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

Abstract

The invention provides a liquid organic composition for extracting lithium, which comprises a component a) a lithium extracting agent, a component b) a synergist and a component c) a diluent, the component a) comprises a component a1) and a component a2), the component a1) is 2-hydroxy-4-C7-16 alkoxy-acetophenone or / and 2-hydroxy-4-C7-16 alkoxy-benzophenone, the C7-16 alkoxy is optionally substituted, and the component a2) is a mixture of a component c) and a component c). The component a2) is a nitration product of the component a1). The invention also provides a preparation method of the liquid organic composition for lithium extraction.

Description

Technical Field

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

[0002] Lithium is an important energy metal element. The explosive growth of electric vehicles with lithium batteries as core components has led to an increasing demand for lithium salts. Lithium salts are mainly derived from lithium-containing ores and lithium-containing brines. The development of both inevitably involves the stage of extracting lithium from aqueous solutions containing alkali metals and alkaline earth metals. Therefore, the development of compounds and combinations that have special selectivity for lithium is the key to efficient lithium extraction.

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

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

[0005] In view of the above problems, the inventors have proposed a concept and preparation process of skipping the synthesis of pure substances of new phenolic ketone lithium extractants and directly preparing a liquid organic composition for lithium extraction. The method disclosed in the present invention avoids: 1) the cumbersome process of first preparing a pure substance of a phenolic ketone lithium extractant and then mixing it with a trialkylphosphine oxide co-extractant and a diluent to prepare a liquid organic composition for lithium extraction; 2) the problem of difficulty in recycling acetic acid solvent in the preparation process of pure substances of phenolic ketone lithium extractants.

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

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

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

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

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

[0011] The process disclosed in the present invention omits the purification process of 2-hydroxy-4-alkoxy-5-nitroacetophenone or / and 2-hydroxy-4-alkoxy-5-nitrobenzophenone solid substances, greatly reduces the energy consumption required for distillation of acetic acid solvent, effectively avoids the potential explosion hazard and other problems faced in the manufacturing process of nitro-containing solid substances, and directly obtains a liquid organic mixture for lithium extraction. While reducing the complexity of the production process and the production cost, it also ensures the safety of the preparation of the extractant and the effectiveness of its use.

[0012] The disclosed process for preparing a liquid organic mixture for lithium extraction has almost no waste organic solvent and wastewater discharge, and the only byproduct is a sodium acetate solution. The obtained byproduct sodium acetate solution can be concentrated and / or crystallized to become an industrial product with a marketable price. DETAILED DESCRIPTION

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

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

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

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

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

[0018] Except in the working examples or otherwise indicated, all numbers of quantitative properties such as dosage stated 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 in the application is intended to include all subranges within the range and any combination of the respective endpoints of the range or subrange.

[0019] The words "include", "contain" or "comprises" and the like used in the present disclosure 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 "includes (comprising)" used herein may be open, semi-closed and closed. In other words, the term also includes "essentially consisting of..." or "consisting of..." Therefore, the liquid organic composition for lithium extraction comprises component a) lithium extractant, component b) synergist and component c) diluent, which means that the liquid organic composition for lithium extraction 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 lithium extraction may further contain an antioxidant such as ascorbic acid.

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

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

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

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

[0024] The term "extractant" in the present disclosure refers to a substance that reacts with the metal to be extracted (e.g., lithium, sodium, potassium, etc.) to form an extractant that is extracted into the organic phase through a coordination chemical reaction, and can also extract the extracted metal from the organic phase to the aqueous phase through a certain chemical reaction, thereby achieving the purification or enrichment of the metal. Extractant can be used interchangeably with extractant in the present disclosure. For example, lithium extractant or lithium extractant is used to achieve the purification or enrichment of lithium by extraction.

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

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

[0027] The term "cycloalkyl" in the present 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 a C3-C6 cycloalkyl. Illustrative examples of cycloalkyl include, but are not limited to, the following groups: cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, etc. In some preferred embodiments, the cycloalkyl is cyclopentyl or cyclohexyl.

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

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

[0030] The term "halo" or "halogen" in the present disclosure 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" in the present disclosure includes straight-chain halogenated hydrocarbons and branched halogenated hydrocarbons.

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

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

[0033] In the liquid organic composition for extracting lithium in the present application, component a) a lithium extractant comprises component a1) and component a2), 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).

