CN119219106A

CN119219106A - A liquid organic composition for lithium extraction and a low-cost green preparation method thereof

Info

Publication number: CN119219106A
Application number: CN202310793022.7A
Authority: CN
Inventors: 曾德文; 李东东; 曾德斌
Original assignee: Beijing Sotelak Technology Development Co ltd
Current assignee: Beijing Sotelak Technology Development Co ltd
Priority date: 2023-06-30
Filing date: 2023-06-30
Publication date: 2024-12-31
Also published as: WO2025002452A1

Abstract

本公开提供一种萃取提锂用液体有机组合物，其包含：组分a)锂提取剂、组分b)协同剂和组分c)稀释剂，其中组分a)包括组分a1)和组分a2)，组分a1)是2‑羟基‑4‑C_7‑16烷氧基‑苯乙酮或/和2‑羟基‑4‑C_7‑16烷氧基‑二苯甲酮，所述C_7‑16烷氧基是任选取代的，所述组分a2)是组分a1)的硝化产物。还提供了萃取提锂用液体有机组合物的制备方法。The present disclosure provides 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) 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 alkoxy group is optionally substituted, and component a2) is a nitration product of component a1). Also provided is a method for preparing a liquid organic composition for extracting lithium.

Description

Liquid organic composition for extracting lithium and low-cost green preparation method thereof

Technical Field

The invention relates to the technical field of lithium extraction, in particular to a preparation method of a novel liquid organic composition for extracting lithium. More particularly, the present invention relates to a liquid organic composition for lithium extraction comprising a phenolic ketone compound, a synergist and a diluent, and a method for preparing the same.

Background

Lithium is an important energy metal element. The explosion of electric vehicles using lithium batteries as core components has led to an increase in the demands of society for lithium salts year by year. Lithium salts are mainly derived from lithium-containing ores and lithium-containing brines, both of which have been developed inevitably involving stages of extraction of lithium from aqueous solutions containing alkali metals and alkaline earth metals. Therefore, the development of compounds and combinations thereof that are capable of specific selectivity for lithium is critical for efficient extraction of lithium.

Patent application 202210918111.5 discloses a novel phenol ketone lithium extractant which can realize high-selectivity separation of lithium from elements such as sodium, potassium, magnesium and the like in brine. However, how to realize low-cost green industrialized preparation of the organic phase for extracting lithium from the extractant is still to be studied. In addition, it is also necessary to optimize specific groups in the general structure thereof and combinations thereof, thereby obtaining a better lithium extraction effect. Preferred lithium extractants are disclosed in the examples of patent application 202210918111.5 as having the structure 2-hydroxy-4-alkoxy-5-nitroacetophenone or/and 2-hydroxy-4-alkoxy-5-nitrobenzophenone. Wherein, 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone intermediate is used as raw material to prepare the lithium extractant with excellent performance through nitration reaction. The acetic acid solvent used in the reaction is removed by adopting a reduced pressure distillation method, and the solid extractant is obtained. This causes problems in that 1) the solid extractant is difficult to separate from acetic acid thoroughly, 2) the solid extractant containing volatile acetic acid is not well handled and is difficult to be taken out from the reactor, and 3) the aqueous acetic acid waste liquid distilled off is difficult to be reused. The preparation process of the lithium extractant has the advantages of high consumption of acetic acid solvent, high production cost and difficult treatment of a large amount of byproduct acetic acid aqueous solution containing impurities.

Therefore, the novel phenolic ketone lithium extractant and the preparation method of the liquid organic phase for lithium extraction are further improved, so that the manufacturing cost and the environmental load of the extractant are reduced, and the phenolic ketone lithium extractant has great significance for industrial application.

Disclosure of Invention

In order to solve the problems, the inventor provides a concept and a preparation process for directly preparing a liquid organic composition for extracting lithium by skipping the synthesis of pure substances of a novel phenolic ketone lithium extractant. The method disclosed by the invention avoids the complicated process of 1) firstly preparing the pure substance of the phenolic ketone lithium extractant, then mixing the pure substance with the trialkylphosphine oxide co-extractant and the diluent to prepare the liquid organic composition for extracting lithium, and 2) solving the problem that the acetic acid solvent is difficult to recycle in the preparation process of the pure substance of the phenolic ketone lithium extractant.

The method for preparing the liquid organic composition for extracting lithium provided by the invention comprises the following steps:

Providing component a 1), component a 1) being 2-hydroxy-4-C _7-16 alkoxy-acetophenone or/and 2-hydroxy-4-C _7-16 alkoxy-benzophenone, said C _7-16 alkoxy being optionally substituted;

Subjecting component a 1) to nitration in acetic acid solvent to obtain a mixture of component a 1) and component a 2), and

And adding sodium hydroxide, a synergist and a diluent into the mixture of the component a 1) and the component a 2) to separate the extractant from the solvent for nitration, and finally obtaining the liquid organic composition for extracting lithium.

By the method provided by the invention, a liquid organic composition for extracting lithium is obtained, which comprises a component a) a lithium extracting agent, a component b) a synergistic agent and a component C) a diluent, wherein the component a) comprises a component a 1) and a component a 2), the component a 1) 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, and the component a 2) is a nitration product of the component a 1).

The process omits the purification process of 2-hydroxy-4-alkoxy-5-nitroacetophenone or/and 2-hydroxy-4-alkoxy-5-nitrobenzophenone solid matters, greatly reduces the energy consumption required by distillation of acetic acid solvent, effectively avoids the potential explosion hazard and other problems in the manufacturing process of the solid matters containing nitro, and simultaneously directly obtains the liquid organic mixture for extracting lithium. The preparation safety and the use effectiveness of the extractant are ensured while the complexity and the production cost of the production flow are reduced.

The preparation process of the liquid organic mixture for extracting lithium has almost no emission of waste organic solvent and waste water, and the only byproduct is sodium acetate solution. The obtained byproduct sodium acetate solution can be prepared into industrial products with commercial value through concentration or/and crystallization.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention will be clearly and completely described below. The following examples are illustrative only and are not to be construed as limiting the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention shall fall within the protection scope of the present invention.

The present invention may be embodied in other specific forms without departing from its essential attributes. It is to be understood that any and all embodiments of the invention may be combined with any other embodiment or features of multiple other embodiments to yield yet further embodiments without conflict. The invention includes additional embodiments resulting from such combinations.

All publications and patents mentioned in this disclosure are incorporated herein by reference in their entirety. If a use or term used in any of the publications and patents incorporated by reference conflicts with the use or term used in the present disclosure, the use or term of the present disclosure controls.

The section headings used herein are for purposes of organizing articles only and should not be construed as limiting the subject matter.

Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning in the art to which the claimed subject matter belongs. In case there are multiple definitions for a term, the definitions herein control.

Except in the operating examples, or where otherwise indicated, all numbers expressing quantities of quantitative properties such as dosages set forth in the specification and claims are to be understood as being modified in all instances by the term "about". It should also be understood that any numerical range recited herein is intended to include all sub-ranges within that range and any combination of the individual endpoints of that range or sub-range.

The use of the terms "comprising," "including," or "containing," and the like, in this disclosure, are intended to cover an element listed after that term and its equivalents, but do not exclude the presence of other elements. The terms "comprising" or "including" as used herein, can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of, or" consisting of. Thus, a liquid organic composition for extraction of lithium comprising component a) a lithium extractant, component b) a synergist and component c) a diluent means that the liquid organic composition for extraction of lithium may or may not comprise other components than components a), b), c). For example, the liquid organic composition for extraction of lithium may additionally contain an antioxidant such as ascorbic acid.

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

In another embodiment, the liquid organic composition for extraction of lithium consists essentially of component a) the lithium extractant, component b) the synergist, and component c) the diluent, the component a) the lithium extractant, the component b) the synergist, and the component c) the diluent comprising 97 wt%, 98wt%, 99 wt% or more than 99.5 wt% of the liquid organic composition for extraction of lithium.

