Naphthalene ring-containing carboxylic acid compound as well as preparation method and application thereof

Abstract

The invention relates to a naphthalene ring-containing carboxylic acid compound as well as a preparation method and application thereof. The naphthalene ring-containing carboxylic acid compound has the structural characteristics as shown in the following formula (I). The naphthalene ring-containing carboxylic acid compound has good extraction selectivity on vanadium ions (V < 5 + >) in a vanadium-based catalyst catalysis waste liquid. (I)

Description

Technical Field

[0001] This application relates to the field of catalyst recovery technology, and in particular to naphthalene-containing carboxylic acid compounds, their preparation methods, and applications. Background Technology

[0002] Vanadium-based catalysts are "star catalysts" in the field of industrial catalysis, mainly used in selective catalytic reduction (SCR) reactions of nitrogen-containing oxides, especially dominating in denitrification scenarios with both stationary and mobile sources. However, vanadium-based catalysts face problems such as irreversible chemical deactivation (arsenic / alkali metal poisoning, phosphorus deposition) and thermal sintering deactivation (V₂O₅ volatilization, TiO₂ anatase phase transformation) during operation, leading to shortened lifespan and high yields of spent catalysts. Therefore, there is an urgent need to develop a method for the recovery and utilization of vanadium from vanadium-based catalyst catalytic waste liquid.

[0003] In addition to vanadium ions (V), the catalytic waste liquid of vanadium-based catalysts contains catalytic waste liquid. 5+ In addition to vanadium-based catalyst promoters, it also mainly contains tungsten ions (W) derived from vanadium-based catalyst promoters. 6+ ), molybdenum ions (Mo) 6+ ) and titanium ions (Ti) derived from vanadium-based catalyst supports or co-used titanium-based catalysts. 4+ Meanwhile, using extractants to extract and separate metal ions from waste liquid is a relatively simple and environmentally friendly recycling method. However, current extraction systems for industrial vanadium, such as amine extraction systems and phosphorus extraction systems, mostly suffer from limitations in removing vanadium ions (V2) from vanadium-based catalyst-catalyzed waste liquid. 5+ The problem of poor extraction selectivity. Summary of the Invention

[0004] Based on this, this application provides a method for treating vanadium ions (V2) in vanadium-based catalyst waste liquid. 5+ Extraction of naphthalene-containing carboxylic acid compounds with good extraction selectivity, their preparation methods, and applications.

[0005] A first aspect of this application provides a naphthalene-containing carboxylic acid compound or a salt thereof having the structural features shown in formula (I):

[0006] (I),

[0007] R1 is a C3~C12 alkyl group;

[0008] R2 is H or a C1~C12 alkyl group.

[0009] In one embodiment, R1 is a C3-C12 straight-chain alkyl group, optionally a C4-C6 straight-chain alkyl group; and / or,

[0010] R2 is a C7 to C10 alkyl group.

[0011] In one embodiment, the naphthalene-containing carboxylic acid compound has the structural features shown in formula (II):

[0012] (II).

[0013] In one embodiment, the naphthalene-containing carboxylic acid compound is one or more of the following compounds:

[0014] , ,

[0015] , ,

[0016] and .

[0017] A second aspect of this application provides a method for preparing the naphthalene-containing carboxylic acid compound or its salt as described in the first aspect, comprising the following steps:

[0018] Compound A and compound B are reacted;

[0019] Compound A has the following structural features:

[0020] X is a halogen;

[0021] Compound B has the following structural features:

[0022] .

[0023] In one embodiment, the preparation method has one or more of the following features:

[0024] (1) The reaction is carried out in the presence of a solvent and a base;

[0025] Optionally, the solvent includes ether solvents, and more preferably tetrahydrofuran;

[0026] Optionally, the volume-to-mass ratio of the solvent to compound B is (1~8) mL:1 g;

[0027] Optionally, the alkali includes one or more of alkali metals and alkali metal hydrides, and is further optionally one or more of sodium metal and sodium hydride;

[0028] Optionally, the molar ratio of the base to compound A is (1~1.5):1;

[0029] (2) The molar ratio of compound A to compound B is 1: (1~1.5);

[0030] (3) The reaction temperature is 60℃~70℃;

[0031] (4) The reaction time is 6h~12h.

