlling reaction conditions such as the amount of nitric acid added. If an excess of nitric acid is added to cause as much of component a1) as possible to undergo nitration, the cost of post-processing will increase.

[0040] In the liquid organic composition for lithium extraction of the present application, the synergist is, for example, tributyl phosphate, trioctyl phosphate, tris(2-ethylhexyl) phosphate, trihexyl phosphate, tripentyl phosphate, dibutyl butyl phosphate, dibutyl butyl phosphate, di-sec-octyl methyl phosphate, diisooctyl methyl phosphate, diisooctyl isopropyl phosphate, diisopentyl methyl phosphate, triphenylphosphine oxide, diphenylbenzylphosphine oxide, diphenyl(2-hydroxyphenylmethyl)phosphine oxide, 2,5-dihydroxyphenyl(diphenyl)phosphine oxide, trioctylphosphine oxide (or Cyanex921), or one or more of trialkylphosphine oxide TRPO (or Cyanex923).

[0041] In the liquid organic composition for extracting lithium in the present application, the diluent is, for example, one or more of industrial white oil, kerosene, sulfonated kerosene, D series solvent oil, n-heptane, cyclohexane, octane, dodecane, petroleum ether, xylene, anisole, methyl isobutyl ketone, toluene, octanone, 5-nonanone, isopentanol, n-butanol, halogenated benzene, ethylbenzene or diethylbenzene.

[0042] For example, in the liquid organic composition for lithium extraction of the present application, the total concentration of the lithium extractant in the liquid organic composition for lithium extraction is 0.03 mol / L to 1.0 mol / L; the concentration of the synergist in the liquid organic composition for lithium extraction is 0.01 mol / L to 2.0 mol / L; the molar ratio of the lithium extractant to the synergist is 3:1 to 0.5:1.

[0043] The present disclosure also provides a method for extracting lithium, which comprises:

[0044] The aforementioned liquid organic composition for lithium extraction is brought into contact with an aqueous solution containing lithium ions, and the lithium ions in the aqueous solution enter the organic layer through liquid-liquid separation, which is then collected.

[0045] In one embodiment of lithium extraction, the pH value of the aqueous solution containing lithium ions is 7 to 13 before contacting the liquid organic composition for lithium extraction.

[0046] For example, the pH of the aqueous solution containing lithium ions is adjusted by adding hydroxide, carbonate, phosphate, or borate of an alkali metal (such as sodium or potassium) or ammonium.

[0047] In one embodiment of lithium extraction, the aqueous solution containing lithium ions is an alkaline natural brine; the alkalinity of the alkaline natural brine is optionally further adjusted by adding an alkali metal or ammonium hydroxide, carbonate, phosphate, or borate. In another embodiment, the aqueous solution containing lithium ions is a lithium precipitation mother liquor for producing lithium carbonate and / or a lithium precipitation mother liquor for producing lithium phosphate.

[0048] For example, the hydroxide of the alkali metal or ammonium is one or more of sodium hydroxide, potassium hydroxide and ammonium hydroxide; the carbonate is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; the phosphate is one or more of trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate and diammonium hydrogen phosphate; the borate is one or more of sodium metaborate, potassium metaborate, ammonium metaborate, sodium tetraborate, potassium tetraborate and ammonium tetraborate.

[0049] In one embodiment of lithium extraction, the pH value of the aqueous solution containing lithium ions before contacting with the liquid organic composition for lithium extraction is 5-8; the liquid organic composition for lithium extraction is first saponified with one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate aqueous solution before contacting with the aqueous solution containing lithium ions.

[0050] In one embodiment of lithium extraction, the volume ratio of the aqueous solution containing lithium ions to the liquid organic composition for lithium extraction is 30:1 to 1:30, for example, 20:1, 10:1, 1:1, 1:5, 1:10, 1:15; and / or, the lithium concentration in the aqueous solution containing lithium ions is 0.01 mol / L to 2.0 mol / L.

[0051] In one embodiment of extracting lithium, a step of contacting a stripping agent with the organic layer to obtain a stripping agent containing lithium may be further included.

[0052] For example, the release agent is an aqueous acid solution.

[0053] In one embodiment of lithium extraction, the desorption agent is an aqueous solution of one or more of carbonic acid, sulfuric acid, sulfurous acid, hydrochloric acid, nitric acid and phosphoric acid; and / or, in the desorption agent, the concentration of hydrogen ions is 0.05 mol / L to 6 mol / L; and the volume ratio of the desorption agent to the organic layer is 1:1 to 1:50.

[0054] In one embodiment of extracting lithium, the lithium concentration in the stripping agent after the stripping agent contacts the organic layer is 0.05 mol / L to 10 mol / L.

[0055] In one embodiment of lithium extraction, the liquid organic composition for lithium extraction is in contact with the aqueous solution containing lithium ions for 3 to 30 minutes.

[0056] In one embodiment of lithium extraction, the time for the removal agent to contact the organic layer is 3 to 30 minutes.

[0057] The above-mentioned contact operation can be carried out in a mixing and settling tank, a centrifugal extractor or an extraction tower.

[0058] In one embodiment of extractive lithium extraction, the liquid organic composition for extractive lithium extraction is contacted one or more times with the same lithium-containing aqueous solution.

[0059] In one embodiment of lithium extraction, concentrated acid is added to the lithium-containing removal agent after the removal agent contacts the organic layer, and the removal agent is used again as the removal agent to contact the organic layer; the concentrated acid is 6-12 mol / L hydrochloric acid, 6-18 mol / L sulfuric acid, 6-14 mol / L nitric acid, or 6-15 mol / L phosphoric acid.

[0060] In one embodiment of the lithium extraction process, the process further comprises concentrating lithium by evaporating water from the lithium-containing stripping agent, and / or further precipitating lithium carbonate from the lithium-containing stripping agent.

[0061] The present disclosure provides a novel method for preparing a liquid organic composition for lithium extraction containing 2-hydroxy-4-alkoxy-5-nitroacetophenone and / or 2-hydroxy-4-alkoxy-5-nitrobenzophenone.

[0062] The preparation method comprises:

[0063] Provide component a1), component a1) is 2-hydroxy-4-C 7-16 Alkoxy-acetophenone or / and 2-hydroxy-4-C 7-16 Alkoxy-benzophenone, the C 7-16 Alkoxy groups are optionally substituted;

[0064] subjecting component a1) to a nitration reaction to obtain a mixture of component a1) and component a2); and

[0065] To the mixture of component a1) and component a2) are added the diluent and the synergist.

[0066] In this preparation method, component a2) is derived from the nitration reaction of component a1), and the mixture of component a1) and component a2) is essentially a mixture of raw materials and reaction products.

[0067] In one embodiment, component a1) 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone is nitrated using nitric acid or a nitric acid / acetic acid mixture in an acetic acid solvent to obtain an acetic acid solution of component a1) and component a2).