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

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

[0036] For example, the component a2) is 2-hydroxy-4-heptyloxy-5-nitroacetophenone, 2-hydroxy-4-octyloxy-5-nitroacetophenone, 2-hydroxy-4-nonyloxy-5-nitroacetophenone, 2-hydroxy-4-decyloxy-5-nitroacetophenone, 2-hydroxy-4-undecyloxy-5-nitroacetophenone, 2-hydroxy-4-dodecyloxy-5-nitroacetophenone, 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone, 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone, 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone, 2-hydroxy-4 -heptyloxy-5-nitrobenzophenone, 2-hydroxy-4-octyloxy-5-nitrobenzophenone, 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, 2-hydroxy-4-decyloxy-5-nitrobenzophenone, 2-hydroxy-4-undedecyloxy-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 of them.

[0037] 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.

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

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

[0040] In the liquid organic composition for extracting lithium of the present application, the synergist is, for example, 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, diisopentyl 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 one or more of trialkyl phosphine oxide TRPO (or Cyanex923).

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

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

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

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

[0045] In one embodiment of lithium extraction, the pH value of the aqueous solution containing lithium ions is 7-13 before contacting with 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 (eg, sodium or potassium) or ammonium.

[0047] In one embodiment of extracting lithium, the aqueous solution containing lithium ions is a natural brine with alkalinity; the alkalinity of the natural brine with alkalinity is optionally further adjusted by adding hydroxides, carbonates, phosphates, or borates of alkali metals or ammonium. 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 an 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 stripping 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 stripping agent, the concentration of hydrogen ions is 0.05 mol / L to 6 mol / L; the volume ratio of the stripping 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 is 0.05 mol / L to 10 mol / L after the stripping agent contacts the organic layer.

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

[0056] In one embodiment of extracting lithium, the time for the stripping 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 aqueous lithium-containing solution.

[0059] In one embodiment of lithium extraction, concentrated acid is added to the lithium-containing stripping agent after the stripping agent contacts the organic layer, and the stripping agent is used again as the stripping 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 the step of concentrating lithium by evaporating water in a lithium-containing stripping agent, and / or further precipitating lithium carbonate from the lithium-containing stripping agent.

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

[0062] The preparation method comprises:

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

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

[0065] To the mixture of component a1) and component a2) are added diluents and synergists.

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

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

[0068] For example, the nitration reaction of the component a1) may include mixing the component a1) with glacial acetic acid or aqueous acetic acid, heating to 30-110° C., preferably to 50-80° 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. At 50-80° C., a considerable portion of the component a1) melts to form a liquid phase, which will help the nitration reaction. In a preferred embodiment, the amount of glacial acetic acid or aqueous acetic acid in the step of mixing the component a1) with glacial acetic acid or aqueous acetic acid is 0.5-5 times the weight of 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone. In a more preferred embodiment, the amount of glacial acetic acid or aqueous acetic acid 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, 2.0 times the weight of 2-hydroxy-4-alkoxy-acetophenone and / or 2-hydroxy-4-alkoxy-benzophenone.

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

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

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

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

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

[0074] Component a1) can be commercially available or homemade. For example, providing component a1) can include the step of 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 a C7-C16 halogenated hydrocarbon mixture.

[0075] The process disclosed in the present invention omits the preparation process of 2-hydroxy-4-alkoxy-5-nitroacetophenone or / and 2-hydroxy-4-alkoxy-5-nitrobenzophenone solid substances, greatly reduces the energy consumption required for distillation of acetic acid solvent, effectively avoids the explosive hazard problem faced in the manufacturing process of nitro-containing solid substances, and directly obtains a liquid organic composition for lithium extraction. While reducing the complexity of the production process and the production cost, it also ensures the safety of the preparation of the extractant.

[0076] The disclosed process for preparing the liquid organic composition for lithium extraction has almost no waste organic solvent and wastewater discharge, and the byproduct is a sodium acetate solution. The obtained byproduct sodium acetate solution can be concentrated and / or crystallized to become an industrial product with economic value.

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

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

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

[0080] (3) adding sodium hydroxide solution to the organic mixture B obtained in (2) to cause a neutralization reaction between sodium hydroxide and acetic acid in B to generate sodium acetate, then allowing the mixture to stand for stratification, discharging the bottom sodium acetate solution, and obtaining an upper deacetic acid-free organic phase C, which is a liquid organic mixture for lithium extraction.