[0032] A third aspect of this application provides the use of the naphthalene-containing carboxylic acid compounds or their salts as described in the first aspect as extractants;

[0033] Optionally, the extractant is used to extract and separate metal ions;

[0034] Further optionally, the metal ions include target ions and ions to be separated, wherein the target ions include vanadium ions, and the ions to be separated include one or more of tungsten ions, molybdenum ions, and titanium ions.

[0035] A fourth aspect of this application provides an extraction composition comprising an extractant and a diluent, said extractant comprising one or more of the naphthalene-containing carboxylic acid compounds and their salts as described in the first aspect;

[0036] Optionally, the diluent is one or more selected from solvent oil, kerosene, hexane, heptane, and dodecane;

[0037] Optionally, in the extraction composition, the molar concentration of the extractant is 0.1 mol / L to 1.5 mol / L.

[0038] A fifth aspect of this application provides an extraction method comprising the following steps:

[0039] The aqueous phase containing metal ions is extracted using the extraction composition described in the fourth aspect, and the organic phase is collected.

[0040] Optionally, the volume ratio of the extraction composition to the aqueous phase containing metal ions is 1:(1~10);

[0041] Optionally, the extraction pH is 7-13, further preferably 10-13, and even more preferably 10-11;

[0042] Optionally, the extraction temperature is 10℃~50℃;

[0043] Optionally, the extraction time is 5 min to 60 min;

[0044] Optionally, the extraction method includes oscillation;

[0045] Optionally, the metal ions include target ions and ions to be separated, wherein the target ions include vanadium ions, and the ions to be separated include one or more of tungsten ions, molybdenum ions, and titanium ions.

[0046] In some embodiments, the extraction method further includes a step of back-extracting the organic phase:

[0047] The organic phase is mixed with an aqueous solution of acid, and the aqueous phase containing the target ion is collected.

[0048] Optionally, the molar concentration of the aqueous solution of the acid is 0.5 mol / L to 5 mol / L;

[0049] Optionally, the acid in the aqueous solution is an inorganic acid, which may include one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid.

[0050] Optionally, the volume ratio of the organic phase to the aqueous solution of the acid is (1~50):1, and more preferably (10~20):1.

[0051] The aforementioned naphthalene-containing carboxylic acid compounds or their salts, through appropriate structural design, mainly employ a naphthalene ring with ortho-carboxyl groups and ether oxygen bonds on the naphthalene ring, are effective against metal ions, especially vanadium ions (V). 5+ It has good affinity and can be used as an extractant for metal ions, especially vanadium ions (V). 5+ ) and other ions (mainly including tungsten ions (W 6+ ), molybdenum ions (Mo) 6 + ), titanium ions (Ti 4+ The extraction and separation of vanadium using methods such as extraction and separation of spent catalysts (e.g., vanadium) exhibits good selectivity and has significant application prospects. It can be used for highly selective extraction and separation of vanadium in various scenarios, including the recovery of spent catalysts.

[0052] Meanwhile, when using the above-mentioned naphthalene-containing carboxylic acid compounds or their salts as extractants, the saturation capacity of metal ions is high, and the resulting organic phase is easy to back-extract, with low back-extraction acidity and high back-extraction rate, which helps to simplify the operation and reduce costs. Attached Figure Description

[0053] Figure 1 The extraction rates (E%-pH curves) of compound WH001 for each ion are shown. Detailed Implementation

[0054] The following detailed description, in conjunction with specific embodiments, illustrates the naphthyl ring carboxylic acid compounds of this application, their preparation methods, and their applications. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0055] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0056] As used herein, the terms “and / or,” “or / and,” and “and / or” may include any one of two or more of the related listed items, as well as any and all combinations of the related listed items, including any two related listed items, any more related listed items, or a combination of all the related listed items.

[0057] In this article, "one or more" refers to any one, two or more of the listed items.

[0058] In this application, terms such as "first aspect," "second aspect," "third aspect," and "fourth aspect" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, terms such as "first," "second," "third," and "fourth" serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0059] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0060] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0061] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0062] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0063] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0064] In this application, room temperature generally refers to 4℃~30℃, and preferably 20±5℃.