In another embodiment, the liquid organic composition for extraction of lithium comprises 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 extraction of lithium is less than 97 wt%. The liquid organic composition for extraction of lithium may comprise other components as long as the other components do not negatively affect the performance of the organic composition for extraction of lithium.

The term "optional" in this disclosure means that the described situation may or may not occur. For example, the composition including an optional diluent means that the composition may or may not include a diluent. Thus, C _7-16 alkoxy is optionally substituted and includes unsubstituted C _7-16 alkoxy and substituted C _7-16 alkoxy, for example, the substituents can be C1-3 alkyl, C1-3 alkoxy, C5-6 cycloalkyl, halogen, nitro, benzyloxy, hydroxy, and the like.

The term "extractant" in this disclosure refers to a complex chemical reaction with an extracted metal (e.g., lithium, sodium, potassium, etc.) to produce an extract that is extracted into an organic phase, and a chemical reaction that causes the extracted metal to be extracted from the organic phase to an aqueous phase, thereby effecting purification or enrichment of the metal. The extractant may be used interchangeably with extractant in this disclosure. For example, lithium extractants or lithium extractants are used to achieve purification or enrichment of lithium by extraction.

The term "alkyl" in this disclosure refers to branched and straight chain monovalent hydrocarbon radicals 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.

The term "alkoxy" in this disclosure means that an alkyl group as defined above is attached to the parent structure through oxygen, and thus also includes straight chain alkoxy groups and branched alkoxy groups. Typical alkyl groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, hexoxy, heptoxy, isoheptoxy, octoxy, 2-ethylhexoxy, nonoxy, isononyl, decyloxy, isodecyloxy, dodecyloxy, hexadecyloxy, and the like. Thus, "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 alkoxy.

The term "cycloalkyl" in this disclosure 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 C ₃-C₆ cycloalkyl. Illustrative examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. In some preferred embodiments, cycloalkyl is cyclopentyl or cyclohexyl.

The term "nitro" refers in the present disclosure to the-NO ₂ group.

The term "benzyloxy" in this disclosure refers to the monovalent group PhCH ₂ O-that remains after benzyl alcohol loses the hydrogen atom on the hydroxyl group.

The term "halo" or "halogen" refers in the present disclosure to fluorine, chlorine, bromine or iodine. In some embodiments, "halo" or "halogen" is chloro or bromo. In other embodiments, "halo" or "halogen" is fluoro. The term "halogenated hydrocarbon" includes both straight chain halogenated hydrocarbons and branched chain halogenated hydrocarbons in this disclosure.

Synergists in the present disclosure refer to agents that are capable of increasing partition rates after their addition to an extractant. Synergists are used interchangeably with synergists in the present disclosure.

Diluents in this disclosure refer to agents that improve the physical properties of the extracted organic phase, such as organic solvents as the extractant, increase the solubility of the extractant in the organic phase, decrease the viscosity of the extractant, increase its flowability, and change the density of the organic phase.

In the liquid organic composition for extraction of lithium according to the present application, component a) the lithium extractant comprises component a 1) and component a 2), wherein component a) comprises component a 1) and component a 2), component a 1) is 2-hydroxy-4-C _7-16 alkoxy-acetophenone or/and 2-hydroxy-4-C _7-16 alkoxy-benzophenone, said C _7-16 alkoxy being optionally substituted, and said component a 2) is the nitration product of component a 1).

In a preferred embodiment, the component a 2) is 2-hydroxy-4-C _7-16 -alkoxy-5-nitroacetophenone or/and 2-hydroxy-4-C _7-16 -alkoxy-5-nitrobenzophenone.

For example, the component a 1) is one or a mixture of several of 2-hydroxy-4-heptyloxy acetophenone, 2-hydroxy-4-octyloxy acetophenone, 2-hydroxy-4-nonyloxy acetophenone, 2-hydroxy-4-decyloxy acetophenone, 2-hydroxy-4-undecyloxy acetophenone, 2-hydroxy-4-dodecyloxy acetophenone, 2-hydroxy-4-tridecyloxy acetophenone, 2-hydroxy-4-tetradecyloxy acetophenone, 2-hydroxy-4-pentadecyloxy acetophenone, 2-hydroxy-4-hexadecyloxy acetophenone, 2-hydroxy-4-heptyloxy benzophenone, 2-hydroxy-4-octyloxy benzophenone, 2-hydroxy-4-nonyloxy benzophenone, 2-hydroxy-4-decyloxy benzophenone, 2-hydroxy-4-dodecyloxy benzophenone, 2-hydroxy-4-tridecyloxy benzophenone, 2-hydroxy-4-tetradecyloxy benzophenone, 2-hydroxy-4-pentadecyloxy benzophenone, 2-hydroxy-4-hexadecyloxy benzophenone.

For example, the component a 2) 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-4-5-decyloxy-5-nitrobenzophenone, 2-hydroxy-4-5-n-decyloxy-5-nitroacetophenone, 5-hydroxy-5-nitrobenzophenone One or a mixture of any more of 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.

In the liquid organic composition for extraction of lithium according to the present application, the ratio of component a 2) to component a 1) may be arbitrary, and it is preferable that the molar ratio of the component a 1) to the component a 2) is 1:1 to 1:1000, more preferably 1:2 to 1:200, still more preferably 1:10 to 1:100.

Component a 1) and component a 2) are both lithium extractants, and typically component a 2) has a better lithium extraction capacity than component a 1). Therefore, the content of component a 2) is preferably higher than component a 1) in the liquid organic composition for extraction of lithium according to the present application.

In the liquid organic composition for extraction of lithium according to the present application, component a 2) is the nitration reaction product of component a 1). When the nitration of x% of component a 1) occurs, the molar ratio of component a 1) to component a 2) is (100-x): x. For example, when 50% of component a 1) is subject to nitration, the molar ratio of component a 1) to component a 2) is 1:1. For example, when 90% of component a 1) is nitrified, the molar ratio of component a 1) to component a 2) is 1:9. For example, when 99% of component a 1) is nitrified, the molar ratio of component a 1) to component a 2) is 1:99. The skilled person can control the reaction degree of the nitration reaction by controlling the reaction conditions such as the addition amount of nitric acid. If an excess of nitric acid is added to bring about the nitration of as much of component a 1) as possible, the cost of the work-up will increase.

In the liquid organic composition for extraction and extraction of lithium of the present application, the synergistic agent is, for example, one or more of tributyl phosphate, trioctyl phosphate, tris (2-ethylhexyl) phosphate, trihexyl phosphate, tripentyl phosphate, dibutyl butyl phosphate, di-sec-octyl methyl phosphate, diisooctyl isopropyl phosphate, diisopentyl methyl phosphate, triphenylphosphine oxide, diphenyl benzyl phosphine oxide, diphenyl (2-hydroxyphenylmethyl) phosphine oxide, 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide, trioctylphosphine oxide (or Cyanex 921), trialkylphosphine oxide TRPO (or Cyanex 923).

In the liquid organic composition for extraction and extraction of lithium of the present application, the diluent is, for example, one or more of technical white oil, kerosene, sulfonated kerosene, D-series solvent oil, n-heptane, cyclohexane, octane, dodecane, petroleum ether, xylene, anisole, methyl isobutyl ketone, toluene, octanone, 5-nonanone, isoamyl alcohol, n-butanol, halobenzene, ethylbenzene or diethylbenzene.

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

The present disclosure also provides a method of extracting lithium, comprising:

The liquid organic composition for extracting lithium is contacted with an aqueous solution containing lithium ions, and lithium ions in the aqueous solution are made to enter an organic layer by liquid-liquid delamination, and the organic layer is collected.

In one embodiment of extracting lithium, the pH of the aqueous solution containing lithium ions is 7 to 13 before contacting with the liquid organic composition for extracting lithium.

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

In one embodiment of the extraction of lithium, the aqueous solution containing lithium ions is a natural brine having an alkalinity, which 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.

For example, the alkali metal or ammonium hydroxide 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, and the borate is one or more of sodium metaborate, potassium metaborate, ammonium metaborate, sodium tetraborate, potassium tetraborate and ammonium tetraborate.

