Liquid organic composition for lithium extraction, and preparation method therefor

Abstract

The present disclosure provides a liquid organic composition for lithium extraction, comprising a component a), i.e., a lithium extractant, a component b), i.e., a synergist, and a component c), i.e., a diluent, wherein the component a) comprises a component a1) and a component a2); the component a1) is 2-hydroxy-4-C7-16alkoxy-acetophenone or / and 2-hydroxy-4-C7-16alkoxy-benzophenone, wherein C7-16alkoxy is optionally substituted; and the component a2) is a nitration product of the component a1). Also provided is a preparation method for the liquid organic composition for lithium extraction.

Description

Liquid organic composition for lithium extraction and preparation method thereof

[0001] This application claims priority to Chinese patent application No. 202310793022.7 filed on June 30, 2023, and the contents of the above-mentioned Chinese patent application disclosure are hereby incorporated by reference in their entirety as a part of this application. Technical Field

[0002] The present disclosure relates to the field of lithium extraction technology, and more particularly to a method for preparing a novel liquid organic composition for lithium extraction. More specifically, the present disclosure 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 same. Background Art

[0003] 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 crucial for efficient lithium extraction.

[0004] A new type of lithium phenolate-based extractant has been reported in recent years, capable of highly selectively separating lithium from other elements, such as sodium, potassium, and magnesium, in brine. However, the cost-effective and environmentally friendly industrial preparation of this extractant and its organic phase for lithium extraction remains to be explored. Furthermore, optimizing the specific groups and their combinations within its general structure to achieve even better lithium extraction is essential.

[0005] 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.

[0006] Summary of the Invention

[0007] 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 a 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.

[0008] The present disclosure provides a method for preparing the aforementioned liquid organic composition for lithium extraction, comprising: providing a component a1), wherein the component a1) is 2-hydroxy-4-C 7-16 Alkoxy-acetophenone or / and 2-hydroxy-4-C 7-16Alkoxy-benzophenone, the C 7-16 The alkoxy group is optionally substituted; component a1) is subjected to a nitration reaction in an acetic acid solvent to obtain a mixture of component a1) and component a2); and 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, thereby obtaining a liquid organic composition for lithium extraction.

[0009] By the method provided by the present disclosure, 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). DETAILED DESCRIPTION

[0010] In order to make the purpose, technical solutions and advantages of the embodiments of the present disclosure more clear, the embodiments of the present disclosure are clearly and completely described below. The embodiments described below are exemplary and are only used to explain the present disclosure, and should not be understood as limiting the present disclosure. Based on the described embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present disclosure.

[0011] The present disclosure may be implemented in other specific forms without departing from the essential attributes of the present disclosure. It should be understood that, without conflict, any and all embodiments of the present disclosure may be combined with the technical features of any other embodiment or multiple other embodiments to obtain additional embodiments. The present disclosure includes additional embodiments obtained by such combinations.

[0012] 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.

[0013] The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described.

[0014] 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.

[0015] 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.

[0016] As used in this disclosure, words such as “include”, “contain” or “comprise” 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.

[0017] With technological advancements, society's demand for lithium salts continues to increase annually. Obtaining lithium from lithium-bearing ores and brines—the primary sources of lithium salts—inevitably requires extracting lithium from aqueous solutions containing alkali and alkaline earth metals. Therefore, the development of compounds and combinations with exceptional selectivity for lithium is crucial for efficient lithium extraction.

[0018] For example, a new type of lithium phenol-ketone extractant can achieve highly selective separation of lithium from elements such as sodium, potassium, and magnesium in brine. However, the cost-effective and green industrial production of this type of extractant and its organic phase for lithium extraction remains to be explored. Furthermore, optimizing the specific groups and their combinations within its general structure to achieve even better lithium extraction is essential.

[0019] For example, a lithium extractant with a structure of 2-hydroxy-4-alkoxy-5-nitroacetophenone and / or 2-hydroxy-4-alkoxy-5-nitrobenzophenone is prepared through a nitration reaction using 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone intermediates as raw materials. This patent application uses vacuum distillation to remove the acetic acid solvent used in the reaction to obtain a solid extractant. This presents 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.

[0020] 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.