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

[0082] Preferably, in step (1), the 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone is 2-hydroxy-4-heptyloxyacetophenone, 2-hydroxy-4-octyloxyacetophenone, 2-hydroxy-4-nonyloxyacetophenone, 2-hydroxy-4-decyloxyacetophenone, 2-hydroxy-4-undecyloxyacetophenone, 2-hydroxy-4-dodecyloxyacetophenone, 2-hydroxy-4-tridecyloxyacetophenone, 2-hydroxy-4-tetradecyloxyacetophenone, 2-hydroxy-4-pentadecyloxyacetophenone, 2-hydroxy-4-decyloxyacetophenone, 2-hydroxy-4-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.

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

[0084] Preferably, in step (1), the water content of the acetic acid solvent is less than 20%. The embodiments disclosed herein found that when glacial acetic acid and acetic acid with a lower water content were used as solvents, the obtained liquid organic composition for lithium extraction had excellent lithium extraction performance. However, when acetic acid with a higher water content or pure water was used as the solvent, the lithium extraction capacity of the liquid organic composition for lithium extraction would be greatly reduced.

[0085] Preferably, in step (1), in order to reduce the amount of acetic acid solvent, 2-hydroxy-4-alkoxy-acetophenone or / and 2-hydroxy-4-alkoxy-benzophenone are first dissolved in a small amount of acetic acid solvent under heating conditions, and the amount of acetic acid 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 an acetic acid solution of dilute nitric acid. Finally, the obtained 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 to 70°C.

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

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

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

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

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

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

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

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

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

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

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

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

[0098] Example

[0099] The following examples are provided to further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in this area or the product instructions are used. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be obtained commercially.

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

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

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

[0103] Example A2: Preparation of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone acetic acid solution Take 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 2.75 mL of 68 wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone.

[0104] Example A3: Preparation of 2-hydroxy-4-isooctyloxy-5-nitrobenzophenone acetic acid solution Take 13.06 g of 2-hydroxy-4-isooctyloxybenzophenone, add it into 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 80°C, add 3 mL of 68wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-isooctyloxy-5-nitrobenzophenone.

[0105] Example A4: Preparation of 2-hydroxy-4-nonyloxy-5-nitrobenzophenone acetic acid solution Take 13.6 g of 2-hydroxy-4-nonyloxybenzophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68 wt% nitric acid, react for 16 h, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-nonyloxy-5-nitrobenzophenone.

[0106] Example A5: Preparation of 2-hydroxy-4-decyloxy-5-nitrobenzophenone acetic acid solution Take 14.2 g of 2-hydroxy-4-decyloxybenzophenone, add it into 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, add 3 mL of 68wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-decyloxy-5-nitrobenzophenone.

[0107] Example A6: Preparation of 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone acetic acid solution Take 15.3 g of 2-hydroxy-4-dodecyloxybenzophenone, 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, add 3 mL of 68wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-dodecyloxy-5-nitrobenzophenone.

[0108] Example A7: Preparation of 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone acetic acid solution Take 15.9 g of 2-hydroxy-4-tridecyloxybenzophenone, add it to a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68wt% nitric acid, react for 12 h, heat to 70°C and react for another 4 h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tridecyloxy-5-nitrobenzophenone.

[0109] Example A8: Preparation of 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone acetic acid solution Take 16.42 g of 2-hydroxy-4-tetradecyloxybenzophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68 wt% nitric acid, react for 12 h, heat to 70°C and react for 4 h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tetradecyloxy-5-nitrobenzophenone.

[0110] Example A9: Preparation of 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone acetic acid solution Take 17.15 g of 2-hydroxy-4-pentadecyloxybenzophenone, add it to a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68 wt% nitric acid, react for 12 h, heat to 70°C and react for another 4 h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-pentadecyloxy-5-nitrobenzophenone.

[0111] Example A10: Preparation of 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone acetic acid solution Take 17.55 g of 2-hydroxy-4-hexadecyloxybenzophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68 wt% nitric acid, react for 12 h, heat to 80°C and react for another 4 h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-hexadecyloxy-5-nitrobenzophenone.

[0112] Example A11: Preparation of 2-hydroxy-4-heptyloxy-5-nitroacetophenone acetic acid solution Take 10.1 g of 2-hydroxy-4-heptyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 70°C, add 3 mL of 68 wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitroacetophenone.