In one embodiment of the lithium extraction, the pH value of the aqueous solution containing lithium ions is 5-8 before the aqueous solution is contacted with the liquid organic composition for lithium extraction, and the liquid organic composition for lithium extraction is saponified with one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate aqueous solutions before the aqueous solution containing lithium ions is contacted with the aqueous solution containing lithium ions.

In one embodiment of the 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 0.01mol/L to 2.0mol/L.

In one embodiment of extracting lithium, the method may further comprise the step of contacting a stripping agent with the organic layer to obtain a lithium-containing stripping agent.

For example, the stripping agent is an aqueous acid solution.

In one embodiment of extracting lithium, the stripping agent is one or more aqueous solutions of carbonic acid, sulfuric acid, sulfurous acid, hydrochloric acid, nitric acid and phosphoric acid, and/or the concentration of hydrogen ions in the stripping agent is 0.05 mol/L-6 mol/L, and the volume ratio of the stripping agent to the organic layer is 1:1-1:50.

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

In one embodiment of extracting lithium, the time for contacting the liquid organic composition for extracting lithium with the aqueous solution containing lithium ions is 3 to 30 minutes.

In one embodiment of extracting lithium, the time for contacting the stripping agent with the organic layer is 3-30 minutes.

The above-described contacting operation may be performed in a mixer-settler, a centrifugal extractor or an extraction column.

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

In one embodiment of extracting lithium, after the stripping agent is contacted with the organic layer, a concentrated acid is supplemented into the stripping agent containing lithium and is used as the stripping agent to be contacted with the organic layer again, wherein 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.

In one embodiment of the extraction of lithium, the method further comprises concentrating the lithium by evaporating water from the lithium-containing extractant, and/or precipitating lithium carbonate from the lithium-containing extractant.

The present disclosure provides a new method for preparing a liquid organic composition for extracting lithium containing 2-hydroxy-4-alkoxy-5-nitroacetophenone or/and 2-hydroxy-4-alkoxy-5-nitrobenzophenone.

The preparation method comprises the following steps:

Subjecting component a 1) to a nitration reaction to give a mixture of component a 1) and component a 2), and

A diluent and a synergist are added to the mixture of components a 1) and a 2).

In this preparation process, component a 2) results from the nitration of component a 1), the mixture of component a 1) and component a 2) being essentially a mixture of starting materials and reaction products.

In one embodiment, component a 1) 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone is nitrated in an acetic acid solvent with nitric acid or a nitric acid/acetic acid mixture to give an acetic acid solution of component a 1) and component a 2).

For example, the nitration reaction of the component a 1) may include mixing the component a 1) with glacial acetic acid or aqueous acetic acid, heating to 30 to 110 ℃, preferably to 50 to 80 ℃, and then adding nitric acid or a mixed acid of nitric acid and acetic acid to react to obtain an acetic acid solution of the lithium extractant. At 50-80 ℃, a substantial part of component a 1) melts to form a liquid phase, which will contribute to the progress of the nitration reaction. In a preferred embodiment, the amount of glacial acetic acid or aqueous acetic acid used in the step of mixing the component a 1) with glacial acetic acid or aqueous acetic acid is 0.5 to 5 times the weight of 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone. In a more preferred embodiment, the glacial acetic acid or aqueous acetic acid in the step of mixing component a 1) with glacial acetic acid or aqueous acetic acid is used in an amount of 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, 2.0 times by weight of 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone.

In a preferred embodiment, glacial acetic acid or aqueous acetic acid is used in an amount of 1 to 2.0 times the weight of 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone in the nitration of component a 1) 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone with nitric acid or nitric acid/acetic acid mixtures in acetic acid solvent. The water content in the aqueous acetic acid accounts for 0.1-10% of the acetic acid content.

In the method for preparing the liquid organic composition for extracting lithium, the method may further comprise a step of adding a base to remove an acid. For example, the base is NaOH solid or aqueous solution. The base may be added to the mixture of component a 1) and component a 2), or to the diluent, or the base may be added after the diluent and the synergist are added to the mixture of component a 1) and component a 2).

In one embodiment, a base is added to the mixture of component a 1) and component a 2) prior to the step of adding a diluent and a synergist to the mixture of component a 1) and component a 2), and the organic phase resulting from the delamination is then mixed with the diluent and the synergist to obtain the useful composition for extracting lithium.

In another preferred embodiment, the addition of a base after the addition of the diluent and the synergist to the mixture of components a 1) and a 2) may facilitate the transfer of the extractant from the aqueous phase to the organic phase.

And (3) carrying out neutralization reaction on alkali (such as sodium hydroxide) and acetic acid to generate sodium acetate, standing for layering, and discharging a bottom sodium acetate solution to obtain an upper-layer deacetylated organic phase, namely the liquid organic composition for extracting lithium.

Component a 1) may be commercially available or self-made. For example, providing component a 1) may comprise the step of preparing component a 1) from the ethereal reaction of 2,4 dihydroxyacetophenone, 2,4 dihydroxybenzophenone, or a mixture of both, with a halogenated hydrocarbon. The halogenated hydrocarbon is, for example, chloroheptane, chlorooctane, chlorononane, chlorodecane, chlorododecane, chlorotridecane, chlorotetradecane, chloropentadecane, chlorohexadecane, bromoheptane, bromon-octane, bromoisooctane, bromononane, bromodecane, bromododecane, bromotridecane, bromotetradecane, bromopentadecane, bromohexadecane, iodoheptane, iodon-octane, iodoisooctane, iodononane, iododecane, iodododecane, iodotridecane, iodotetradecane, iodopentadecane, iodohexadecane, or a C7-C16 halogenated hydrocarbon mixture.

The process omits the preparation process of 2-hydroxy-4-alkoxy-5-nitroacetophenone or/and 2-hydroxy-4-alkoxy-5-nitrobenzophenone solid matters, greatly reduces the energy consumption required by distillation of acetic acid solvent, effectively avoids the explosive danger problem in the manufacturing process of the solid matters containing nitro, and simultaneously directly obtains the liquid organic composition for extracting lithium. The production process complexity and the production cost are reduced, and the safety of the preparation of the extractant is ensured.

The liquid organic composition preparation process for extracting lithium has almost no emission of waste organic solvent and waste water, and the byproduct is sodium acetate solution. The obtained byproduct sodium acetate solution can be prepared into an industrial product with economic value through concentration or/and crystallization.

In one embodiment, a method of preparing a liquid organic composition for lithium extraction includes:

(1) Nitrifying 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone by using nitric acid or nitric acid/acetic acid mixed acid in an acetic acid solvent to obtain 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 step (1) with a synergist and solvent oil to obtain an organic mixture B, and

(3) And (3) adding sodium hydroxide solution into the organic mixture B obtained in the step (2), neutralizing the sodium hydroxide with acetic acid in the step B to generate sodium acetate, standing for layering, and discharging the bottom sodium acetate solution to obtain an upper-layer deacetylated organic phase C which is a liquid organic mixture for extracting lithium.

Preferably, the alkoxy in the 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone is C7-C16.

Preferably, in the step (1), the 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone is 2-hydroxy-4-heptyloxy-acetophenone, 2-hydroxy-4-octyloxy-acetophenone, 2-hydroxy-4-nonyloxy-acetophenone, 2-hydroxy-4-decyloxy-acetophenone, 2-hydroxy-4-undecyloxy-acetophenone, 2-hydroxy-4-dodecyloxy-acetophenone, 2-hydroxy-4-tridecyloxy-acetophenone, 2-hydroxy-4-tetradecyloxy-acetophenone, 2-hydroxy-4-pentadecyloxy-acetophenone, 2-hydroxy-4-hexadecyloxy-acetophenone, 2-hydroxy-4-heptyloxy-benzophenone, 2-hydroxy-4-octyloxy-benzophenone, 2-hydroxy-4-decyloxy-benzophenone, 2-hydroxy-4-undecyloxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-tridecyloxy-benzophenone, 2-hydroxy-4-tetradecyloxy-benzophenone, 2-hydroxy-4-pentadecyloxy-benzophenone, one or a mixture of any of 2-hydroxy-4-hexadecyloxy benzophenone.