[0021] To solve the above and other technical problems, in one embodiment of the present disclosure, a liquid organic composition for lithium extraction is provided, which comprises component a) a lithium extractant, component b) a synergist, and component c) a diluent.

[0022] In another embodiment, a liquid organic composition for lithium extraction is provided, which is essentially composed 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 99.5 weight% or more of the liquid organic composition for lithium extraction.

[0023] In another embodiment, a liquid organic composition for lithium extraction is provided, comprising component a) a lithium extractant, component b) a synergist, and component c) a diluent, wherein the content of component a) the lithium extractant, component b) the synergist, and component c) the diluent in the liquid organic composition for lithium extraction is less than 97% by weight. The liquid organic composition for lithium extraction may contain other components, as long as the other components do not negatively affect the lithium extraction performance of the organic composition.

[0024] 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 C 1-3 Alkyl, C 1-3 Alkoxy, C 5-6 Cycloalkyl, halogen, nitro, benzyloxy, hydroxy, etc.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] The term "nitro" in this disclosure refers to a -NO2 group.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] In the liquid organic composition for extracting lithium in the present application, component a) lithium extractant 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).

[0035] 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.

[0036] 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.

[0037] 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.

[0038] In the liquid organic composition for lithium extraction of the present application, component a2) and component a1) can be in any ratio. Preferably, the molar ratio of component a1) to component a2) is 1:1 to 1:1000, more preferably 1:2 to 1:200, and even more preferably 1:10 to 1:100.

[0039] 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).

[0040] In the liquid organic composition for lithium extraction described herein, component a2) is the nitration 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. Adding excess nitric acid to maximize nitration of component a1) increases post-processing costs.

[0041] 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).

[0042] 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.

[0043] 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.

[0044] The present disclosure also provides a method for extracting lithium, which comprises: contacting the aforementioned liquid organic composition for extracting lithium with an aqueous solution containing lithium ions, allowing the lithium ions in the aqueous solution to enter the organic layer through liquid-liquid separation, and collecting the organic layer.

[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: providing component a1), wherein 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; subjecting component a1) to a nitration reaction to obtain a mixture of component a1) and component a2); and adding a diluent and a synergist to the mixture of component a1) and component a2).

[0063] 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.

[0064] 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).

[0065] 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.

[0066] 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.

[0067] 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).

[0068] 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.

[0069] 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.

[0070] 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.

[0071] Component a1) can be commercially available or homemade. For example, providing component a1) may include the step of preparing component a1) by reacting 2,4-dihydroxyacetophenone, 2,4-dihydroxybenzophenone or a mixture of the two with a halogenated hydrocarbon to form an ether. 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 C7-C 16 mixture of halogenated hydrocarbons.

[0072] 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.

[0073] 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.

[0074] In one embodiment, a method for preparing a liquid organic composition for lithium extraction comprises: (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; (2) mixing the acetic acid solution A obtained in (1) with a synergist and solvent oil to obtain an organic mixture B; and (3) adding a sodium hydroxide solution to the organic mixture B obtained in (2) to neutralize the sodium hydroxide with the acetic acid in B to generate sodium acetate, then allowing the mixture to stand for stratification, discharging the bottom sodium acetate solution, and obtaining an upper deaceticated organic phase C, which is the liquid organic composition for lithium extraction.

[0075] Preferably, the alkoxy group in the 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone is C7-C 16 Alkoxy.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] Preferably, in step (1), the temperature of the nitration reaction is 40-70°C.

[0082] 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.

[0083] 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.

[0084] 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).

[0085] 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.

[0086] 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.

[0087] Preferably, the solvent oil in step (2) is 2 to 20 L / mol lithium extractant.

[0088] Preferably, the organic mixture B in step (2) is cooled to 0-30° C. before step (3).

[0089] Preferably, the concentration of the sodium hydroxide solution added in step (3) is 20wt% to 40wt%.

[0090] Preferably, the sodium hydroxide solution in step (3) is gradually added to the organic mixture B.

[0091] 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.

[0092] The following paragraphs provide a further understanding of the disclosed liquid organic compound for lithium extraction and its preparation method.

[0093] 1. A liquid organic composition for lithium extraction, comprising: 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).

[0094] 2. The liquid organic composition for lithium extraction as described in paragraph 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.