[0113] Example A12: Preparation of 2-hydroxy-4-n-octyloxy-5-nitroacetophenone acetic acid solution Take 10.6 g of 2-hydroxy-4-n-octyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 70°C, add 2.75 mL of 68 wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitroacetophenone.

[0114] Example A13: Preparation of 2-hydroxy-4-isooctyloxy-5-nitroacetophenone acetic acid solution Take 10.6 g of 2-hydroxy-4-isooctyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 70°C, add 3 mL of 68 wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-isooctyloxy-5-nitroacetophenone.

[0115] Example A14: Preparation of 2-hydroxy-4-nonyloxy-5-nitroacetophenone acetic acid solution Take 11.1 g of 2-hydroxy-4-nonyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68 wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-nonyloxy-5-nitroacetophenone.

[0116] Example A15: Preparation of 2-hydroxy-4-decyloxy-5-nitroacetophenone acetic acid solution Take 11.7 g of 2-hydroxy-4-decyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68 wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-decyloxy-5-nitroacetophenone.

[0117] Example A16: Preparation of 2-hydroxy-4-dodecyloxy-5-nitroacetophenone acetic acid solution Take 12.8 g of 2-hydroxy-4-dodecyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68 wt% nitric acid, react for 16 hours, and cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-dodecyloxy-5-nitroacetophenone.

[0118] Example A17: Preparation of 2-hydroxy-4-tridecyloxy-5-nitroacetophenone acetic acid solution Take 13.4 g of 2-hydroxy-4-tridecyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68wt% nitric acid, react for 12 h, heat to 80°C and react for another 4 h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tridecyloxy-5-nitroacetophenone.

[0119] Example A18: Preparation of 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone acetic acid solution Take 13.9 g of 2-hydroxy-4-tetradecyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68wt% nitric acid, react for 12 h, heat to 80°C and react for another 4 h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone.

[0120] Example A19: Preparation of 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone acetic acid solution Take 14.7 g of 2-hydroxy-4-pentadecyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68wt% nitric acid, react 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-pentadecyloxy-5-nitroacetophenone.

[0121] Example A20: Preparation of 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone acetic acid solution Take 15.1 g of 2-hydroxy-4-hexadecyloxyacetophenone, add it into a three-necked flask charged with 80 mL of glacial acetic acid, stir to completely dissolve it, then place the flask in an oil bath at 50°C, add 3 mL of 68wt% nitric acid, react for 12 h, heat to 80°C and react for another 4 h, then cool to room temperature to obtain an acetic acid solution of 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone.

[0122] Example Group B: Preparation of a composite lithium extraction liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone Example B1: Preparation of a composite lithium extraction liquid organic composition containing 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone (synergist: trialkylphosphine oxide; solvent: D80 solvent oil)

[0123] Take 80 mL of acetic acid solution 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 respectively. Take 400 mL of D80 solvent oil separately, add 13.2 g 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 acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, and then add 60 g of anhydrous NaOH, mix thoroughly, stand for stratification, release the lower aqueous phase, obtain the upper oil phase, and wash the oil phase with water several times as an extractant for lithium extraction. The composite liquid organic compositions STLK-Z7AN, STLK-Z8AN, STLK-Y8AN, STLK-Z9AN and STLK-Z10AN for extracting lithium were obtained respectively.

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

[0125] Take 80 mL of 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. Take 400 mL of 15# industrial white oil, add 15.5 g of tri-n-octylphosphine oxide, and stir until a uniform solution is formed. After that, mix all the prepared D80 solvent oil containing trialkylphosphine oxide with the acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, and then add 280 g of 20 wt% NaOH aqueous solution, mix thoroughly, stand for stratification, 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 compositions STLK-Z12AN, STLK-Z13AN, STLK-Y14AN, STLK-Z15AN and STLK-Z16AN for extracting lithium were obtained respectively.

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

[0127] Take 80 mL 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-A15. Take 400 mL of diethylbenzene, add 15.5 g of tri-n-octylphosphine oxide, and stir until a uniform 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, and then add 186.5 g of 30 wt% NaOH aqueous solution, mix thoroughly, stand for stratification, release the lower aqueous phase, and 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 compositions STLK-Z7BN, STLK-Z8BN, STLK-Y8BN, STLK-Z9BN and STLK-Z10BN for extracting lithium were obtained respectively.