Preferably, in the step (1), the 2-hydroxy-4-alkoxy-5-nitroacetophenone or/and the 2-hydroxy-4-alkoxy-5-nitroacetophenone 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-nitroacetophenone, 2-hydroxy-4-5-nitroacetophenone, 2-hydroxy-4-decyloxy-5-nitroacetophenone, 2-hydroxy-4-5-nitroacetophenone and/or the 2-hydroxy-4-5-nitroacetophenone is/, one or a mixture of any of 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 and 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone.

Preferably, in step (1), the acetic acid solvent has a water content of less than 20%. The examples of the present disclosure find that when glacial acetic acid and acetic acid having a relatively low water content are used as solvents, the resulting liquid organic composition for extracting lithium has excellent lithium extraction properties. When acetic acid having a relatively high water content is used as a solvent or pure water, the lithium extraction capacity of the liquid organic composition for extracting lithium is greatly reduced.

Preferably, in the step (1), in order to reduce the consumption of the acetic acid solvent, under the condition of heating, the 2-hydroxy-4-alkoxy-acetophenone or/and the 2-hydroxy-4-alkoxy-benzophenone are dissolved in a small amount of acetic acid solvent, and the consumption of acetic acid is 0.5-5 times of the weight of the 2-hydroxy-4-alkoxy-acetophenone or/and the 2-hydroxy-4-alkoxy-benzophenone. Then, concentrated nitric acid having a concentration of 68wt% was mixed with acetic acid to prepare an acetic acid solution of dilute nitric acid. Finally, the resulting acetic acid solution of dilute nitric acid is added to the hot acetic acid solution of 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone. Preferably, the heating temperature is 40-70 ℃.

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

Preferably, in the step (1), the temperature of the nitration reaction is 40-70 ℃.

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

Preferably, in the step (1), when the intermediate raw materials cannot be directly purchased, the 2-hydroxy-4-alkoxy-acetophenone or/and the 2-hydroxy-4-alkoxy-benzophenone are prepared by using 2, 4-dihydroxyacetophenone or/and 2, 4-dihydroxybenzophenone and halogenated hydrocarbon as raw materials through Williamson ether formation reaction.

Preferably, the synergist in the step (2) is one or more of tributyl phosphate, trioctyl phosphate, tributyl phosphine oxide, trioctyl phosphine oxide (or Cyanex 921), and trialkyl phosphine oxide TRPO (or Cyanex 923).

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

Preferably, the solvent oil in the step (2) is one or a mixture of several of technical white oil, kerosene, sulfonated kerosene, D-series solvent oil, toluene, xylene, ethylbenzene or diethylbenzene.

Preferably, in the step (2), the solvent oil is 2-20 liters/mol of lithium extractant.

Preferably, the organic mixture B in the step (2) is cooled to 0-30 ℃ before the step (3) is carried out.

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

Preferably, the sodium hydroxide solution in step (3) is added stepwise to the organic mixture B.

Preferably, the mixing of the sodium hydroxide solution with the organic mixture B in step (3) is carried out in a mixer equipped with cooling means.

Examples

The following examples are provided to further illustrate the invention. It should be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.

Unless defined otherwise, technical or scientific terms used in the following examples should be given the ordinary meaning as understood by one of ordinary skill in the art to which the present invention pertains.

Example A group preparation of 2-hydroxy-4-alkoxy-5-nitrobenzophenone/acetophenone acetic acid solutions of different structures

Example A1 preparation of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone acetic acid solution 12.6g of 2-hydroxy-4-heptyloxy-benzophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 80℃and 3mL of 68wt% nitric acid was added to react for 16 hours, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone.

Example A2 preparation of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone acetic acid solution 13.06g of 2-hydroxy-4-n-octoxybenzophenone was taken and added to a three-necked flask containing 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 2.75mL of 68wt% nitric acid was added thereto, after 16 hours of reaction, it was cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone.

Example A3 preparation of 2-hydroxy-4-isooctyloxy-5-nitrobenzophenone acetic acid solution 13.06g of 2-hydroxy-4-isooctyloxy-benzophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 80℃and 3mL of 68wt% nitric acid was added to react for 16 hours, followed by cooling to room temperature to obtain 2-hydroxy-4-isooctyloxy-5-nitrobenzophenone acetic acid solution.

Example A4 preparation of 2-hydroxy-4-nonyloxy-5-nitrobenzophenone acetic acid solution 13.6g of 2-hydroxy-4-nonyloxy-benzophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, and then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added thereto, and after 16 hours of reaction, it was cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-nonyloxy-5-nitrobenzophenone.

Example A5 preparation of 2-hydroxy-4-decyloxy-5-nitrobenzophenone acetic acid solution 14.2g of 2-hydroxy-4-decyloxy-benzophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, and then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added thereto, and after 16 hours of reaction, it was cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-decyloxy-5-nitrobenzophenone.

Example A6 preparation of 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone acetic acid solution 15.3g of 2-hydroxy-4-dodecyloxy-benzophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 16 hours, and then cooled to room temperature to obtain 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone acetic acid solution.

Example A7 preparation of 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone acetic acid solution 15.9g of 2-hydroxy-4-tridecyloxy-benzophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 12 hours, then the temperature was raised to 70℃to react for 4 hours again, and then cooled to room temperature to obtain acetic acid solution of 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone.

Example A8 preparation of 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone acetic acid solution 16.42g of 2-hydroxy-4-tetradecyloxy-benzophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to be completely dissolved, then the flask was placed in an oil bath pot at 50℃and 3mL of 68% by weight nitric acid was added thereto, after reaction for 12 hours, the temperature was raised to 70℃and reaction was further carried out for 4 hours, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone.

Example A9 preparation of 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone acetic acid solution 17.15g of 2-hydroxy-4-pentadecyloxy-benzophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68% by weight nitric acid was added to react for 12 hours, then the temperature was raised to 70℃to react for 4 hours again, and then cooled to room temperature to obtain acetic acid solution of 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone.

Example A10 preparation of 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone acetic acid solution 17.55g of 2-hydroxy-4-hexadecyloxy-benzophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68% by weight nitric acid was added to react for 12 hours, then the temperature was raised to 80℃to react for 4 hours again, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone.

Example A11 preparation of 2-hydroxy-4-heptyloxy-5-nitroacetophenone acetic acid solution 10.1g of 2-hydroxy-4-heptyloxy acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, and then the flask was placed in an oil bath pot at 70℃and 3mL of 68wt% nitric acid was added to react for 16 hours, followed by cooling to room temperature to obtain an acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitroacetophenone.

Example A12 preparation of 2-hydroxy-4-n-octyloxy-5-nitroacetophenone acetic acid solution 10.6g of 2-hydroxy-4-n-octyloxy acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 70℃and 2.75mL of 68wt% nitric acid was added to react for 16 hours, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitroacetophenone.

Example A13 preparation of 2-hydroxy-4-isooctyloxy-5-nitroacetophenone acetic acid solution 10.6g of 2-hydroxy-4-isooctyloxy acetophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 70℃and 3mL of 68wt% nitric acid was added to react for 16 hours, followed by cooling to room temperature to give an acetic acid solution of 2-hydroxy-4-isooctyloxy-5-nitroacetophenone.

Example A14 preparation of 2-hydroxy-4-nonyloxy-5-nitroacetophenone acetic acid solution 11.1g of 2-hydroxy-4-nonyloxy acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, and then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 16 hours, followed by cooling to room temperature to obtain an acetic acid solution of 2-hydroxy-4-nonyloxy-5-nitroacetophenone.

Example A15 preparation of 2-hydroxy-4-decyloxy-5-nitroacetophenone acetic acid solution 11.7g of 2-hydroxy-4-decyloxy acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, and then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 16 hours, followed by cooling to room temperature to obtain an acetic acid solution of 2-hydroxy-4-decyloxy-5-nitroacetophenone.