[0068] For example, the nitration reaction of component a1) can include mixing component a1) with glacial acetic acid or aqueous acetic acid, heating the mixture to 30-110°C, preferably 50-80°C, and then adding nitric acid or a mixture of nitric acid and acetic acid to react to produce an acetic acid solution of the lithium extractant. At 50-80°C, a substantial portion of component a1) melts to form a liquid phase, which facilitates the nitration reaction. In a preferred embodiment, the amount of glacial acetic acid or aqueous acetic acid used in the mixing step of component a1) and glacial acetic acid or aqueous acetic acid is 0.5-5 times the weight of the 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone. In a more preferred embodiment, the amount of glacial acetic acid or aqueous acetic acid used in the step of mixing component a1) with glacial acetic acid or aqueous acetic acid is 0.5 to 2.0 times, for example, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 times the weight of 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone.

[0069] In a preferred embodiment, during the nitration of component a1) 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone using nitric acid or a nitric acid / acetic acid mixture in acetic acid solvent, the amount of glacial acetic acid or aqueous acetic acid used is 1 to 2.0 times the weight of the 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone. The water content in the aqueous acetic acid is 0.1% to 10% of the acetic acid content.

[0070] The method for preparing a liquid organic composition for lithium extraction may further include a step of adding a base to remove the acid. For example, the base is solid or aqueous NaOH. The base may be added to the mixture of components a1) and a2), or to the diluent, or after the diluent and synergist are added to the mixture of components a1) and a2).

[0071] In one embodiment, a base is added to the mixture of component a1) and component a2) before the step of adding the diluent and the synergist to the mixture of component a1) and component a2), and then the organic phase obtained by separation is mixed with the diluent and the synergist to obtain a composition for lithium extraction.

[0072] In another preferred embodiment, the base is added after the diluent and the synergist are added to the mixture of components a1) and a2), which promotes the transfer of the extractant from the aqueous phase to the organic phase.

[0073] A base (such as sodium hydroxide) reacts with acetic acid to neutralize and generate sodium acetate, which is then allowed to stand for stratification. The bottom sodium acetate solution is discharged to obtain an upper deacetic acidized organic phase, which is a liquid organic composition for lithium extraction.

[0074] Component a1) can be commercially available or homemade. For example, providing component a1) can include the step of reacting 2,4-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, or a mixture thereof with a halogenated hydrocarbon to form an ether to produce component a1). The halogenated hydrocarbon is, for example, heptane chloride, octane chloride, nonane chloride, decane chloride, dodecane chloride, tridecane chloride, tetradecane chloride, pentadecane chloride, hexadecane chloride, heptane bromide, n-octane bromide, isooctane bromide, nonane bromide, decane bromide, dodecane bromide, tridecane bromide, tetradecane bromide, pentadecane bromide, hexadecane bromide, heptane iodide, n-octane iodide, isooctane iodide, nonane iodide, decane iodide, dodecane iodide, tridecane iodide, tetradecane iodide, pentadecane iodide, hexadecane iodide, or a mixture of C7-C16 halogenated hydrocarbons.

[0075] The process disclosed herein omits the preparation of solid 2-hydroxy-4-alkoxy-5-nitroacetophenone and / or 2-hydroxy-4-alkoxy-5-nitrobenzophenone, significantly reducing the energy consumption required for distillation of the acetic acid solvent and effectively avoiding the explosive hazard associated with the production of nitro-containing solid materials. Furthermore, the process directly yields a liquid organic composition for lithium extraction. This reduces the complexity and cost of the production process while also ensuring the safety of the extractant preparation.

[0076] The disclosed process for preparing a liquid organic composition for lithium extraction produces virtually no waste organic solvents or wastewater, and produces a sodium acetate solution as a byproduct. The resulting sodium acetate solution can be converted into an economically valuable industrial product through concentration and / or crystallization.

[0077] In one embodiment, the method for preparing a liquid organic composition for lithium extraction comprises:

[0078] (1) nitrating 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone using nitric acid or a nitric acid / acetic acid mixture in an acetic acid solvent to obtain an acetic acid solution A of 2-hydroxy-4-alkoxy-5-nitroacetophenone or / and 2-hydroxy-4-alkoxy-5-nitrobenzophenone;

[0079] (2) mixing the acetic acid solution A obtained in (1) with a synergist and solvent oil to obtain an organic mixture B; and

[0080] (3) Sodium hydroxide solution is added to the organic mixture B obtained in (2) to cause a neutralization reaction between sodium hydroxide and acetic acid in B to generate sodium acetate. The mixture is then allowed to stand and separate into layers. The bottom sodium acetate solution is discharged to obtain an upper deacetic acidized organic phase C, which is a liquid organic mixture for lithium extraction.

[0081] Preferably, the alkoxy group in the 2-hydroxy-4-alkoxy-acetophenone and / or the 2-hydroxy-4-alkoxy-benzophenone is C7 to C16.

[0082] Preferably, in step (1), the 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone is 2-hydroxy-4-heptyloxyacetophenone, 2-hydroxy-4-octyloxyacetophenone, 2-hydroxy-4-nonyloxyacetophenone, 2-hydroxy-4-decyloxyacetophenone, 2-hydroxy-4-undecyloxyacetophenone, 2-hydroxy-4-dodecyloxyacetophenone, 2-hydroxy-4-tridecyloxyacetophenone, 2-hydroxy-4-tetradecyloxyacetophenone, 2-hydroxy-4-pentadecyloxyacetophenone, 2-hydroxy-4-decyloxyacetophenone, 2-Hydroxy-4-decyloxybenzophenone, 2-hydroxy-4-undecyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-tridecyloxybenzophenone, 2-hydroxy-4-tetradecyloxybenzophenone, 2-hydroxy-4-pentadecyloxybenzophenone, 2-hydroxy-4-hexadecyloxybenzophenone or a mixture of any of them.

[0083] Preferably, in step (1), the 2-hydroxy-4-alkoxy-5-nitroacetophenone or / and 2-hydroxy-4-alkoxy-5-nitrobenzophenone is 2-hydroxy-4-heptyloxy-5-nitroacetophenone, 2-hydroxy-4-octyloxy-5-nitroacetophenone, 2-hydroxy-4-nonyloxy-5-nitroacetophenone, 2-hydroxy-4-decyloxy-5-nitroacetophenone, 2-hydroxy-4-undecyloxy-5-nitroacetophenone, 2-hydroxy-4-dodecyloxy-5-nitroacetophenone, 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone, 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone, 2-hydroxy- 4-hexadecyloxy-5-nitroacetophenone, 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, 2-hydroxy-4-octyloxy-5-nitrobenzophenone, 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, 2-hydroxy-4-decyloxy-5-nitrobenzophenone, 2-hydroxy-4-undecyloxy-5-nitrobenzophenone, 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone, 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone, 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone, 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone, 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone or a mixture of any two thereof.

[0084] Preferably, in step (1), the acetic acid solvent has a water content of less than 20%. The disclosed embodiments found that when glacial acetic acid and acetic acid with a low water content were used as solvents, the resulting liquid organic composition for lithium extraction had excellent lithium extraction performance. However, when acetic acid with a high water content or pure water was used as the solvent, the lithium extraction capacity of the liquid organic composition for lithium extraction was significantly reduced.

[0085] Preferably, in step (1), in order to reduce the amount of acetic acid solvent, 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone are first dissolved in a small amount of acetic acid solvent under heating conditions, and the amount of acetic acid used is 0.5 to 5 times the weight of 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone. Then, concentrated nitric acid with a concentration of 68wt% is mixed with acetic acid to prepare a dilute nitric acid acetic acid solution. Finally, the obtained dilute nitric acid acetic acid solution is added to the hot 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone acetic acid solution. Preferably, the heating temperature is 40 to 70°C.