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

[0129] Take 80 mL of the acetic acid solutions of 2-hydroxy-4-dodecyloxy-5-nitroacetophenone, 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone, 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone and 2-hydroxy-4-hexadecyloxy-5-nitroacetophenone prepared in Examples A6-A10 respectively. Take 400 mL of kerosene, add 15.5 g of tri-n-octylphosphine oxide, and stir until a uniform solution is formed. After that, all the prepared D80 solvent oil containing trialkylphosphine oxide is mixed with the acetic acid solution of 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, and then add 140 g of a 40 wt% NaOH aqueous solution, mix thoroughly, stand for stratification, 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 compositions STLK-Z12BN, STLK-Z13BN, STLK-Y14BN, STLK-Z15BN and STLK-Z16BN for extracting lithium were obtained respectively.

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

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

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

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

[0134] Example C3: Preparation of 2-hydroxy-4-isooctyloxybenzophenone intermediate Take 27.6g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL N,N-dimethylformamide (DMF) and 17.8g of anhydrous potassium carbonate. Place the flask in an oil bath at 50°C, add 25g of bromoisooctane (raw material D) dropwise while stirring, then raise the oil bath temperature to 70°C and allow the system 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 to the flask until pH=4-6. After separating the aqueous phase, 30g of oily 2-hydroxy-4-isooctyloxybenzophenone (raw material intermediate A) product is obtained.

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

[0136] Take 25.7g of 2,4-dihydroxyacetophenone (raw material C), add it to a three-necked flask containing 50mL N,N-dimethylformamide (DMF) and 16.6g of anhydrous potassium carbonate, place the flask in an oil bath at 70°C, add 25g of bromononane (raw material D) dropwise while stirring, and let the system 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 to the flask until pH = 4-6. After separating the aqueous phase, obtain 2-hydroxy-4-nonyloxybenzophenone (raw material intermediate A) solid, and recrystallize with 20mL 95 ethanol to obtain 29g of product.

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

[0138] Take 25.4g of 2,4-dihydroxyacetophenone (raw material C), add it to a three-necked flask containing 50mL N,N-dimethylformamide (DMF) and 16.4g of anhydrous potassium carbonate, then add 0.5g of potassium iodide, place the flask in an oil bath at 70°C, add 25g of bromodecane (raw material D) dropwise while stirring, and let the system 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 to the flask until pH = 4-6. After separating the aqueous phase, obtain 2-hydroxy-4-decyloxybenzophenone (raw material intermediate A) solid, and obtain 31g of product after recrystallization with 20mL of 95 ethanol.

[0139] Example C6: Preparation of 2-hydroxy-4-dodecyloxybenzophenone intermediate Take 22.5g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 50mL N,N-dimethylformamide (DMF) and 14.5g of anhydrous potassium carbonate. Place the flask in an oil bath at 70°C, add 25g of bromododecane (raw material D) dropwise while stirring, and react the system 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 to the flask until pH=4-6. After separating the aqueous phase, obtain 2-hydroxy-4-dodecyloxybenzophenone (raw material intermediate A) solid, and recrystallize with 20mL of 95 ethanol to obtain 30g of product.

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

[0141] Take 21.4g of 2,4-dihydroxyacetophenone (raw material C), add it to a three-necked flask containing 50mL of N,N-dimethylformamide (DMF) and 13.8g of anhydrous potassium carbonate, place the flask in an oil bath at 70°C, add 25g of brominated tridecane (raw material D) dropwise while stirring, and let the system 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 to the flask until pH = 4-6. After separating the aqueous phase, obtain 2-hydroxy-4-tridecyloxybenzophenone (raw material intermediate A) solid, and obtain 29g of product after recrystallization with 20mL of 95 ethanol.

[0142] Example C8: Preparation of 2-hydroxy-4-tetradecyloxybenzophenone intermediate Take 21.4g of 2,4-dihydroxyacetophenone (raw material C), add it to a three-necked flask containing 40mL N,N-dimethylformamide (DMF) and 13.8g of anhydrous potassium carbonate, then add 0.5g of tetrabutylammonium bromide, place the flask in an oil bath at 70°C, add 25g of bromotetradecane (raw material D) dropwise while stirring, and react the system 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 to the flask until pH=4-6. After separating the aqueous phase, obtain 2-hydroxy-4-tetradecyloxybenzophenone (raw material intermediate A) solid, and recrystallize with 20mL of 95 ethanol to obtain 32g of product.