Example A16 preparation of 2-hydroxy-4-dodecyloxy-5-nitroacetophenone acetic acid solution 12.8g of 2-hydroxy-4-dodecyloxy-acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 16 hours, and then cooled to room temperature to obtain 2-hydroxy-4-dodecyloxy-5-nitroacetophenone acetic acid solution.

Example A17 preparation of 2-hydroxy-4-tridecyloxy-5-nitroacetophenone acetic acid solution 13.4g of 2-hydroxy-4-tridecyloxy acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 12 hours, after which the temperature was raised to 80℃for further reaction for 4 hours, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tridecyloxy-5-nitroacetophenone.

Example A18 preparation of 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone acetic acid solution 13.9g of 2-hydroxy-4-tetradecyloxy acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 12 hours, then the temperature was raised to 80℃to react for 4 hours again, and then cooled to room temperature to obtain acetic acid solution of 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone.

Example A19 preparation of 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone acetic acid solution 14.7g of 2-hydroxy-4-pentadecyloxy acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 12 hours, then the temperature was raised to 80℃to react for 4 hours again, and then cooled to room temperature to obtain acetic acid solution of 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone.

Example A20 preparation of 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone acetic acid solution 15.1g of 2-hydroxy-4-hexadecyloxy acetophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath pot at 50℃and 3mL of 68wt% nitric acid was added to react for 12 hours, then the temperature was raised to 80℃to react for 4 hours again, and then cooled to room temperature to obtain acetic acid solution of 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone.

Example B group preparation of Compound lithium-extracted liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone/acetophenone example B1 preparation of Compound lithium-extracted liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone/acetophenone (synergist: trialkylphosphine oxide; solvent: D80 solvent oil)

80ML of the 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 to A5 were taken, respectively. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. And mixing all the prepared D80 solvent oil containing trialkylphosphine oxide with an acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, adding 60g of anhydrous NaOH, fully mixing, standing for layering, discharging a lower water phase, and obtaining an upper oil phase, and washing the oil phase with water for multiple times to obtain the extractant for lithium extraction. The compound liquid organic compositions STLK-Z7AN, STLK-Z8AN, STLK-Y8AN, STLK-Z9AN and STLK-Z10AN for extracting lithium are respectively obtained.

Example B2 preparation of a liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone/acetophenone (synergist: tri-n-octylphosphine oxide; solvent: 15# technical white oil)

80ML 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 to A10 were taken, respectively. 400mL of 15# technical white oil was added with 15.5g of tri-n-octylphosphine oxide and stirred until a homogeneous solution formed. Mixing all the prepared D80 solvent oil containing trialkylphosphine oxide with acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, adding 280g of aqueous solution of NaOH with concentration of 20wt%, fully mixing, standing for layering, discharging lower aqueous phase, obtaining upper oil phase, and washing the oil phase with water for multiple times to obtain the extractant for extracting lithium. The compound liquid organic compositions STLK-Z12AN, STLK-Z13AN, STLK-Y14AN, STLK-Z15AN and STLK-Z16AN for extracting lithium are respectively obtained.

Example B3 preparation of a liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone/acetophenone (synergist: tri-n-octylphosphine oxide; solvent: diethylbenzene)

80ML of the 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 to A15 were taken, respectively. 400mL of diethylbenzene was added to 15.5g of tri-n-octylphosphine oxide, and the mixture was stirred until a homogeneous solution was formed. Then, the whole prepared D80 solvent oil containing trialkylphosphine oxide is mixed with acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, 186.5g of 30wt% NaOH aqueous solution is added, after full mixing, standing and layering are carried out, a lower aqueous phase is discharged, an upper oil phase is obtained, and the oil phase is washed with water for multiple times to be used as an extracting agent for lithium extraction. The compound liquid organic compositions STLK-Z7BN, STLK-Z8BN, STLK-Y8BN, STLK-Z9BN and STLK-Z10BN for extracting lithium are respectively obtained.

Example B4 preparation of a liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone/acetophenone (synergist: tri-n-octylphosphine oxide; solvent: kerosene)

80ML of the acetic acid solutions of 2-hydroxy-4-dodecoxy-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 to A10 were taken, respectively. Another 400mL of kerosene was added with 15.5g of tri-n-octylphosphine oxide and stirred until a homogeneous solution was formed. And mixing all the prepared D80 solvent oil containing trialkylphosphine oxide with acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, adding 140g of 40wt% NaOH aqueous solution, fully mixing, standing for layering, discharging a lower aqueous phase, and obtaining an upper oil phase, and washing the oil phase with water for multiple times to obtain the extracting agent for lithium extraction. The compound liquid organic compositions STLK-Z12BN, STLK-Z13BN, STLK-Y14BN, STLK-Z15BN and STLK-Z16BN for extracting lithium are respectively obtained.

Example group C preparation of intermediate raw materials for nitration reactions of 2-hydroxy-4-alkoxy-5-nitrobenzophenones of different Structure

EXAMPLE C1 preparation of 2-hydroxy-4-heptyloxy-benzophenone intermediate

31.37G of 2, 4-dihydroxyacetophenone (raw material C) was charged into a three-necked flask containing 100mL of acetone and 20.23g of anhydrous potassium carbonate, the flask was placed in an oil bath at 50℃with 25g of bromoheptane (raw material D) being added dropwise while stirring, then the temperature of the oil bath was raised to 60℃and the condenser was opened to allow water to enter, so that the system was refluxed for 14 hours. After the reaction, the acetone solvent was distilled off, cooled to room temperature, and a 1M hydrochloric acid solution was added dropwise to the flask until ph=4 to 6, and after separating the aqueous phase, 47g of oily 2-hydroxy-4-heptanoxybenzophenone (raw material intermediate a) was obtained.

Example C2 preparation of 2-hydroxy-4-n-octoxybenzophenone intermediate 27.6g of 2, 4-dihydroxyacetophenone (raw material C) was charged into a three-necked flask equipped with 50mL of N, N-Dimethylformamide (DMF) and 17.8g of anhydrous potassium carbonate, the flask was placed in an oil bath pot at 50℃and 25g of n-octyl bromide (raw material D) was added dropwise with stirring, and then the temperature of the oil bath was raised to 70℃to allow the system to react for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added to the flask, and a 6M hydrochloric acid solution was added dropwise to ph=4 to 6, and after separating the aqueous phase, a solid of 2-hydroxy-4-n-octoxybenzophenone (raw material intermediate a) was obtained, and 36g of a product was obtained after recrystallization from 20mL of 95 ethanol.

Example C3 preparation of 2-hydroxy-4-isooctoxybenzophenone intermediate 27.6g of 2, 4-dihydroxyacetophenone (raw material C) was charged into a three-necked flask containing 50mL of N, N-Dimethylformamide (DMF) and 17.8g of anhydrous potassium carbonate, the flask was placed in an oil bath pot at 50℃and 25g of bromoisooctane (raw material D) was added dropwise with stirring, and then the temperature of the oil bath was raised to 70℃to allow the system to react for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added to the flask, and a 6M hydrochloric acid solution was added dropwise to the flask to ph=4 to 6, and after separating the aqueous phase, 30g of an oily 2-hydroxy-4-isooctoxybenzophenone (raw material intermediate a) product was obtained.

EXAMPLE C4 preparation of 2-hydroxy-4-nonoxybenzophenone intermediate

25.7G of 2, 4-dihydroxyacetophenone (raw material C) was charged into a three-necked flask containing 50mL of N, N-Dimethylformamide (DMF) and 16.6g of anhydrous potassium carbonate, and the flask was placed in an oil bath at 70℃and 25g of bromononane (raw material D) was added dropwise with stirring to react the system for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added to the flask, and a 6M hydrochloric acid solution was added dropwise to the flask to ph=4 to 6, and after separating the aqueous phase, a solid of 2-hydroxy-4-nonoxybenzophenone (raw material intermediate a) was obtained, and after recrystallization with 20mL of 95 ethanol, 29g of the product was obtained.