[0095] 3. The liquid organic composition for lithium extraction according to paragraph 1 or 2, 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. oxyacetophenone, 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 two thereof.

[0096] 4. The liquid organic composition for lithium extraction according to any one of paragraphs 1 to 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.

[0097] 5. The liquid organic composition for lithium extraction according to any one of paragraphs 1 to 4, wherein the molar ratio of the component a1) to the component a2) is 1:1 to 1:1000, preferably 1:10 to 1:100.

[0098] 6. The liquid organic composition for lithium extraction as described in any one of paragraphs 1 to 5, 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).

[0099] 7. The liquid organic composition for lithium extraction according to any one of paragraphs 1 to 6, 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, isopentanol, n-butanol, halogenated benzene, ethylbenzene or diethylbenzene.

[0100] 8. The liquid organic composition for lithium extraction as described in any one of paragraphs 1 to 7, wherein the total concentration of the lithium extraction agents 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 extraction agent to the synergist is 3:1 to 0.5:1.

[0101] 9. A method for preparing a liquid organic composition for lithium extraction as described in any one of paragraphs 1 to 8, comprising:

[0102] 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;

[0103] subjecting component a1) to a nitration reaction to obtain a mixture of component a1) and component a2); and

[0104] To the mixture of component a1) and component a2) are added the diluent and the synergist.

[0105] 10. The preparation method according to paragraph 9, wherein the 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone of component a1) 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).

[0106] 11. The preparation method according to paragraph 10, wherein the nitration reaction of component a1) comprises mixing 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 lithium extractant.

[0107] 12. The preparation method according to paragraph 11, wherein the amount of glacial acetic acid or aqueous acetic acid is 0.5 to 5 times the weight of a1).

[0108] 13. The preparation method according to any one of paragraphs 9 to 12, further comprising, before the step of adding the diluent and the synergist to the acetic acid solution of component a1) and component a2), adding a base to the solution, and then mixing the obtained mixture with the diluent and the synergist to obtain a composition for lithium extraction.

[0109] 14. The preparation method according to any one of paragraphs 9 to 12, further comprising, after adding the diluent and the synergist to the acetic acid solution of component a1) and component a2), adding a base, and separating the layers to obtain an organic phase.

[0110] 15. The preparation method according to paragraph 13 or 14, wherein the base is solid or aqueous NaOH solution.

[0111] 16. The preparation method according to any one of paragraphs 9 to 15, wherein the component a1) is commercially available or is prepared by etherification reaction of 2,4-dihydroxyacetophenone, 2,4-dihydroxybenzophenone or a mixture thereof with a halogenated hydrocarbon.

[0112] 17. The preparation method according to paragraph 16, wherein the halogenated hydrocarbon is chloroheptane, chlorooctane, chlorononane, chlorodecane, chlorododecane, chlorotridecane, chlorotetradecane, chloropentadecane, chlorohexadecane, bromoheptane, bromooctane, bromononane, bromodecane, bromododecane, bromotridecane, bromotetradecane, bromopentadecane, bromohexadecane, iodoheptane, iodooctane, iodononane, iododecane, iodododecane, iodotridecane, iodotetradecane, iodopentadecane, iodohexadecane, or C7-C 16 mixtures of halogenated hydrocarbons, and isomers of these halogenated hydrocarbons.

[0113] Example

[0114] The following examples are provided to further illustrate the present disclosure. It should be understood that these examples are intended to illustrate the present disclosure only and are not intended to limit the scope of the present disclosure. 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 were used. Where the manufacturer of the reagents or instruments used is not specified, all are commercially available conventional products.

[0115] 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 disclosure belongs.

[0116] Example A: Preparation of 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone acetic acid solutions with different structures

[0117] Example A1: Preparation of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone acetic acid solution

[0118] 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. The flask was then placed in an 80°C oil bath 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-nitrobenzophenone.

[0119] Example A2: Preparation of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone acetic acid solution

[0120] 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. The flask was then placed in an oil bath at 50°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-nitrobenzophenone.

[0121] Example A3: Preparation of 2-hydroxy-4-isooctyloxy-5-nitrobenzophenone acetic acid solution

[0122] 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. The flask was then placed in an 80°C oil bath 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-nitrobenzophenone.