[0143] Example C9: Preparation of 2-hydroxy-4-pentadecanyloxybenzophenone intermediate Take 7.7g of 2,4-dihydroxyacetophenone (raw material C) and add it to a three-necked flask containing 40mL N,N-dimethylformamide (DMF) and 5.5g of anhydrous potassium carbonate. Place the flask in an oil bath at 70°C, add 10g of bromopentadecane (raw material D) dropwise while stirring, and react the system 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 to the flask until pH=4-6. After separating the aqueous phase, obtain 2-hydroxy-4-pentadecanyloxybenzophenone (raw material intermediate A) solid, and obtain 13g of product after recrystallization with 20mL of 95 ethanol.

[0144] Example D Group: Performance results of different compositions of prepared composite lithium extraction liquid organic compositions Example D1: Performance test of lithium extraction agent prepared by the present invention I (YL-1: natural alkaline brine)

[0145] The organic phase for lithium extraction (STLK-Z7AN: 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, STLK-Y8AN: 2-hydroxy-4-octyloxy-5-nitrobenzophenone, STLK-Z9AN: 2-hydroxy-4-nonyloxy-5-nitrobenzophenone) prepared in Examples B1-B3 was prepared by compounding 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone, trioctylphosphine oxide or / and trialkylphosphine oxide, and solvent oil (STLK-Y8AN: 2-hydroxy-4-octyloxy-5-nitrobenzophenone, STLK-Z9AN: 2-hydroxy-4-nonyloxy-5-nitrobenzophenone) with 2-hydroxy-4-alkoxy-5-nitrobenzophenone. 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- 4-dodecyloxy-5-nitroacetophenone, STLK-Z13BN: 2-hydroxy-4-tridecyloxy-5-nitroacetophenone, STLK-Z14BN: 2-hydroxy-4-tetradecyloxy-5-nitroacetophenone, STLK-Z15BN: 2-hydroxy-4-pentadecyloxy-5-nitroacetophenone), the lithium in a natural alkaline brine was separated by extraction method, so that the lithium in the brine was selectively extracted into the organic phase. The composition of the natural alkaline brine used is: Li: 0.258g / L, Na: 41.051g / L, K: 7.891g / L, Mg: 0.082g / L, Cl: 46g / L, SO4: 12.77g / L, B: 0.56g / L, pH = 9.43. Temperature: room temperature (25℃~27℃). Organic phase: 20mL. Organic phase / aqueous phase volume ratio (O / A) 4.

[0146]

[0147] Example D2: Performance test of lithium extractant prepared by the present invention II (YL-2: lithium precipitation mother liquor)

[0148] The organic phase for lithium extraction (STLK-Z7AN: 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, STLK-Y8AN: 2-hydroxy-4-octyloxy-5-nitrobenzophenone, STLK-Z9AN: 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, STLK-Z10AN: 2-hydroxy-4-decyloxy-5-nitrobenzophenone) prepared in Examples B1-B3 was prepared by mixing 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone, trioctylphosphine oxide or / and trialkylphosphine oxide, and solvent oil (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) with 2-hydroxy-4-decyloxy-5-nitrobenzophenone. 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), the lithium in a lithium carbonate mother liquor is separated by extraction, so that the lithium in the brine is selectively extracted into the organic phase. The composition of the lithium carbonate mother liquor used is: Li: 1.089g / L, Na: 76.611g / L, Cl: 118.08g / L, CO3: 4.7g / L, pH = 10.74. Temperature: room temperature (25℃~27℃). Organic phase: 20mL. Organic phase / aqueous phase volume ratio (O / A) 4.

[0149]

[0150] Example D3: Performance test III of lithium extractant prepared by the present invention (YL-3: boron-containing lithium sodium alkaline solution) The 2-hydroxy-4-alkoxy-5-nitrobenzophenone / acetophenone, trioctylphosphine oxide or / and trialkylphosphine oxide, and solvent oil prepared in Examples B1-B3 were used to prepare a lithium extraction organic phase (STLK-Z7AN: 2-hydroxy-4-heptyloxy-5-nitrobenzophenone, STLK-Y8AN: 2-hydroxy-4-octyloxy-5-nitrobenzophenone, STLK-Z9AN: 2-hydroxy-4-nonyloxy-5-nitrobenzophenone, STLK- 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), the lithium in a boron lithium sodium alkaline solution is separated by extraction method, so that the lithium in the brine is selectively extracted into the organic phase. The boron lithium sodium alkaline solution YL-3 used is composed of: Li: 0.515g / L, Na: 85.472g / L, Cl: 131.7g / L, B: 0.82g / L, pH = 10.00. Temperature: room temperature (25℃~27℃). Organic phase: 20 mL. Organic phase / aqueous phase volume ratio (O / A) 4.