EXAMPLE C5 preparation of 2-hydroxy-4-decyloxy benzophenone intermediate

25.4G of 2, 4-dihydroxyacetophenone (raw material C) was charged into a three-necked flask containing 50mL of N, N-Dimethylformamide (DMF) and 16.4g of anhydrous potassium carbonate, 0.5g of potassium iodide was further added, and the flask was placed in an oil bath at 70℃and 25g of bromodecane (raw material D) was added dropwise with stirring to react the system for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added to the flask, and a 6M hydrochloric acid solution was added dropwise to the flask until ph=4 to 6, and after separating the aqueous phase, 2-hydroxy-4-decyloxy benzophenone (raw material intermediate a) was obtained as a solid, which was recrystallized from 20mL of 95 ethanol to obtain 31g of a product.

EXAMPLE C6 preparation of 2-hydroxy-4-dodecyloxybenzophenone intermediate 22.5g of 2, 4-dihydroxyacetophenone (raw material C) was charged into 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℃and 25g of bromododecane (raw material D) was added dropwise with stirring, and the system was allowed to react for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added to the flask, and a 6M hydrochloric acid solution was added dropwise to the flask until ph=4 to 6, and after separating the aqueous phase, a solid of 2-hydroxy-4-dodecyloxybenzophenone (raw material intermediate a) was obtained, and 30g of the product was obtained after recrystallization from 20mL of 95 ethanol.

EXAMPLE C7 preparation of 2-hydroxy-4-tridecyloxybenzophenone intermediate

21.4G of 2, 4-dihydroxyacetophenone (raw material C) was charged into a three-necked flask containing 50mL of N, N-Dimethylformamide (DMF) and 13.8g of anhydrous potassium carbonate, and the flask was placed in an oil bath at 70℃and 25g of bromotridecane (raw material D) was added dropwise with stirring to react the system for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added to the flask, and a 6M hydrochloric acid solution was added dropwise to the flask to ph=4 to 6, and after separating the aqueous phase, a solid of 2-hydroxy-4-tridecyloxybenzophenone (raw material intermediate a) was obtained, and after recrystallization with 20mL of 95 ethanol, 29g of the product was obtained.

EXAMPLE C8 preparation of 2-hydroxy-4-tetradecyloxy benzophenone intermediate 21.4g of 2,4 dihydroxy acetophenone (raw material C) was charged into a three-necked flask containing 40mL of N, N-Dimethylformamide (DMF) and 13.8g of anhydrous potassium carbonate, 0.5g of tetrabutylammonium bromide was further added, and the flask was placed in an oil bath at 70℃and 25g of bromotetradecane (raw material D) was added dropwise while stirring, and the system was allowed to react for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added to the flask, and a 6M hydrochloric acid solution was added dropwise to the flask until ph=4 to 6, and after separating the aqueous phase, 2-hydroxy-4-tetradecyloxy benzophenone (raw material intermediate a) was obtained as a solid, which was recrystallized from 20mL of 95 ethanol to obtain 32g of a product.

Example C9 preparation of 2-hydroxy-4-pentadecylbenzophenone intermediate 7.7g of 2, 4-dihydroxyacetophenone (raw material C) was charged into a three-necked flask containing 40mL of N, N-Dimethylformamide (DMF) and 5.5g of anhydrous potassium carbonate, the flask was placed in an oil bath at 70℃and 10g of bromopentadecane (raw material D) was added dropwise with stirring, and the system was allowed to react for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 100mL of water was added to the flask, and a 6M hydrochloric acid solution was added dropwise to the flask until ph=4 to 6, and after separating the aqueous phase, 2-hydroxy-4-pentadecylbenzophenone (raw material intermediate a) was obtained as a solid, which was recrystallized from 20mL of 95 ethanol to obtain 13g of a product.

Example D group test of performance results of different compositions of the prepared lithium liquid organic Compound example D1 preparation of lithium extractant according to the invention Performance test I (YL-1: natural alkaline brine)

Using 2-hydroxy-4-alkoxy-5-nitrobenzophenone/acetophenone prepared in examples B1 to B3 trioctylphosphine oxide or/and trialkylphosphine oxide and solvent oil are compounded to extract lithium organic phase (STLK-Z7 AN: 2-hydroxy-4-heptyloxy-5-nitrobenzophenone STLK-Y8AN 2-hydroxy-4-octoxy-5-nitrobenzophenone STLK-Z9AN 2-hydroxy-4-nonyloxy-5-nitrobenzophenone STLK-Z10AN 2-hydroxy-4-decyloxy-5-nitrobenzophenone STLK-Z12AN 2-hydroxy-4-dodecoxy-5-nitrobenzophenone STLK-Z13AN 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone STLK-Z14AN 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone STLK-Z15AN 2-hydroxy-4-pentadecoxy-5-nitrobenzophenone STLK-Z7BN 2-hydroxy-4-heptyloxy-5-nitrobenzophenone STLK-Y8BN 2-hydroxy-4-octoxy-5-nitrobenzophenone STLK-Z9BN 2-hydroxy-4-nonyloxy-5-nitrobenzophenone STLK-Z14AN 2-hydroxy-pentadecoxy-5-nitrobenzophenone, STLK-Z12BN, 2-hydroxy-4-dodecyloxy-5-nitroacetophenone, STLK-Z13BN, 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, STLK-Z14BN, 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone and STLK-Z15BN, 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone), and separating lithium in certain natural alkaline brine by an extraction method, so that lithium in the brine is selectively extracted into an organic phase. The composition of the used natural alkaline brine is 0.258g/L of Li, 41.051g/L of Na, 7.891g/L of K, 0.082g/L of Mg, 46g/L of Cl, 12.77g/L of SO ₄, 0.56g/L of B and pH=9.43, and the temperature is room temperature (25 ℃ to 27 ℃). Organic phase 20mL. Organic phase/aqueous phase volume ratio (O/A) 4.

Example D2 preparation of lithium extractant Performance test II (YL-2: lithium sinking mother liquor) according to the invention

Lithium was extracted into a lithium extraction mother solution by using the lithium organic phase (STLK-Z7 AN: 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, 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-Z15: 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone) prepared in examples B1-B3 in a compounding manner. The lithium carbonate precipitation mother solution comprises 1.089g/L of Li, 76.611g/L of Na, 118.08g/L of Cl, 4.7g/L of CO ₃ and pH=10.74, and the temperature is room temperature (25 ℃ to 27 ℃). Organic phase 20mL. Organic phase/aqueous phase volume ratio (O/A) 4.

Example D3 preparation of lithium extractant Performance test III (YL-3: sodium alkaline solution containing boron) lithium organic phase (STLK-Z7 AN: 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, STLK-Z12AN: 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone, STLK-Z13AN: 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone, STLK-Z14: 2-hydroxy-4-tetradecyloxy-5-nitro-42-AN, and STLK-hydroxy-5-AN) was extracted with the 2-hydroxy-4-alkoxy-5-nitrobenzophenone prepared in examples B1-B3, and the lithium extractant was separated from the aqueous alkaline solution by selective extraction of sodium to sodium in the aqueous alkaline phase. The alkaline solution YL-3 of the sodium boron is composed of 0.515g/L of Li, 85.472g/L of Na, 131.7g/L of Cl, 0.82g/L of B, pH=10.00 and room temperature (25 ℃ to 27 ℃). Organic phase 20mL. Organic phase/aqueous phase volume ratio (O/A) 4.

Example D4 preparation of lithium extractant Performance test IV (YL-4: lithium hydroxide and sodium chloride Mixed solution) according to the invention

Using one of the methods described in examples B1-B3, 0.1M STLK-Z7AN+ STLK-Z9AN (molar ratio 1:1) was prepared as 20mL of 0.1M TRPO organic phase, 0.1M STLK-Y8AN+ STLK-Z10AN (molar ratio 1:1) as 20mL of 0.1M TRPO organic phase, 0.1M STLK-Z12AN as 20mL of 0.1M TRPO organic phase, 0.2M STLK-Y8AN as 40mL of 0.2M TRPO organic phase. And (3) separating lithium in certain lithium-containing alkaline brine YL-4 by an extraction method, so that the lithium in the brine is selectively extracted into an organic phase. The composition of the lithium alkaline brine YL-4 is Li 0.619g/L, na 66.261g/L, cl 102.13g/L, pH=12.52, and the temperature is room temperature (25 ℃ to 27 ℃). Organic phase 20mL.