[0123] Example A4: Preparation of 2-hydroxy-4-nonyloxy-5-nitrobenzophenone acetic acid solution

[0124] 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. 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-nitrobenzophenone.

[0125] Example A5: Preparation of 2-hydroxy-4-decyloxy-5-nitrobenzophenone acetic acid solution

[0126] 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. 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-nitrobenzophenone.

[0127] Example A6: Preparation of 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone acetic acid solution

[0128] 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. 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-nitrobenzophenone.

[0129] Example A7: Preparation of 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone acetic acid solution

[0130] 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. The flask was then placed in an oil bath at 50 ° C. 3 mL of 68 wt% nitric acid was added and the mixture was allowed to react for 12 h. The mixture was then heated to 70 ° 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-nitrobenzophenone.

[0131] Example A8: Preparation of 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone acetic acid solution

[0132] 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. The flask was then placed in an oil bath at 50 ° C. 3 mL of 68 wt% nitric acid was added and the mixture was allowed to react for 12 h. The mixture was then heated to 70 ° 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-nitrobenzophenone.

[0133] Example A9: Preparation of 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone acetic acid solution

[0134] 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. The flask was then placed in an oil bath at 50 ° C. 3 mL of 68 wt% nitric acid was added and the mixture was reacted for 12 h. The mixture was then heated to 70 ° 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-nitrobenzophenone.

[0135] Example A10: Preparation of 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone acetic acid solution

[0136] 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. The flask was then placed in an oil bath at 50 ° C. 3 mL of 68 wt% nitric acid was added and the mixture was allowed to react for 12 h. The mixture was 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-nitrobenzophenone.

[0137] Example A11: Preparation of 2-hydroxy-4-heptyloxy-5-nitroacetophenone acetic acid solution

[0138] 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. 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.

[0139] Example A12: Preparation of 2-hydroxy-4-n-octyloxy-5-nitroacetophenone acetic acid solution

[0140] 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. 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.

[0141] Example A13: Preparation of 2-hydroxy-4-isooctyloxy-5-nitroacetophenone acetic acid solution

[0142] 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. 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.

[0143] Example A14: Preparation of 2-hydroxy-4-nonyloxy-5-nitroacetophenone acetic acid solution

[0144] 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. 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.

[0145] Example A15: Preparation of 2-hydroxy-4-decyloxy-5-nitroacetophenone acetic acid solution

[0146] 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. 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.

[0147] Example A16: Preparation of 2-hydroxy-4-dodecyloxy-5-nitroacetophenone acetic acid solution

[0148] 12.8 g of 2-hydroxy-4-dodecyloxyacetophenone was added to 80 mL of glacial acetic acid in a three-necked flask and stirred to completely dissolve. 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.

[0149] Example A17: Preparation of 2-hydroxy-4-tridecyloxy-5-nitroacetophenone acetic acid solution

[0150] 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. 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.

[0151] Example A18: Preparation of 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone acetic acid solution

[0152] 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. 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.

[0153] Example A19: Preparation of 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone acetic acid solution

[0154] 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. 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.

[0155] Example A20: Preparation of 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone acetic acid solution

[0156] Take 15.1 g of 2-hydroxy-4-hexadecyloxyacetophenone and add it to a three-necked flask containing 80 mL of glacial acetic acid. Stir to completely dissolve it. Then place the flask in an oil bath at 50°C and add 3 mL of 68 wt% nitric acid. After reacting for 12 hours, heat to 80°C and react for another 4 hours. Then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone.

[0157] Example Group B: Preparation of a composite lithium-extraction liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone

[0158] 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)

[0159] 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.

[0160] 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)

[0161] 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.

[0162] 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)

[0163] 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.

[0164] 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)

[0165] 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.

[0166] Example Group C: Preparation of intermediate raw materials for nitration reaction of 2-hydroxy-4-alkoxy-5-nitrobenzophenone with different structures

[0167] Example C1: Preparation of 2-hydroxy-4-heptyloxybenzophenone intermediate

[0168] 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.

[0169] Example C2: Preparation of 2-hydroxy-4-n-octyloxybenzophenone intermediate

[0170] Take 27.6g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL of N,N-dimethylformamide (DMF) and 17.8g of anhydrous potassium carbonate. The flask is placed in a 50°C oil bath 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 a pH of 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.