[0086] Preferably, in step (1), the amount of nitric acid used is 0.95 to 1.2 times the molar equivalent of 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone.

[0087] Preferably, in step (1), the temperature of the nitration reaction is 40-70°C.

[0088] Preferably, in step (1), before carrying out the preparation step (2), the acetic acid solution A obtained in step (1) is cooled to room temperature.

[0089] Preferably, in step (1), when the intermediate raw materials of 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone cannot be directly purchased, 2,4-dihydroxyacetophenone and / or 2,4-dihydroxybenzophenone are used as raw materials and prepared by Williamson etherification reaction.

[0090] Preferably, the synergist in step (2) is one or more of tributyl phosphate, trioctyl phosphate, tributylphosphine oxide, trioctylphosphine oxide (or Cyanex921), and trialkylphosphine oxide TRPO (or Cyanex923).

[0091] Preferably, the amount of the synergist added in step (2) is 0.5 to 2 times the molar equivalent of 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone.

[0092] Preferably, the solvent oil in step (2) is one or a mixture of industrial white oil, kerosene, sulfonated kerosene, D series solvent oil, toluene, xylene, ethylbenzene or diethylbenzene.

[0093] Preferably, the solvent oil in step (2) is 2 to 20 liters / mol of lithium extractant.

[0094] Preferably, the organic mixture B in step (2) is cooled to 0-30° C. before step (3).

[0095] Preferably, the concentration of the sodium hydroxide solution added in step (3) is 20 wt.% to 40 wt.%.

[0096] Preferably, the sodium hydroxide solution in step (3) is gradually added to the organic mixture B.

[0097] Preferably, the mixing process of the sodium hydroxide solution and the organic mixture B in step (3) is carried out in a mixer equipped with a cooling device.

[0098] Example

[0099] The following examples are provided to further illustrate the present invention. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the present invention. Where specific techniques or conditions are not specified in the examples, the techniques or conditions described in the literature in the art or in accordance with the product instructions are used. Where the manufacturer of the reagents or instruments used is not specified, they are all commercially available conventional products.

[0100] Unless otherwise defined, technical or scientific terms used in the following embodiments should have the same general meanings as those generally understood by persons having ordinary skills in the field to which the present invention belongs.

[0101] Example A: Preparation of 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone acetic acid solutions with different structures

[0102] Example A1: Preparation of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone acetic acid solution 12.6 g of 2-hydroxy-4-heptyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an 80°C oil bath and 3 mL of 68 wt% nitric acid was added. The reaction was allowed to proceed for 16 h, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone.

[0103] Example A2: Preparation of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone acetic acid solution 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C, 2.75 mL of 68 wt% nitric acid was added, and the reaction was allowed to proceed for 16 h. The mixture was cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone.

[0104] Example A3: Preparation of 2-hydroxy-4-isooctyloxy-5-nitrobenzophenone acetic acid solution 13.06 g of 2-hydroxy-4-isooctyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an 80°C oil bath and 3 mL of 68 wt% nitric acid was added. The reaction was allowed to react for 16 h and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-isooctyloxy-5-nitrobenzophenone.

[0105] Example A4: Preparation of 2-hydroxy-4-nonyloxy-5-nitrobenzophenone acetic acid solution 13.6 g of 2-hydroxy-4-nonyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. After reacting for 16 h, the mixture was cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-nonyloxy-5-nitrobenzophenone.

[0106] Example A5: Preparation of 2-hydroxy-4-decyloxy-5-nitrobenzophenone acetic acid solution 14.2 g of 2-hydroxy-4-decyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The reaction was allowed to proceed for 16 h, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-decyloxy-5-nitrobenzophenone.

[0107] Example A6: Preparation of 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone acetic acid solution 15.3 g of 2-hydroxy-4-dodecyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The reaction was allowed to react for 16 h and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone.

[0108] Example A7: Preparation of 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone acetic acid solution 15.9 g of 2-hydroxy-4-tridecyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C, 3 mL of 68 wt% nitric acid was added, and the reaction was carried out for 12 h. The temperature was then raised to 70°C and the reaction was continued for another 4 h. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone.

[0109] Example A8: Preparation of 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone acetic acid solution 16.42 g of 2-hydroxy-4-tetradecyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C, 3 mL of 68 wt% nitric acid was added, and the reaction was carried out for 12 h. The temperature was then raised to 70°C and the reaction was continued for another 4 h. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone.

[0110] Example A9: Preparation of 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone acetic acid solution: 17.15 g of 2-hydroxy-4-pentadecyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C, 3 mL of 68 wt% nitric acid was added, and the reaction was carried out for 12 h. The temperature was then raised to 70°C and the reaction was continued for another 4 h. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone.

[0111] Example A10: Preparation of 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone acetic acid solution: 17.55 g of 2-hydroxy-4-hexadecyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C, 3 mL of 68 wt% nitric acid was added, and the reaction was carried out for 12 h. The temperature was then raised to 80°C and the reaction was continued for another 4 h. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone.

[0112] Example A11: Preparation of 2-hydroxy-4-heptyloxy-5-nitroacetophenone acetic acid solution: 10.1 g of 2-hydroxy-4-heptyloxyacetophenone was added to 80 mL of glacial acetic acid in a three-necked flask and stirred to completely dissolve it. The flask was then placed in an oil bath at 70°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 16 h and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitroacetophenone.

[0113] Example A12: Preparation of 2-hydroxy-4-n-octyloxy-5-nitroacetophenone acetic acid solution: 10.6 g of 2-hydroxy-4-n-octyloxyacetophenone was added to 80 mL of glacial acetic acid in a three-necked flask and stirred to completely dissolve it. The flask was then placed in an oil bath at 70°C and 2.75 mL of 68 wt% nitric acid was added. The mixture was reacted for 16 h and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitroacetophenone.

[0114] Example A13: Preparation of 2-hydroxy-4-isooctyloxy-5-nitroacetophenone acetic acid solution: 10.6 g of 2-hydroxy-4-isooctyloxyacetophenone was added to 80 mL of glacial acetic acid in a three-necked flask and stirred to completely dissolve it. The flask was then placed in an oil bath at 70°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 16 h and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-isooctyloxy-5-nitroacetophenone.

[0115] Example A14: Preparation of 2-hydroxy-4-nonyloxy-5-nitroacetophenone acetic acid solution: 11.1 g of 2-hydroxy-4-nonyloxyacetophenone was added to 80 mL of glacial acetic acid in a three-necked flask and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 16 h and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-nonyloxy-5-nitroacetophenone.

[0116] Example A15: Preparation of 2-hydroxy-4-decyloxy-5-nitroacetophenone acetic acid solution: 11.7 g of 2-hydroxy-4-decyloxyacetophenone was added to 80 mL of glacial acetic acid in a three-necked flask and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 16 h and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-decyloxy-5-nitroacetophenone.