[0151]

[0152] Example D4: Performance test IV of lithium extractant prepared by the present invention (YL-4: mixed solution of lithium hydroxide and sodium chloride)

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

[0154]

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

[0156] Example E1: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (the amount of nitric acid used is 0.95 times the molar equivalent of the intermediate 2-hydroxy-4-n-octyloxy-benzophenone) 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid, stirred to completely dissolve it, and then the flask was placed in an oil bath at 50°C, 2.6 mL of 68 wt% nitric acid was added, and after reacting for 12 h, the temperature was raised to 50°C and the reaction was continued for 4 h, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. 400 mL of D80 solvent oil was taken separately, 13.2 g of trialkylphosphine oxide was added, and stirred to form a uniform solution. Afterwards, all the prepared D80 solvent oil containing trialkylphosphine oxide was mixed with the above acetic acid solution, and then 60g of anhydrous NaOH was added, and after sufficient mixing, the mixture was allowed to stand for stratification, and the lower aqueous phase was released to obtain the upper oil phase, which was washed with water several times and used as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-E1 for lithium extraction was obtained respectively.

[0157] 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) 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid, stirred to completely dissolve, and then the flask was placed in an oil bath at 50°C, 3.0 mL of 68 wt% nitric acid was added, and after reacting for 12 h, the temperature was raised to 50°C and the reaction was continued for 4 h, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. 400 mL of D80 solvent oil was taken separately, 13.2 g of trialkylphosphine oxide was added, and stirred to form a uniform solution. Afterwards, all the prepared D80 solvent oil containing trialkylphosphine oxide was mixed with the above acetic acid solution, and then 60g of anhydrous NaOH was added, and after sufficient mixing, the mixture was allowed to stand for stratification, and the lower aqueous phase was released to obtain the upper oil phase, which was washed with water several times and used as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-E2 for lithium extraction was obtained respectively.

[0158] Example E3: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (the amount of nitric acid used is 1.2 times the molar equivalent of the intermediate 2-hydroxy-4-n-octyloxy-benzophenone) 13.06 g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 80 mL of glacial acetic acid, stirred to completely dissolve it, and then the flask was placed in an oil bath at 50°C, 3.3 mL of 68 wt% nitric acid was added, and after reacting for 12 h, the temperature was raised to 50°C and the reaction was continued for 4 h, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. 400 mL of D80 solvent oil was taken separately, 13.2 g of trialkylphosphine oxide was added, and stirred to form a uniform solution. Afterwards, all the prepared D80 solvent oil containing trialkylphosphine oxide was mixed with the above acetic acid solution, and then 60g of anhydrous NaOH was added, and after sufficient mixing, the mixture was allowed to stand for stratification, and the lower aqueous phase was released to obtain the upper oil phase, which was washed with water several times and used as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-E3 for lithium extraction was obtained respectively.

[0159] 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, take 60mL of the lithium-containing solution YL-2, and act with the composite liquid organic composition in a separatory funnel for 5 minutes, then stand for 10 minutes to separate the layers, and release the lower aqueous solution; repeat the above process 3 times, so that all the extractants in the composite liquid organic composition act with the metal ions to reach the extraction saturation state. Afterwards, the obtained saturated extracted organic phase is acted with 20mL of 0.6mol / L hydrochloric acid aqueous solution 3 times, and all the stripping solutions obtained for 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.

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

[0161] The results are as follows:

[0162]

[0163] Example F Group: Effect of different acetic acid dosages on extraction performance

[0164] Example F1: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (acetic acid dosage: 2L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octyloxy-benzophenone) 13.06g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 80mL of glacial acetic acid, stirred to completely dissolve, then placed the flask in an oil bath at 50°C, added 2.75mL of 68wt% nitric acid, reacted for 12h, heated to 50°C and continued to react for 4h, then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. Separately, 400mL of D80 solvent oil was added, 13.2g of trialkylphosphine oxide was added, and stirred to form a uniform solution. Afterwards, all the prepared D80 solvent oil containing trialkylphosphine oxide was mixed with the above acetic acid solution, and then 60g of anhydrous NaOH was added, and after being fully mixed, the mixture was allowed to stand for stratification, and the lower aqueous phase was released to obtain the upper oil phase, which was washed with water several times and used as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-F1 for lithium extraction was obtained respectively.