[0171] Example C3: Preparation of 2-hydroxy-4-isooctyloxybenzophenone intermediate

[0172] Take 27.6g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL of N,N-dimethylformamide (DMF) and 17.8g of anhydrous potassium carbonate. Place the flask in a 50°C oil bath and add 25g of bromoisooctane (raw material D) dropwise while stirring. Then raise the oil bath temperature to 70°C and let the system 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.

[0173] Example C4: Preparation of 2-hydroxy-4-nonyloxybenzophenone intermediate

[0174] 25.7g of 2,4-dihydroxyacetophenone (raw material C) was added to a three-necked flask containing 50mL of N,N-dimethylformamide (DMF) and 16.6g of anhydrous potassium carbonate. The flask was placed in a 70°C oil bath and 25g of bromononane (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 100mL of water was added to the flask. A 6M 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-nonyloxybenzophenone (raw material intermediate A) was obtained. The product was recrystallized from 20mL of 95% ethanol to obtain 29g of the product.

[0175] Example C5: Preparation of 2-hydroxy-4-decyloxybenzophenone intermediate

[0176] 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 a 70°C oil bath and add 25g of bromodecane (raw material D) dropwise while stirring. 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, 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.

[0177] Example C6: Preparation of 2-hydroxy-4-dodecyloxybenzophenone intermediate

[0178] 22.5g of 2,4-dihydroxyacetophenone (raw material C) was added to a three-necked flask containing 50mL of N,N-dimethylformamide (DMF) and 14.5g of anhydrous potassium carbonate. The flask was placed in an oil bath at 70°C and 25g of bromododecane (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 100mL of water was added to the flask. 6M 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-dodecyloxybenzophenone (raw material intermediate A) was obtained. 30g of the product was obtained after recrystallization from 20mL of 95% ethanol.

[0179] Example C7: Preparation of 2-hydroxy-4-tridecyloxybenzophenone intermediate

[0180] 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. A 6M hydrochloric acid solution was then 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. The product was recrystallized from 20 mL of 95% ethanol to obtain 29 g of the product.

[0181] Example C8: Preparation of 2-hydroxy-4-tetradecyloxybenzophenone intermediate

[0182] Take 21.4g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 40mL of N,N-dimethylformamide (DMF) and 13.8g of anhydrous potassium carbonate. Then add 0.5g of tetrabutylammonium bromide. Place the flask in a 70°C oil bath and add 25g of tetradecane bromide (raw material D) dropwise while stirring. 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 added 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.

[0183] Example C9: Preparation of 2-hydroxy-4-pentadecyloxybenzophenone intermediate

[0184] 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 a 70°C oil bath and 10 g of pentadecane 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. A 6M 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-pentadecyloxybenzophenone (raw material intermediate A) was obtained. The product was recrystallized from 20 mL of 95% ethanol to obtain 13 g of the product.

[0185] Example D Group: Performance results of different prepared composite lithium extraction liquid organic compositions

[0186] Example D1: Performance Test of Lithium Extractant Prepared by the Present Disclosure I (YL-1: Natural Alkaline Brine)

[0187] 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 to 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. The volume ratio of organic phase to aqueous phase (O / A) was 4.

[0188] Example D2: Performance Test II of Lithium Extraction Agent Prepared by the Present Disclosure (YL-2: Lithium Precipitation Mother Liquor)

[0189] 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 to B3 (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) 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-27°C). The organic phase was 20 mL. The volume ratio of organic phase to aqueous phase (O / A) was 4.

[0190] Example D3: Performance Test III of Lithium Extractant Prepared by the Present Disclosure (YL-3: Boron-Containing Lithium Sodium Alkaline Solution)

[0191] 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 to B3 (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) Lithium was extracted from a sodium borate lithium alkaline solution 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 sodium borate lithium alkaline solution YL-3 used had a composition of: Li: 0.515 g / L, Na: 85.472 g / L, Cl: 131.7 g / L, B: 0.82 g / L, pH = 10.00. Temperature: Room temperature (25°C to 27°C). The organic phase was 20 mL. The volume ratio of organic phase to aqueous phase (O / A) was 4.

[0192] Example D4: Performance Test IV of the Lithium Extractant Prepared by the Present Disclosure (YL-4: Mixed Solution of Lithium Hydroxide and Sodium Chloride)

[0193] 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, and pH = 12.52. Temperature: room temperature (25°C to 27°C). Organic phase: 20 mL.