[0117] Example A16: Preparation of 2-hydroxy-4-dodecyloxy-5-nitroacetophenone acetic acid solution: 12.8 g of 2-hydroxy-4-dodecyloxyacetophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 16 h and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-dodecyloxy-5-nitroacetophenone.

[0118] Example A17: Preparation of 2-hydroxy-4-tridecyloxy-5-nitroacetophenone acetic acid solution: 13.4 g of 2-hydroxy-4-tridecyloxyacetophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 12 h, then heated to 80°C and reacted for another 4 h. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tridecyloxy-5-nitroacetophenone.

[0119] Example A18: Preparation of 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone acetic acid solution: 13.9 g of 2-hydroxy-4-tetradecyloxyacetophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 12 h, then heated to 80°C and reacted for another 4 h. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone.

[0120] Example A19: Preparation of 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone acetic acid solution: 14.7 g of 2-hydroxy-4-pentadecyloxyacetophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 12 h, then heated to 80°C and reacted for another 4 h. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone.

[0121] Example A20: Preparation of 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone acetic acid solution: 15.1 g of 2-hydroxy-4-hexadecyloxyacetophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred to completely dissolve it. The flask was then placed in an oil bath at 50°C and 3 mL of 68 wt% nitric acid was added. The mixture was reacted for 12 h, then heated to 80°C and reacted for another 4 h. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone.

[0122] Example Group B: Preparation of a Composite Lithium Extraction Liquid Organic Composition Containing 2-Hydroxy-4-alkoxy-5-nitrobenzophenone / Acetophenone Example B1: Preparation of a Composite Lithium Extraction Liquid Organic Composition Containing 2-Hydroxy-4-alkoxy-5-nitrobenzophenone / Acetophenone (Synergist: Trialkylphosphine Oxide; Solvent: D80 Solvent Oil)

[0123] 80 mL of acetic acid solutions of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone, 2-hydroxy-4-isooctyloxy-5-nitrobenzophenone, 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, and 2-hydroxy-4-decyloxy-5-nitrobenzophenone prepared in Examples A1-A5 were taken. Separately, 400 mL of D80 solvent oil was added, 13.2 g of trialkylphosphine oxide was added, and stirred until a homogeneous solution was formed. Subsequently, all the prepared D80 solvent oil containing trialkylphosphine oxide was mixed with the acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, and 60 g of anhydrous NaOH was added. After thorough mixing, the mixture was allowed to stand for separation, and the lower aqueous phase was discharged to obtain an upper oily phase. The oily phase was washed with water several times and then used as an extractant for lithium extraction. The composite liquid organic compositions STLK-Z7AN, STLK-Z8AN, STLK-Y8AN, STLK-Z9AN and STLK-Z10AN for extracting lithium were obtained respectively.

[0124] Example B2: Preparation of a composite lithium-extraction liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone (synergist: tri-n-octylphosphine oxide; solvent: 15# industrial white oil)

[0125] Take 80 mL of the acetic acid solutions of 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone, 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone, 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone, 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone, and 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone prepared in Examples A6-A10, respectively. Separately, take 400 mL of 15# industrial white oil, add 15.5 g of tri-n-octylphosphine oxide, and stir until a homogeneous solution is formed. Then, mix all the prepared D80 solvent oil containing trialkylphosphine oxide with the acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, then add 280 g of a 20 wt% aqueous NaOH solution. After thorough mixing, allow the mixture to stand and separate into layers. The lower aqueous phase is discharged to obtain the upper oil phase, which is washed with water multiple times before being used as an extractant for lithium extraction. The composite liquid organic compositions STLK-Z12AN, STLK-Z13AN, STLK-Y14AN, STLK-Z15AN and STLK-Z16AN for extracting lithium were obtained respectively.

[0126] Example B3: Preparation of a composite lithium-extraction liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone (synergist: tri-n-octylphosphine oxide; solvent: diethylbenzene)

[0127] 80 mL of acetic acid solutions of 2-hydroxy-4-heptyloxy-5-nitroacetophenone, 2-hydroxy-4-n-octyloxy-5-nitroacetophenone, 2-hydroxy-4-isooctyloxy-5-nitroacetophenone, 2-hydroxy-4-nonyloxy-5-nitroacetophenone, and 2-hydroxy-4-decyloxy-5-nitroacetophenone prepared in Examples A11-A15 were taken. Separately, 400 mL of diethylbenzene was added, 15.5 g of tri-n-octylphosphine oxide was added, and the mixture was stirred until a homogeneous solution was formed. The resulting D80 solvent oil containing trialkylphosphine oxide was then mixed with the acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone. 186.5 g of a 30 wt% aqueous NaOH solution was then added. After thorough mixing, the mixture was allowed to stand for separation. The lower aqueous phase was discharged to obtain an upper oily phase, which was washed with water several times before being used as an extractant for lithium extraction. The composite liquid organic compositions STLK-Z7BN, STLK-Z8BN, STLK-Y8BN, STLK-Z9BN and STLK-Z10BN for extracting lithium were obtained respectively.

[0128] Example B4: Preparation of a composite lithium-extraction liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone (synergist: tri-n-octylphosphine oxide; solvent: kerosene)

[0129] Take 80 mL of the acetic acid solutions of 2-hydroxy-4-dodecyloxy-5-nitroacetophenone, 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone, 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone, and 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone prepared in Examples A6-A10, respectively. Separately, add 15.5 g of tri-n-octylphosphine oxide to 400 mL of kerosene and stir until a homogeneous solution forms. Next, mix all of the prepared D80 solvent oil containing trialkylphosphine oxide with the acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, then add 140 g of a 40 wt% aqueous NaOH solution. After thorough mixing, allow the mixture to stand and separate into layers. The lower aqueous phase is then discharged to obtain an upper oily phase, which is then washed with water several times before being used as an extractant for lithium extraction. The composite liquid organic compositions STLK-Z12BN, STLK-Z13BN, STLK-Y14BN, STLK-Z15BN and STLK-Z16BN for extracting lithium were obtained respectively.

[0130] Example Group C: Preparation of intermediate raw materials for nitration reaction of 2-hydroxy-4-alkoxy-5-nitrobenzophenone with different structures

[0131] Example C1: Preparation of 2-hydroxy-4-heptyloxybenzophenone intermediate

[0132] Take 31.37g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 100mL of acetone and 20.23g of anhydrous potassium carbonate. Place the flask in a 50°C oil bath and add 25g of bromoheptane (raw material D) dropwise while stirring. Then raise the oil bath temperature to 60°C, open the condenser and let water in, and reflux the system for 14 hours. After the reaction is completed, distill off the acetone solvent, cool to room temperature, and add 1M hydrochloric acid solution to the flask until the pH is 4-6. After separating the aqueous phase, 47g of oily 2-hydroxy-4-heptyloxybenzophenone (raw material intermediate A) is obtained.

[0133] Example C2: Preparation of 2-hydroxy-4-n-octyloxybenzophenone intermediate Take 27.6g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL N,N-dimethylformamide (DMF) and 17.8g of anhydrous potassium carbonate. The flask is placed in an oil bath at 50°C and 25g of bromooctane (raw material D) is added dropwise while stirring. The oil bath temperature is then raised to 70°C and the system is allowed to react for 14 hours. After the reaction is completed, cool to room temperature, add 100mL of water to the flask, and add 6M hydrochloric acid solution dropwise to pH = 4-6. After separating the aqueous phase, a solid of 2-hydroxy-4-n-octyloxybenzophenone (raw material intermediate A) is obtained. After recrystallization with 20mL of 95% ethanol, 36g of the product is obtained.