Example E group influence of the different nitric acid usage on the extraction Performance

Example E1 preparation of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone containing a liquid organic composition (nitric acid was used in an amount of 0.95 times the molar equivalent of the intermediate 2-hydroxy-4-n-octoxy-benzophenone) 13.06g of 2-hydroxy-4-n-octoxy-benzophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, and then the flask was placed in a 50℃oil bath pot, 2.6mL of 68wt% nitric acid was added, reacted for 12 hours, then the temperature was raised to 50℃for further reaction for 4 hours, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. Then, the whole prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the acetic acid solution, 60g of anhydrous NaOH is added, after full mixing, standing and layering are carried out, a lower water phase is discharged, an upper oil phase is obtained, and the oil phase is washed with water for multiple times to be used as an extracting agent for lithium extraction. And respectively obtaining the compound liquid organic composition STLK-Z8AN-E1 for extracting lithium.

Example E2 preparation of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone containing a liquid organic composition (nitric acid was used in an amount 1.1 times the molar equivalent of the intermediate 2-hydroxy-4-n-octoxy-benzophenone) 13.06g of 2-hydroxy-4-n-octoxy-benzophenone was added to a three-necked flask equipped with 80mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in a 50℃oil bath, 3.0mL of 68wt% nitric acid was added, after 12 hours of reaction, the temperature was raised to 50℃for further reaction for 4 hours, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. Then, the whole prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the acetic acid solution, 60g of anhydrous NaOH is added, after full mixing, standing and layering are carried out, a lower water phase is discharged, an upper oil phase is obtained, and the oil phase is washed with water for multiple times to be used as an extracting agent for lithium extraction. And respectively obtaining the compound liquid organic composition STLK-Z8AN-E2 for extracting lithium.

Example E3 preparation of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone containing a liquid organic composition (nitric acid in an amount 1.2 times the molar equivalent of the intermediate 2-hydroxy-4-n-octoxy-benzophenone) 13.06g of 2-hydroxy-4-n-octoxy-benzophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to dissolve completely, the flask was placed in a 50℃oil bath, 3.3mL of 68wt% nitric acid was added, after 12h of reaction, the temperature was raised to 50℃and the reaction was continued for 4h, after which the reaction was cooled to room temperature, an acetic acid solution of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone was obtained. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. Then, the whole prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the acetic acid solution, 60g of anhydrous NaOH is added, after full mixing, standing and layering are carried out, a lower water phase is discharged, an upper oil phase is obtained, and the oil phase is washed with water for multiple times to be used as an extracting agent for lithium extraction. And respectively obtaining the compound liquid organic composition STLK-Z8AN-E3 for extracting lithium.

The lithium-containing solution YL-2 in example D2 was used as the original test intermediate for the capacities of the lithium-extracting compound liquid organic compositions STLK-Z8AN, STLK-Z8AN-E1, STLK-Z8AN-E2 and STLK-Z8AN-E3 prepared under the nitric acid ratio. The method comprises the steps of taking 20mL of the compound liquid organic composition, taking 60mL of lithium-containing solution YL-2, reacting with the compound liquid organic composition in a separating funnel for 5min, standing for 10min for layering, discharging the lower layer aqueous solution, repeating the process for 3 times, and enabling all the extractant in the compound liquid organic composition to act with metal ions to reach an extraction saturated state. And then, the obtained saturated extraction organic phase is acted for 3 times with 20mL of 0.6mol/L hydrochloric acid aqueous solution, all 3 times of obtained stripping liquid are diluted and fixed to a volume of 1L in a volumetric flask, the concentration of Li and Na in the stripping liquid is measured, and the concentration of an effective extractant in the compound liquid organic composition is calculated by utilizing the following formula.

c_{Extraction agent}(mol/L)＝(c_Li(mol/L)+c_Na(mol/L))*1L/20mL*1000

The results obtained are as follows:

Example F group influence of different acetic acid usage on extraction Performance

Example F1 preparation of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone containing a liquid organic composition (acetic acid in an amount of 2L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octoxy-benzophenone) 2-hydroxy-4-n-octoxy benzophenone was taken, 13.06g was added to a three-necked flask equipped with 80mL glacial acetic acid, stirred to dissolve completely, and then the flask was placed in an oil bath pot at 50℃and 2.75mL of 68wt% nitric acid was added, after 12 hours of reaction, the temperature was raised to 50℃for further reaction for 4 hours, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. Then, the whole prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the acetic acid solution, 60g of anhydrous NaOH is added, after full mixing, standing and layering are carried out, a lower water phase is discharged, an upper oil phase is obtained, and the oil phase is washed with water for multiple times to be used as an extracting agent for lithium extraction. And respectively obtaining the compound liquid organic composition STLK-Z8AN-F1 for extracting lithium.

Example F2 preparation of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone containing a liquid organic composition (acetic acid in an amount of 1L of glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octoxy-benzophenone) 2-hydroxy-4-n-octoxy benzophenone was taken, 13.06g was added to a three-necked flask equipped with 40mL of glacial acetic acid, stirred to dissolve completely, and then the flask was placed in an oil bath pot at 50℃and 2.75mL of 68wt% nitric acid was added, after 12 hours of reaction, the temperature was raised to 50℃for further reaction for 4 hours, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. Then, the whole prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the acetic acid solution, then 30g of anhydrous NaOH is added, after full mixing, standing and layering are carried out, a lower water phase is discharged, an upper oil phase is obtained, and the oil phase is washed with water for multiple times to be used as an extracting agent for lithium extraction. And respectively obtaining the compound liquid organic composition STLK-Z8AN-F2 for extracting lithium.

Example F3 preparation of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone containing a liquid organic composition (acetic acid in an amount of 0.5L of glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octoxy-benzophenone) 2-hydroxy-4-n-octoxy benzophenone was taken, 13.06g was added to a three-necked flask equipped with 20mL of glacial acetic acid, stirred to dissolve completely, then the flask was placed in an oil bath at 50℃and 2.75mL of 68wt% nitric acid was added, after 12h of reaction, the reaction was continued at 50℃until the temperature was raised to 50℃and then cooled to room temperature, to give an acetic acid solution of 2-hydroxy-4-n-octoxy-5-nitrobenzophenone. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. Then, the whole prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the acetic acid solution, then 15g of anhydrous NaOH is added, after full mixing, standing and layering are carried out, a lower water phase is discharged, an upper oil phase is obtained, and the oil phase is washed with water for multiple times to be used as an extracting agent for lithium extraction. And respectively obtaining the compound liquid organic composition STLK-Z8AN-F3 for extracting lithium.

Example F4 preparation of a 2-hydroxy-4-n-octoxy-5-nitrobenzophenone containing Compound liquid organic composition (acetic acid in an amount of 0.25L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octoxy-benzophenone)

13.06G of 2-hydroxy-4-n-octoxybenzophenone is taken and added into a three-necked flask filled with 10mL of glacial acetic acid, the mixture is stirred to be completely dissolved, then the flask is placed into an oil bath pot at 50 ℃, 2.75mL of 68wt% nitric acid is added, after the reaction is carried out for 12 hours, the temperature is raised to 50 ℃ for continuous reaction for 4 hours, and then the mixture is cooled to room temperature, thus obtaining the acetic acid solution of 2-hydroxy-4-n-octoxy5-nitrobenzophenone. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. Then, the whole of the obtained D80 solvent oil containing trialkylphosphine oxide was mixed with the acetic acid solution, 7.5g of anhydrous NaOH was added thereto, and after sufficient mixing, the mixture was allowed to stand for delamination, and the lower aqueous phase was discharged to obtain an upper oil phase, and the oil phase was washed with water several times to obtain an extractant for lithium extraction. And respectively obtaining the compound liquid organic composition STLK-Z8AN-F4 for extracting lithium.