[0165] Example F2: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (acetic acid dosage: 1L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octyloxy-benzophenone) 13.06g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 40mL of glacial acetic acid, stirred to completely dissolve, and then the flask was placed in an oil bath at 50°C, 2.75mL of 68wt% nitric acid was added, and after reacting for 12h, the temperature was raised to 50°C and the reaction was continued for 4h, and then cooled to room temperature to obtain an acetic acid solution of 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone. 400mL of D80 solvent oil was taken separately, 13.2g of trialkylphosphine oxide was added, and stirred to form a uniform solution. Afterwards, all the prepared D80 solvent oil containing trialkylphosphine oxide was mixed with the above acetic acid solution, and then 30g of anhydrous NaOH was added, and after sufficient mixing, the mixture was allowed to stand for stratification, and the lower aqueous phase was released to obtain the upper oil phase, which was washed with water several times and used as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-F2 for lithium extraction was obtained respectively.

[0166] Example F3: Preparation of a composite liquid organic composition containing 2-hydroxy-4-n-octyloxy-5-nitrobenzophenone (acetic acid dosage: 0.5L glacial acetic acid per mole of intermediate 2-hydroxy-4-n-octyloxy-benzophenone) 13.06g of 2-hydroxy-4-n-octyloxybenzophenone was added to a three-necked flask containing 20mL of glacial acetic acid, stirred to completely dissolve, and then placed the flask in an oil bath at 50°C, added 2.75mL of 68wt% nitric acid, reacted for 12h, heated to 50°C and continued to react for 4h, and then cooled 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. Afterwards, all the prepared D80 solvent oil containing trialkylphosphine oxide was mixed with the above acetic acid solution, and then 15g of anhydrous NaOH was added. After being fully mixed, the mixture was allowed to stand for stratification, and the lower aqueous phase was released to obtain the upper oil phase, which was washed with water several times and used as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-F3 for lithium extraction was obtained respectively.

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

[0168] Take 13.06g of 2-hydroxy-4-octyloxybenzophenone, add it to a three-necked flask containing 10mL of glacial acetic acid, stir it to completely dissolve, 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-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 fully mixing, stand for stratification, release the lower aqueous phase, obtain the upper oil phase, and wash the oil phase with water several times as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-F4 for lithium extraction is obtained respectively.

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

[0170] Take 13.06g of 2-hydroxy-4-octyloxybenzophenone, 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-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 after sufficient mixing, stand for stratification, release the lower aqueous phase, obtain the upper oil phase, and wash the oil phase with water several times as an extractant for lithium extraction. The composite liquid organic composition STLK-Z8AN-F5 for lithium extraction is obtained respectively.

[0171] The lithium-containing solution YL-2 in Example D2 was used as the original test 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 under different intermediates: nitric acid ratios. The specific operation is: take 20mL of the composite liquid organic composition, take 60mL of the lithium-containing solution YL-2, and act with the composite liquid organic composition in a separatory funnel for 5 minutes, then stand for 10 minutes to separate the layers, and release the lower aqueous solution; repeat the above process 3 times, so that all the extractants in the composite liquid organic composition act with the metal ions to reach the extraction saturation state. Afterwards, the obtained saturated extracted organic phase is acted with 20mL of 0.6mol / L hydrochloric acid aqueous solution 3 times, and all the stripping solutions obtained for 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.

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

[0173] The results are as follows:

[0174]

Claims

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

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

100.

6. The liquid organic composition for extracting lithium as claimed in 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, isoamyl alcohol, 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 of claim 16, wherein the halogenated hydrocarbon is heptyl chloride, octane chloride, nonane chloride, decane chloride, dodecane chloride, tridecane chloride, tetradecane chloride, pentadecane chloride, hexadecane chloride, heptyl bromide, octane bromide, nonane bromide, decane bromide, dodecane bromide, tridecane bromide, tetradecane bromide, pentadecane bromide, hexadecane bromide, heptyl iodide, octane iodide, nonane iodide, decane iodide, dodecane iodide, tridecane iodide, tetradecane iodide, pentadecane iodide, hexadecane iodide, or a C7-C16 halogenated hydrocarbon mixture, and isomers of these halogenated hydrocarbons.

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