[0134] Example C3: Preparation of 2-hydroxy-4-isooctyloxybenzophenone intermediate Take 27.6g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL N,N-dimethylformamide (DMF) and 17.8g of anhydrous potassium carbonate. The flask is placed in an oil bath at 50°C and 25g of bromoisooctane (raw material D) is added dropwise while stirring. The oil bath temperature is then raised to 70°C and the system is allowed to react for 14 hours. After the reaction is completed, cool to room temperature and add 100mL of water to the flask. 6M hydrochloric acid solution is also added dropwise to the flask until the pH reaches 4-6. After separating the aqueous phase, 30g of oily 2-hydroxy-4-isooctyloxybenzophenone (raw material intermediate A) is obtained.

[0135] Example C4: Preparation of 2-hydroxy-4-nonyloxybenzophenone intermediate

[0136] Take 25.7g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL of N,N-dimethylformamide (DMF) and 16.6g of anhydrous potassium carbonate. The flask is placed in an oil bath at 70°C and 25g of bromononane (raw material D) is added dropwise while stirring. The system is allowed to react for 14 hours. After the reaction is completed, it is cooled to room temperature and 100mL of water is added to the flask. 6M hydrochloric acid solution is also added dropwise to the flask until the pH is 4-6. After separating the aqueous phase, a solid of 2-hydroxy-4-nonyloxybenzophenone (raw material intermediate A) is obtained. After recrystallization with 20mL of 95% ethanol, 29g of the product is obtained.

[0137] Example C5: Preparation of 2-hydroxy-4-decyloxybenzophenone intermediate

[0138] Take 25.4g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL of N,N-dimethylformamide (DMF) and 16.4g of anhydrous potassium carbonate. Then add 0.5g of potassium iodide. Place the flask in an oil bath at 70°C and add 25g of bromodecane (raw material D) dropwise while stirring. Let the system react for 14 hours. After the reaction is completed, cool to room temperature and add 100mL of water to the flask. Then add 6M hydrochloric acid solution dropwise to the flask until the pH is 4-6. After separating the aqueous phase, a solid of 2-hydroxy-4-decyloxybenzophenone (raw material intermediate A) is obtained. After recrystallization with 20mL of 95% ethanol, 31g of the product is obtained.

[0139] Example C6: Preparation of 2-hydroxy-4-dodecyloxybenzophenone intermediate Take 22.5g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL of N,N-dimethylformamide (DMF) and 14.5g of anhydrous potassium carbonate. Place the flask in an oil bath at 70°C and add 25g of bromododecane (raw material D) dropwise while stirring. The system is allowed to react for 14 hours. After the reaction is completed, cool to room temperature, add 100mL of water to the flask, and add 6M hydrochloric acid solution dropwise to the flask until the pH is 4-6. After separating the aqueous phase, a solid of 2-hydroxy-4-dodecyloxybenzophenone (raw material intermediate A) is obtained. After recrystallization with 20mL of 95% ethanol, 30g of the product is obtained.

[0140] Example C7: Preparation of 2-hydroxy-4-tridecyloxybenzophenone intermediate

[0141] 21.4 g of 2,4-dihydroxyacetophenone (raw material C) was added to a three-necked flask containing 50 mL of N,N-dimethylformamide (DMF) and 13.8 g of anhydrous potassium carbonate. The flask was placed in an oil bath at 70°C and 25 g of tridecane bromide (raw material D) was added dropwise while stirring. The system was allowed to react for 14 hours. After the reaction was completed, the mixture was cooled to room temperature and 100 mL of water was added to the flask. 6 M hydrochloric acid solution was also added dropwise to the flask until the pH reached 4-6. After separating the aqueous phase, a solid of 2-hydroxy-4-tridecyloxybenzophenone (raw material intermediate A) was obtained. After recrystallization from 20 mL of 95% ethanol, 29 g of the product was obtained.

[0142] Example C8: Preparation of 2-hydroxy-4-tetradecyloxybenzophenone intermediate Take 21.4g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 40mL N,N-dimethylformamide (DMF) and 13.8g of anhydrous potassium carbonate. Then add 0.5g of tetrabutylammonium bromide. Place the flask in an oil bath at 70°C and add 25g of bromotetradecane (raw material D) dropwise while stirring. The system is allowed to react for 14 hours. After the reaction is completed, cool to room temperature, add 100mL of water to the flask, and add 6M hydrochloric acid solution dropwise to the flask until the pH is 4-6. After separating the aqueous phase, a solid of 2-hydroxy-4-tetradecyloxybenzophenone (raw material intermediate A) is obtained. After recrystallization with 20mL of 95% ethanol, 32g of the product is obtained.

[0143] Example C9: Preparation of 2-hydroxy-4-pentadecyloxybenzophenone intermediate 7.7 g of 2,4-dihydroxyacetophenone (raw material C) was added to a three-necked flask containing 40 mL of N,N-dimethylformamide (DMF) and 5.5 g of anhydrous potassium carbonate. The flask was placed in an oil bath at 70°C and 10 g of bromopentadecane (raw material D) was added dropwise while stirring. The system was allowed to react for 14 hours. After the reaction was completed, the mixture was cooled to room temperature and 100 mL of water was added to the flask. 6 M hydrochloric acid solution was added dropwise to the flask until the pH reached 4-6. After separating the aqueous phase, a solid of 2-hydroxy-4-pentadecyloxybenzophenone (raw material intermediate A) was obtained. 13 g of the product was obtained after recrystallization with 20 mL of 95% ethanol.

[0144] Example D Group: Performance Results of Compound Lithium Extraction Liquid Organic Compositions with Different Compositions Prepared by Testing Example D1: Performance Test of Lithium Extraction Agent Prepared by the Present Invention I (YL-1: Natural Alkaline Brine)

[0145] The organic phase for lithium extraction (STLK-Z7AN: 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, STLK-Y8AN: 2-hydroxy-4-octyloxy-5-nitrobenzophenone, STLK-Z9AN: 2-hydroxy-4-nonyloxy-5-nitrobenzophenone) was prepared by compounding 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone, trioctylphosphine oxide or / and trialkylphosphine oxide, and solvent oil in Examples B1-B3. Benzophenone, STLK-Z10AN: 2-Hydroxy-4-decyloxy-5-nitrobenzophenone, STLK-Z12AN: 2-Hydroxy-4-dodecyloxy-5-nitrobenzophenone, STLK-Z13AN: 2-Hydroxy-4-tridecyloxy-5-nitrobenzophenone, STLK-Z14AN: 2-Hydroxy-4-tetradecyloxy-5-nitrobenzophenone, STLK-Z15AN: 2-Hydroxy- 4-pentadecyloxy-5-nitrobenzophenone, STLK-Z7BN: 2-hydroxy-4-heptyloxy-5-nitroacetophenone, STLK-Y8BN: 2-hydroxy-4-octyloxy-5-nitroacetophenone, STLK-Z9BN: 2-hydroxy-4-nonyloxy-5-nitroacetophenone, STLK-Z10BN: 2-hydroxy-4-decyloxy-5-nitroacetophenone, STLK-Z12BN: 2-hydroxy- Lithium was selectively extracted from a natural alkaline brine using a mixture of 4-dodecyloxy-5-nitroacetophenone (STLK-Z13BN, 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, STLK-Z14BN, 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone, and STLK-Z15BN), resulting in the selective extraction of lithium into the organic phase. The natural alkaline brine composition used was: Li: 0.258 g / L, Na: 41.051 g / L, K: 7.891 g / L, Mg: 0.082 g / L, Cl: 46 g / L, SO4: 12.77 g / L, B: 0.56 g / L, pH = 9.43. Temperature: room temperature (25°C-27°C). The organic phase was 20 mL. Organic phase / aqueous phase volume ratio (O / A) 4.