Example F5 preparation of a 2-hydroxy-4-n-octoxy-5-nitrobenzophenone containing liquid organic composition (acetic acid 0. Water as solvent, 2L of 2-hydroxy-4-n-octoxy-benzophenone as intermediate was added per mole)

13.06G of 2-hydroxy-4-n-octoxybenzophenone is taken and added into a three-necked flask filled with 80mL of water, then the flask is placed into an oil bath pot at 50 ℃, 2.75mL of 68wt% nitric acid is added for reaction for 12 hours, the temperature is raised to 50 ℃ for continuous reaction for 4 hours, and then the acetic acid solution of 2-hydroxy-4-n-octoxybenzophenone is obtained after cooling to room temperature. Another 400mL of D80 solvent oil was added with 13.2g of trialkylphosphine oxide and stirred until a homogeneous solution was formed. And mixing all the prepared D80 solvent oil containing trialkylphosphine oxide with the acetic acid solution, fully mixing, standing for layering, discharging a lower water phase to obtain an upper oil phase, and washing the oil phase with water for multiple times to obtain the extracting agent for lithium extraction. And respectively obtaining the compound liquid organic composition STLK-Z8AN-F5 for extracting lithium.

The lithium-containing solution YL-2 in example D2 was used as the original test for the capacities of the different intermediates, STLK-Z8AN-F1, STLK-Z8AN-F2, STLK-Z8AN-F3, STLK-Z8AN-F4 and STLK-Z8AN-F5, for the lithium extraction prepared under the nitric acid ratio. The method comprises the steps of taking 20mL of the compound liquid organic composition, taking 60mL of lithium-containing solution YL-2, reacting with the compound liquid organic composition in a separating funnel for 5min, standing for 10min for layering, discharging the lower layer aqueous solution, repeating the process for 3 times, and enabling all the extractant in the compound liquid organic composition to act with metal ions to reach an extraction saturated state. And then, the obtained saturated extraction organic phase is acted for 3 times with 20mL of 0.6mol/L hydrochloric acid aqueous solution, all 3 times of obtained stripping liquid are diluted and fixed to a volume of 1L in a volumetric flask, the concentration of Li and Na in the stripping liquid is measured, and the concentration of an effective extractant in the compound liquid organic composition is calculated by utilizing the following formula.

c_{Extraction agent}(mol/L)＝(c_Li(mol/L)+c_Na(mol/L))*1L/20mL*1000

The results obtained are as follows:

Claims

1. A liquid organic composition for extraction of lithium comprising component a) a lithium extractant, component b) a synergist and component C) a diluent, wherein component a) comprises component a 1) and component a 2), component a 1) is 2-hydroxy-4-C _7-16 alkoxy-acetophenone or/and 2-hydroxy-4-C _7-16 alkoxy-benzophenone, said C _7-16 alkoxy being optionally substituted, and component a 2) is the nitration product of component a 1).

2. The liquid organic composition for extracting lithium as claimed in claim 1, wherein the component a 2) 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 extracting lithium according to claim 1 or 2, wherein the component a 1) is one or a mixture of 2-hydroxy-4-heptyloxy acetophenone, 2-hydroxy-4-octyloxy acetophenone, 2-hydroxy-4-nonyloxy acetophenone, 2-hydroxy-4-decyloxy acetophenone, 2-hydroxy-4-undecyloxy acetophenone, 2-hydroxy-4-dodecyloxy acetophenone, 2-hydroxy-4-tridecyloxy acetophenone, 2-hydroxy-4-tetradecyloxy acetophenone, 2-hydroxy-4-pentadecyloxy acetophenone, 2-hydroxy-4-hexadecyloxy acetophenone, 2-hydroxy-4-heptyloxy benzophenone, 2-hydroxy-4-octyloxy benzophenone, 2-hydroxy-4-nonyloxy benzophenone, 2-hydroxy-4-undecyloxy benzophenone, 2-hydroxy-4-dodecyloxy benzophenone, 2-hydroxy-4-tridecyloxy benzophenone, 2-hydroxy-4-tetradecyloxy benzophenone, 2-hydroxy-4-pentadecyloxy benzophenone, 2-hydroxy-4-hexadecyloxy benzophenone.

4. The liquid organic composition for extracting lithium as claimed in claim 3, wherein the component a 2) 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-nitroacetophenone, 2-hydroxy-5-decyloxy-5-nitroacetophenone One or a mixture of any more of 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.

5. The liquid organic composition for extraction of lithium according to any one of claims 1-4, wherein the molar ratio of component a 1) to component a 2) is from 1:1 to 1:1000, preferably from 1:10 to 1:100.

6. The liquid organic composition for extraction of lithium of any one of claims 1-5, wherein the synergist is one or more of tributyl phosphate, trioctyl phosphate, tris (2-ethylhexyl) phosphate, trihexyl phosphate, tripentyl phosphate, dibutyl butyl phosphate, dibutyl phosphate, di-sec-octyl methyl phosphate, diisooctyl isopropyl phosphate, diisopentyl methyl phosphate, triphenylphosphine oxide, diphenyl benzyl phosphine oxide, diphenyl (2-hydroxyphenylmethyl) phosphine oxide, 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide, trioctylphosphine oxide (or Cyanex 921), trialkylphosphine oxide TRPO (or Cyanex 923).

7. The liquid organic composition for extracting lithium of any one of claims 1-6, wherein the diluent is one or more of technical white oil, kerosene, sulfonated kerosene, D-series solvent oil, n-heptane, cyclohexane, octane, dodecane, petroleum ether, xylene, anisole, methyl isobutyl ketone, toluene, octanone, 5-nonanone, isoamyl alcohol, n-butanol, halobenzene, ethylbenzene, or diethylbenzene.

8. The liquid organic composition for extraction of lithium according to any one of claims 1 to 7, wherein the total concentration of the lithium extractants a 1) and a 2) in the liquid organic composition for extraction of lithium is 0.03mol/L to 1.0mol/L, the concentration of the synergist in the liquid organic composition for extraction of lithium is 0.01mol/L to 2.0mol/L, and the molar ratio of the lithium extractant to the synergist is 3:1 to 0.5:1.

9. A method of preparing the liquid organic composition for extraction of lithium according to any one of claims 1 to 8, comprising:

A diluent and a synergist are added to the mixture of components a 1) and a 2).

10. The process according to claim 9, wherein component a 1) 2-hydroxy-4-alkoxy-acetophenone or/and 2-hydroxy-4-alkoxy-benzophenone is nitrated in an acetic acid solvent with nitric acid or a nitric acid/acetic acid mixture to give an acetic acid solution of component a 1) and component a 2).

11. The preparation method of claim 10, wherein the component a 1) is subjected to nitration reaction, which comprises mixing the component a 1) with glacial acetic acid or aqueous acetic acid, heating to 30-110 ℃, and then adding nitric acid or mixed acid of nitric acid and acetic acid for reaction to obtain an acetic acid solution of the lithium extractant.

12. The process according to claim 11, wherein the glacial acetic acid or aqueous acetic acid is used in an amount of 0.5 to 5 times the weight of a 1).

13. The production process 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 a 1) and component a 2), adding a base to the solution, and then mixing the resulting mixture with the diluent and the synergist to obtain the lithium-extracting useful composition.

14. The process according to any one of claims 9 to 12, further comprising adding a base after adding a diluent and a synergist to the acetic acid solution of components a 1) and a 2), and allowing the organic phase to separate.

15. The process of claim 13 or 14, wherein the base is NaOH solid or aqueous solution.

16. The process according to any one of claims 9 to 15, wherein the providing component a 1) is commercially available or is obtainable by the ethereal reaction of 2, 4-dihydroxyacetophenone, 2, 4-dihydroxybenzophenone or a mixture of the two with a halogenated hydrocarbon.

17. The process of claim 16 wherein the halocarbon 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 a C7-C16 halocarbon mixture, and isomers of these halocarbons.