[0194] Example E: Effect of different nitric acid dosages on extraction performance

[0195] Example E1: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (the amount of nitric acid used is 0.95 times the molar equivalent of the intermediate 2-hydroxy-4-n-octyloxy-benzophenone)

[0196] Take 13.06g of 2-hydroxy-4-n-octyloxybenzophenone and add it to a three-necked flask containing 80mL of glacial acetic acid. Stir until it is completely dissolved. Then place the flask in an oil bath at 50°C, add 2.6mL 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 60g 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-E1 for lithium extraction is obtained respectively.

[0197] Example E2: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (the amount of nitric acid used is 1.1 times the molar equivalent of the intermediate 2-hydroxy-4-n-octyloxy-benzophenone)

[0198] Take 13.06g of 2-hydroxy-4-n-octyloxybenzophenone and add it to a three-necked flask containing 80mL of glacial acetic acid. Stir until it is completely dissolved. Then place the flask in an oil bath at 50°C, add 3.0mL 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 D80 solvent oil containing trialkylphosphine oxide prepared is mixed with the above acetic acid solution, and then 60g 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-E2 for lithium extraction is obtained respectively.

[0199] 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)

[0200] Take 13.06g of 2-hydroxy-4-n-octyloxybenzophenone and add it to a three-necked flask containing 80mL of glacial acetic acid. Stir until it is completely dissolved. Then place the flask in an oil bath at 50°C, add 3.3mL 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 D80 solvent oil containing trialkylphosphine oxide prepared is mixed with the above acetic acid solution, and then 60g 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-E3 for lithium extraction is obtained respectively.

[0201] The lithium-containing solution YL-2 in Example D2 was used as the original test for 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 intermediates: nitric acid ratios. The specific operation is: take 20mL of the composite liquid organic composition and 60mL of the lithium-containing solution YL-2, respectively, and react with the composite liquid organic composition in a separatory funnel for 5 minutes, then let it stand for 10 minutes to separate the layers, and release the lower aqueous solution; repeat the above process 3 times to allow all the extractants in the composite liquid organic composition to react with the metal ions to reach the extraction saturation state. Afterwards, the obtained saturated extracted organic phase is reacted with 20mL of 0.6mol / L hydrochloric acid aqueous solution 3 times, and all the stripping solutions obtained 3 times are diluted and fixed to a 1L volumetric flask, and the Li and Na concentrations therein are determined, and the concentration of the effective extractant in the composite liquid organic composition is calculated using the following formula. c 萃取剂 (mol / L)=(c Li (mol / L)+c Na (mol / L))*1L / 20mL*1000

[0202] The results are as follows:

[0203] Example F Group: Effect of Different Acetic Acid Amounts on Extraction Performance

[0204] 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-5-nitrobenzophenone)

[0205] Take 13.06g of 2-hydroxy-4-n-octyloxybenzophenone and add it to a three-necked flask containing 80mL 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 60g 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-F1 for lithium extraction is obtained respectively.

[0206] 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-5-nitrobenzophenone)

[0207] Take 13.06g of 2-hydroxy-4-n-octyloxybenzophenone and add it to a three-necked flask containing 40mL 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 30g 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-F2 for lithium extraction is obtained respectively.

[0208] 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-5-nitrobenzophenone)

[0209] Take 13.06g of 2-hydroxy-4-n-octyloxybenzophenone and add it to a three-necked flask containing 20mL 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 15g 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-F3 for lithium extraction is obtained respectively.

[0210] 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)

[0211] 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.

[0212] 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)

[0213] 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.

[0214] The lithium-containing solution YL-2 in Example D2 was used as the original test for 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 intermediates: nitric acid ratios. The specific operation is: take 20mL of the composite liquid organic composition and 60mL of the lithium-containing solution YL-2, and react with the composite liquid organic composition in a separatory funnel for 5 minutes, then let it stand for 10 minutes to separate the layers, and release the lower aqueous solution; repeat the above process 3 times to allow all the extractants in the composite liquid organic composition to react with the metal ions to reach the extraction saturation state. Afterwards, the obtained saturated extracted organic phase is reacted with 20mL of 0.6mol / L hydrochloric acid aqueous solution 3 times, and all the stripping solutions obtained 3 times are diluted and fixed to a 1L volumetric flask, and the Li and Na concentrations therein are determined, and the concentration of the effective extractant in the composite liquid organic composition is calculated using the following formula. c 萃取剂 (mol / L)=(c Li (mol / L)+c Na (mol / L))*1L / 20mL*1000

[0215] The results are as follows:

Claims

1. A liquid organic composition for extracting lithium, comprising: 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).