[0146]

[0147] Example D2: Performance Test II of Lithium Extraction Agent Prepared by the Present Invention (YL-2: Lithium Precipitation Mother Liquor)

[0148] The organic phase for lithium extraction (STLK-Z7AN: 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, STLK-Y8AN: 2-hydroxy-4-octyloxy-5-nitrobenzophenone, STLK-Z9AN: 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, STLK-Z10AN: 2-hydroxy-4-decyloxy-5-nitrobenzophenone) was prepared by compounding 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone, trioctylphosphine oxide or / and trialkylphosphine oxide, and solvent oil in Examples B1-B3. Lithium was extracted from a lithium carbonate mother liquor using a mixture of nitrobenzophenone (STLK-Z12AN: 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone, STLK-Z13AN: 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone, STLK-Z14AN: 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone, and STLK-Z15AN: 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone), resulting in the selective extraction of lithium from the brine into the organic phase. The composition of the lithium carbonate mother liquor used was: Li: 1.089 g / L, Na: 76.611 g / L, Cl: 118.08 g / L, CO3: 4.7 g / L, pH = 10.74. Temperature: room temperature (25°C to 27°C). The organic phase was 20 mL. Organic phase / aqueous phase volume ratio (O / A) 4.

[0149]

[0150] Example D3: Performance test of lithium extractant prepared by the present invention III (YL-3: boron-containing lithium sodium alkaline solution) The 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone, trioctylphosphine oxide or / and trialkylphosphine oxide, and solvent oil prepared in Examples B1-B3 were used to prepare a lithium extraction organic phase (STLK-Z7AN: 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, STLK-Y8AN: 2-hydroxy-4-octyloxy-5-nitrobenzophenone, STLK-Z9AN: 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, STLK- The lithium in a sodium borate lithium alkaline solution was separated by extraction using a mixture of the following reagents: STLK-Z10AN: 2-hydroxy-4-decyloxy-5-nitrobenzophenone, STLK-Z12AN: 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone, STLK-Z13AN: 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone, STLK-Z14AN: 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone, and STLK-Z15AN: 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone. The lithium in the brine was selectively extracted into the organic phase. The sodium borate lithium alkaline solution YL-3 had a composition of: Li: 0.515 g / L, Na: 85.472 g / L, Cl: 131.7 g / L, B: 0.82 g / L, and a pH of 10.00. The temperature was room temperature (25°C to 27°C). Organic phase: 20 mL. Organic phase / aqueous phase volume ratio (O / A) 4.

[0151]

[0152] Example D4: Performance Test IV of Lithium Extractant Prepared by the Present Invention (YL-4: Mixed Solution of Lithium Hydroxide and Sodium Chloride)

[0153] Using one of the methods described in Examples B1-B3, 20 mL of a 0.1M STLK-Z7AN + STLK-Z9AN (molar ratio 1:1): 0.1M TRPO organic phase, 20 mL of a 0.1M STLK-Y8AN + STLK-Z10AN (molar ratio 1:1): 0.1M TRPO organic phase, 20 mL of a 0.1M STLK-Z12AN: 0.1M TRPO organic phase, and 40 mL of a 0.2M STLK-Y8AN: 0.2M TRPO organic phase were prepared. Lithium was extracted from a lithium-containing alkaline brine, YL-4, to selectively extract the lithium from the brine into the organic phase. The composition of the lithium alkaline brine YL-4 used was: Li: 0.619 g / L, Na: 66.261 g / L, Cl: 102.13 g / L, pH = 12.52. The temperature was room temperature (25°C to 27°C). Organic phase: 20 mL.

[0154]

[0155] Example E: Effect of different nitric acid dosages on extraction performance

[0156] Example E1: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (the amount of nitric acid used was 0.95 times the molar equivalent of the intermediate 2-hydroxy-4-n-octyloxy-benzophenone). 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred until completely dissolved. The flask was then placed in a 50°C oil bath and 2.6 mL of 68 wt% nitric acid was added. After reacting for 12 hours, the temperature was raised to 50°C and the reaction continued for another 4 hours. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Separately, 400 mL of D80 solvent oil was added to 13.2 g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. The trialkylphosphine oxide-containing D80 solvent oil prepared was then mixed with the acetic acid solution, followed by the addition of 60 g of anhydrous NaOH. After thorough mixing, the mixture was allowed to stand for separation, and the lower aqueous phase was discharged to obtain an upper oil phase. The oil phase was washed with water several times and then used as an extractant for lithium extraction. This resulted in the composite liquid organic composition STLK-Z8AN-E1 for lithium extraction.

[0157] Example E2: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (the amount of nitric acid used was 1.1 times the molar equivalent of the intermediate 2-hydroxy-4-n-octyloxy-benzophenone). 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred until completely dissolved. The flask was then placed in a 50°C oil bath and 3.0 mL of 68 wt% nitric acid was added. After reacting for 12 hours, the temperature was raised to 50°C and the reaction continued for another 4 hours. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Separately, 400 mL of D80 solvent oil was added to 13.2 g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. The trialkylphosphine oxide-containing D80 solvent oil prepared was then mixed with the acetic acid solution, followed by the addition of 60 g of anhydrous NaOH. After thorough mixing, the mixture was allowed to stand for separation, and the lower aqueous phase was discharged to obtain an upper oil phase. The oil phase was washed with water several times and then used as an extractant for lithium extraction. This resulted in the composite liquid organic composition STLK-Z8AN-E2 for lithium extraction.

[0158] Example E3: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (the amount of nitric acid used is 1.2 times the molar equivalent of the intermediate 2-hydroxy-4-n-octyloxy-benzophenone). 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid and stirred until completely dissolved. The flask was then placed in a 50°C oil bath and 3.3 mL of 68 wt% nitric acid was added. After reacting for 12 hours, the temperature was raised to 50°C and the reaction was continued for another 4 hours. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Separately, 400 mL of D80 solvent oil was added to 13.2 g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. The trialkylphosphine oxide-containing D80 solvent oil prepared was then mixed with the acetic acid solution, followed by the addition of 60 g of anhydrous NaOH. After thorough mixing, the mixture was allowed to stand for separation, and the lower aqueous phase was discharged to obtain an upper oil phase. The oil phase was washed with water several times and then used as an extractant for lithium extraction. This resulted in the composite liquid organic composition STLK-Z8AN-E3 for lithium extraction.

[0159] The lithium-containing solution YL-2 in Example D2 was used as the original test material to test the capacity of the composite liquid organic compositions STLK-Z8AN, STLK-Z8AN-E1, STLK-Z8AN-E2, and STLK-Z8AN-E3 for lithium extraction prepared at different intermediate: nitric acid ratios. The specific operation was as follows: 20 mL of the composite liquid organic composition and 60 mL of the lithium-containing solution YL-2 were taken, and the composite liquid organic composition was reacted in a separatory funnel for 5 minutes. After standing for 10 minutes to separate the layers, the lower aqueous solution was released; the above process was repeated three times to allow all the extractants in the composite liquid organic composition to react with the metal ions and reach extraction saturation. Afterwards, the saturated extracted organic phase was reacted with 20 mL of 0.6 mol / L hydrochloric acid aqueous solution three times. All three stripping solutions were diluted and fixed to a 1 L volumetric flask. The Li and Na concentrations therein were determined, and the concentration of the effective extractant in the composite liquid organic composition was calculated using the following formula.

[0160] c 萃取剂 (mol / L)=(c Li (mol / L)+c Na (mol / L))*1L / 20mL*1000

[0161] The results are as follows:

[0162]

[0163] Example F Group: Effect of Different Acetic Acid Amounts on Extraction Performance

[0164] Example F1: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (acetic acid dosage: 2 L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octyloxy-benzophenone). 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to 80 mL of glacial acetic acid in a three-necked flask and stirred until completely dissolved. The flask was then placed in an oil bath at 50°C and 2.75 mL of 68 wt% nitric acid was added. After reacting for 12 hours, the temperature was raised to 50°C and the reaction continued for another 4 hours. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Separately, 400 mL of D80 solvent oil was added to 13.2 g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. The trialkylphosphine oxide-containing D80 solvent oil prepared was then mixed with the acetic acid solution, followed by the addition of 60 g of anhydrous NaOH. After thorough mixing, the mixture was allowed to stand for separation, and the lower aqueous phase was discharged to obtain an upper oil phase. The oil phase was washed with water several times and then used as an extractant for lithium extraction. This resulted in the composite liquid organic composition STLK-Z8AN-F1 for lithium extraction.

[0165] Example F2: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (acetic acid dosage: 1 L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octyloxy-benzophenone). 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to 40 mL of glacial acetic acid in a three-necked flask and stirred until completely dissolved. The flask was then placed in an oil bath at 50°C and 2.75 mL of 68 wt% nitric acid was added. After reacting for 12 hours, the temperature was raised to 50°C and the reaction continued for another 4 hours. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Separately, 400 mL of D80 solvent oil was added to 13.2 g of trialkylphosphine oxide and stirred until a homogeneous solution formed. The trialkylphosphine oxide-containing D80 solvent oil prepared was then mixed with the acetic acid solution, followed by the addition of 30 g of anhydrous NaOH. After thorough mixing, the mixture was allowed to stand for separation, and the lower aqueous phase was discharged to obtain an upper oil phase. The oil phase was washed with water several times and then used as an extractant for lithium extraction. This resulted in the composite liquid organic composition STLK-Z8AN-F2 for lithium extraction.

[0166] Example F3: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (acetic acid dosage: 0.5 L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octyloxy-benzophenone). 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 20 mL of glacial acetic acid and stirred until completely dissolved. The flask was then placed in a 50°C oil bath and 2.75 mL of 68 wt% nitric acid was added. After reacting for 12 hours, the temperature was raised to 50°C and the reaction continued for another 4 hours. The mixture was then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Separately, 400 mL of D80 solvent oil was added to 13.2 g of trialkylphosphine oxide and stirred until a homogeneous solution formed. The trialkylphosphine oxide-containing D80 solvent oil prepared was then mixed with the acetic acid solution, followed by the addition of 15 g of anhydrous NaOH. After thorough mixing, the mixture was allowed to stand for separation, and the lower aqueous phase was discharged to obtain an upper oil phase. The oil phase was washed with water several times and then used as an extractant for lithium extraction. This resulted in the composite liquid organic composition STLK-Z8AN-F3 for lithium extraction.

[0167] Example F4: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (acetic acid dosage: 0.25 L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone)

[0168] Take 13.06g of 2-hydroxy-4-n-octyloxybenzophenone and add it to a three-necked flask containing 10mL of glacial acetic acid. Stir until it is completely dissolved. Then place the flask in an oil bath at 50°C, add 2.75mL of 68wt% nitric acid, react for 12h, heat to 50°C and continue to react for 4h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Take another 400mL of D80 solvent oil, add 13.2g of trialkylphosphine oxide, and stir until a uniform solution is formed. After that, all the prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the above acetic acid solution, and then 7.5g of anhydrous NaOH is added. After thorough mixing, stand and separate, release the lower aqueous phase, obtain the upper oil phase, wash the oil phase with water several times and use it as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-F4 for lithium extraction is obtained respectively.

[0169] Example F5: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (the amount of acetic acid used was 0. Water was used as the solvent, and the amount of water added was 2 liters per mole of the intermediate 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone)

[0170] Take 13.06g of 2-hydroxy-4-n-octyloxybenzophenone and add it to a three-necked flask containing 80mL of water. Then place the flask in an oil bath at 50°C, add 2.75mL of 68wt% nitric acid, react for 12h, heat to 50°C and continue to react for 4h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Separately take 400mL of D80 solvent oil, add 13.2g of trialkylphosphine oxide, and stir until a uniform solution is formed. Afterwards, all the prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the above acetic acid solution, mixed thoroughly, allowed to stand and separated, the lower aqueous phase is discharged, and the upper oil phase is obtained. The oil phase is washed with water several times and used as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-F5 for lithium extraction is obtained respectively.

[0171] The lithium-containing solution YL-2 in Example D2 was used as the original test material to determine the capacity of the composite liquid organic compositions STLK-Z8AN-F1, STLK-Z8AN-F2, STLK-Z8AN-F3, STLK-Z8AN-F4, and STLK-Z8AN-F5 for lithium extraction, prepared at different intermediate:nitric acid ratios. The specific procedure was as follows: 20 mL of the composite liquid organic composition and 60 mL of the lithium-containing solution YL-2 were each taken and reacted with the composite liquid organic composition in a separatory funnel for 5 minutes. The mixture was then allowed to stand for 10 minutes to separate the layers, and the lower aqueous solution was discharged. This process was repeated three times to allow all the extractants in the composite liquid organic composition to react with the metal ions and reach saturated extraction. The saturated extracted organic phase was then reacted three times with 20 mL of 0.6 mol / L aqueous hydrochloric acid. The stripping solutions obtained from all three extractions were diluted and fixed to a 1 L volumetric flask. The Li and Na concentrations were determined, and the concentration of the effective extractant in the composite liquid organic composition was calculated using the following formula.

[0172] c 萃取剂 (mol / L)=(c Li (mol / L)+c Na (mol / L))*1L / 20mL*1000

[0173] The results are as follows:

[0174]

Claims

1. A liquid organic composition for lithium extraction, comprising: component a) a lithium extractant, component b) a synergist, and component c) a diluent, wherein the component a) comprises component a1) and component a2), the component a1) is 2-hydroxy-4-C 7-16 Alkoxy-acetophenone and / or 2-hydroxy-4-C 7-16 Alkoxy-benzophenone, the C 7-16 The alkoxy group is optionally substituted, and the component a2) is the nitration product of the component a1).