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 or 2, wherein: The component a1) is 2-hydroxy-4-heptyloxyacetophenone, 2-hydroxy-4-octyloxyacetophenone, 2-hydroxy-4-nonyloxyacetophenone, 2-hydroxy-4-decyloxyacetophenone, 2-hydroxy-4-undedecyloxyacetophenone, 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.

4. The liquid organic composition for lithium extraction according to any one of claims 1 to 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, preferably 1:10 to 1:

100.

6. The liquid organic composition for lithium extraction according to any one of claims 1 to 5, wherein the synergist is one or more of tributyl phosphate, trioctyl phosphate, tri(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, triphenyl phosphine oxide, diphenyl benzyl phosphine oxide, diphenyl (2-hydroxyphenylmethyl) phosphine oxide, 2,5-dihydroxyphenyl (diphenyl) phosphine oxide, trioctyl phosphine oxide (or Cyanex921), and trialkyl phosphine oxide TRPO (or Cyanex923).

7. The liquid organic composition for extracting lithium as claimed in any one of claims 1 to 6, 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, isopentanol, n-butanol, halogenated benzene, ethylbenzene or diethylbenzene.

8. The liquid organic composition for lithium extraction according to any one of claims 1 to 7, 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; the molar ratio of the lithium extractant to the synergist is 3:1 to 0.5:

1.

9. A method for preparing a liquid organic composition for lithium extraction as claimed in any one of claims 1 to 8, comprising: 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 is optionally substituted; subjecting component a1) to a nitration reaction 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.

10. The preparation method according to claim 9, wherein the component a1) 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone is nitrated with nitric acid or a nitric acid / acetic acid mixture in an acetic acid solvent to obtain an acetic acid solution of the component a1) and the component a2).

11. The preparation method according to claim 10, wherein the nitration reaction of the component a1) comprises mixing the component a1) with glacial acetic acid or aqueous acetic acid, heating to 30-110°C, and then adding nitric acid or a mixed acid of nitric acid and acetic acid to react to obtain an acetic acid solution of a lithium extractant.

12. The preparation method according to claim 11, wherein the amount of glacial acetic acid or aqueous acetic acid is 0.5 to 5 times the weight of a1).

13. The preparation method according to any one of claims 9 to 12, further comprising, before the step of adding a diluent and a synergist to the acetic acid solution of component a1) and component a2), adding a base to the solution, and then mixing the obtained mixture with the diluent and the synergist to obtain a composition for lithium extraction.

14. The preparation method according to any one of claims 9 to 12, further comprising, after adding the diluent and the synergist to the acetic acid solution of component a1) and component a2), adding a base, and separating the layers to obtain an organic phase.

15. The preparation method according to claim 13 or 14, wherein the base is solid or aqueous NaOH solution.

16. The preparation method according to any one of claims 9 to 15, wherein the component a1) is commercially available or is prepared by etherification reaction of 2,4-dihydroxyacetophenone, 2,4-dihydroxybenzophenone or a mixture of the two with a halogenated hydrocarbon.

17. The preparation method according to claim 16, wherein the halogenated hydrocarbon is heptane chloride, octane chloride, nonane chloride, decane chloride, dodecane chloride, tridecane chloride, tetradecane chloride, pentadecane chloride, hexadecane chloride, heptane bromide, octane bromide, nonane bromide, decane bromide, dodecane bromide, tridecane bromide, tetradecane bromide, pentadecane bromide, hexadecane bromide, heptane iodide, octane iodide, nonane iodide, decane iodide, dodecane iodide, tridecane iodide, tetradecane iodide, pentadecane iodide, hexadecane iodide, or C7-C 16 Mixtures of halogenated hydrocarbons, and isomers of these halogenated hydrocarbons.

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