2. The liquid organic composition for lithium extraction according to claim 1, wherein: The component a2) is 2-hydroxy-4-C 7-16 Alkoxy-5-nitroacetophenone or / and 2-hydroxy-4-C 7-16 Alkoxy-5-nitrobenzophenone.

3. The liquid organic composition for lithium extraction according to claim 1, wherein: The component a1) is 2-hydroxy-4-heptyloxyacetophenone, 2-hydroxy-4-octyloxyacetophenone, 2-hydroxy-4-nonyloxyacetophenone, 2-hydroxy-4-decyloxyacetophenone, 2-hydroxy-4-undecyloxyacetophenone, 2-hydroxy-4-dodecyloxyacetophenone, 2-hydroxy-4-tridecyloxyacetophenone, 2-hydroxy-4-tetradecyloxyacetophenone, 2-hydroxy-4-pentadecyloxyacetophenone, 2-hydroxy-4-hexadecyloxyacetophenone, 2-hydroxy-4- Heptyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-nonyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4-undecyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-tridecyloxybenzophenone, 2-hydroxy-4-tetradecyloxybenzophenone, 2-hydroxy-4-pentadecyloxybenzophenone, 2-hydroxy-4-hexadecyloxybenzophenone or a mixture of any of them.

4. The liquid organic composition for lithium extraction according to claim 3, wherein: The component a2) is 2-hydroxy-4-heptyloxy-5-nitroacetophenone, 2-hydroxy-4-octyloxy-5-nitroacetophenone, 2-hydroxy-4-nonyloxy-5-nitroacetophenone, 2-hydroxy-4-decyloxy-5-nitroacetophenone, 2-hydroxy-4-undecyloxy-5-nitroacetophenone, 2-hydroxy-4-dodecyloxy-5-nitroacetophenone, 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone, 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone, 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone, 2-hydroxy-4- Heptyloxy-5-nitrobenzophenone, 2-hydroxy-4-octyloxy-5-nitrobenzophenone, 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, 2-hydroxy-4-decyloxy-5-nitrobenzophenone, 2-hydroxy-4-undecyloxy-5-nitrobenzophenone, 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone, 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone, 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone, 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone, 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone or a mixture of any two thereof.

5. The liquid organic composition for lithium extraction according to any one of claims 1 to 4, wherein the molar ratio of the component a1) to the component a2) is 1:1 to 1:1000.

6. The liquid organic composition for lithium extraction according to claim 5, wherein the molar ratio of the component a1) to the component a2) is 1:10 to 1:

100.

7. The liquid organic composition for lithium extraction according to any one of claims 1 to 4, wherein the synergist is one or more of tributyl phosphate, trioctyl phosphate, tris(2-ethylhexyl) phosphate, trihexyl phosphate, tripentyl phosphate, dibutyl butyl phosphate, dibutyl butyl phosphate, di-sec-octyl methyl phosphate, diisooctyl methyl phosphate, diisooctyl isopropyl phosphate, diisoamyl methyl phosphate, triphenylphosphine oxide, diphenylbenzylphosphine oxide, diphenyl(2-hydroxyphenylmethyl)phosphine oxide, 2,5-dihydroxyphenyl(diphenyl)phosphine oxide, trioctylphosphine oxide (or Cyanex921), and trialkylphosphine oxide TRPO (or Cyanex923).

8. The liquid organic composition for lithium extraction according to any one of claims 1 to 4, wherein the diluent is one or more of industrial white oil, kerosene, sulfonated kerosene, D series solvent oil, n-heptane, cyclohexane, octane, dodecane, petroleum ether, xylene, anisole, methyl isobutyl ketone, toluene, octanone, 5-nonanone, isoamyl alcohol, n-butanol, halogenated benzene, ethylbenzene or diethylbenzene.

9. The liquid organic composition for lithium extraction according to any one of claims 1 to 4, wherein: The total concentration of the lithium extractants a1) and a2) in the liquid organic composition for lithium extraction is 0.03 mol / L to 1.0 mol / L; the concentration of the synergist in the liquid organic composition for lithium extraction is 0.01 mol / L to 2.0 mol / L; and the molar ratio of the lithium extractant to the synergist is 3:1 to 0.5:

1.

10. A method for preparing a liquid organic composition for lithium extraction according to any one of claims 1 to 8, comprising: Providing component a1); nitrating component a1) to obtain a mixture of component a1) and component a2); and To the mixture of component a1) and component a2) are added diluents and synergists.

11. The preparation method according to claim 10, wherein the component a1) is nitrated using nitric acid or a nitric acid / acetic acid mixture in an acetic acid solvent to obtain a mixture of the component a1) and the component a2), and the mixture of the component a1) and the component a2) is an acetic acid solution of the component a1) and the component a2).

12. The preparation method according to claim 11, wherein the nitration of component a1) comprises mixing the component a1) with glacial acetic acid or aqueous acetic acid, heating the mixture to 30-110°C, and then adding nitric acid or a mixture of nitric acid and acetic acid to react to obtain an acetic acid solution of the component a1) and the component a2).

13. The preparation method according to claim 12, wherein the amount of glacial acetic acid or aqueous acetic acid is 0.5 to 5 times the weight of the component a1).

14. The preparation method according to any one of claims 10 to 13, further comprising, before adding the diluent and the synergist to the mixture of the component a1) and the component a2), adding a base to the mixture of the component a1) and the component a2), and then mixing the resulting mixture with the diluent and the synergist to obtain a composition for lithium extraction.

15. The preparation method according to any one of claims 10 to 13, further comprising, after adding a diluent and a synergist to the mixture of component a1) and component a2), adding a base to the mixture of component a1) and component a2), and then separating the layers to obtain an organic phase. The preparation method according to claim 14 , wherein the base is solid or aqueous NaOH solution. The preparation method according to claim 15 , wherein the base is solid or aqueous NaOH solution.

18. The preparation method according to any one of claims 10 to 13, wherein the component a1) is a commercially available product, or the component a1) is homemade.

19. The preparation method according to claim 18, wherein the component a1) is prepared by reacting 2,4-dihydroxyacetophenone, 2,4-dihydroxybenzophenone or a mixture thereof with a halogenated hydrocarbon to form an ether.

20. The preparation method of claim 18, wherein the halogenated hydrocarbon is a heptane chloride, an octane chloride, a nonane chloride, a decane chloride, a dodecane chloride, a tridecane chloride, a tetradecane chloride, a pentadecane chloride, a hexadecane chloride, a heptane bromide, an octane bromide, a nonane bromide, a decane bromide, a dodecane bromide, a tridecane bromide, a tetradecane bromide, a pentadecane bromide, a hexadecane bromide, a heptane iodide, an octane iodide, a nonane iodide, a decane iodide, a dodecane iodide, a tridecane iodide, a tetradecane iodide, a pentadecane iodide, a hexadecane iodide, or a C7-C16 halogenated hydrocarbon mixture, or an isomer of these halogenated hydrocarbons.

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