[0065] In this application, the term "alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. Accordingly, an alkyl group can be a straight-chain alkyl group or a linear alkyl group. Phrases containing this term, such as "C1~C12 alkyl," refer to alkyl groups containing 1 to 12 carbon atoms, and each occurrence can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, or C12 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butyl(-CH2CH(CH3)CH2CH3), 1-hexyl(-CH2CH2CH2CH2CH2CH3), 2-hexyl(-CH(CH3)CH2CH2CH2CH3), 3-hexyl(-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl(-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl(-CH(CH3)CH( CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3 and octyl (-(CH2)7CH3).

[0066] In this application, the term "halogen" refers to fluorine, chlorine, bromine, or iodine, optionally chlorine or bromine, and further optionally bromine.

[0067] In this application, the extraction rate E is the percentage of the extracted substance transferred from the aqueous phase to the organic phase during the extraction process, relative to the total amount of the extracted substance in the original aqueous phase, i.e.:

[0068] E = 100% × (C'aq - Caq) / C'aq

[0069] Caq represents the concentration of metal ions in the aqueous phase at equilibrium after one extraction; C'aq represents the concentration of metal ions in the aqueous phase before one extraction.

[0070] Some embodiments of this application provide naphthalene-containing carboxylic acid compounds or salts thereof having the structural features shown in formula (I):

[0071] (I)

[0072] R1 is a C3~C12 alkyl group;

[0073] R2 is H or a C1~C12 alkyl group.

[0074] Without limitation, the salts containing naphthalene ring carboxylic acids may include, for example, one or more of sodium salts, potassium salts, or ammonium salts.

[0075] In some embodiments, R1 is a C3-C12 straight-chain alkyl group. Further, R1 is a C4-C6 straight-chain alkyl group. Without limitation, R1 includes, but is not limited to, n-butyl, n-pentyl, n-hexyl, or n-octyl.

[0076] In some embodiments, R2 is a C7 to C10 alkyl group. Without limitation, R2 includes, but is not limited to, straight-chain or straight-chain octyl, or straight-chain or straight-chain nonyl.

[0077] In some embodiments, the sum of the carbon numbers n of R1 and R2 is 3 to 20. Specifically, n includes, but is not limited to: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or any range between the two aforementioned.

[0078] In some embodiments, the naphthalene-containing carboxylic acid compound has the structural features shown in formula (II):

[0079] (II).

[0080] Without limitation, the naphthalene-containing carboxylic acid compound is one or more of the following compounds:

[0081] , ,

[0082] , ,

[0083] and .

[0084] Other embodiments of this application provide a method for preparing the aforementioned naphthalene-containing carboxylic acid compound or its salt, comprising the following steps:

[0085] Compound A and compound B are reacted;

[0086] Compound A has the following structural features:

[0087] X is a halogen;

[0088] Compound B has the following structural features:

[0089] .

[0090] Understandably, the salts of the naphthalene-containing carboxylic acid compounds can be prepared by reacting the naphthalene-containing carboxylic acid compound with a corresponding alkali in an acid-base salt-forming reaction at a molar ratio of 1:1. The alkali can be a conventional alkali in the art, such as an alkali metal hydroxide or ammonia, specifically sodium hydroxide, potassium hydroxide, or ammonia. Therefore, the salts of the naphthalene-containing carboxylic acid compounds can be sodium, potassium, or ammonium salts.

[0091] In some of these embodiments, the reaction is carried out in the presence of a solvent and a base.

[0092] Furthermore, the solvent includes ether solvents, and may be further selected as tetrahydrofuran.

[0093] Further, the volume-to-mass ratio of the solvent to compound B is (1~8) mL:1 g. Specifically, this volume-to-mass ratio includes, but is not limited to: 1 mL:1 g, 1.5 mL:1 g, 2 mL:1 g, 2.5 mL:1 g, 3 mL:1 g, 3.5 mL:1 g, 4 mL:1 g, 4.5 mL:1 g, 5 mL:1 g, 5.5 mL:1 g, 6 mL:1 g, 6.5 mL:1 g, 7 mL:1 g, 7.5 mL:1 g, 8 mL:1 g, or a range between any two of the foregoing.

[0094] Further, the alkali includes one or more of alkali metals and alkali metal hydrides, and may further be one or more of sodium metal and sodium hydride.

[0095] Further, the molar ratio of the base to compound A is (1~1.5):1. Specifically, this molar ratio includes, but is not limited to: 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, or any range between the two aforementioned.

[0096] Furthermore, the molar ratio of compound A to compound B is 1:(1~1.5). Specifically, this molar ratio includes, but is not limited to: 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5 or any range between the two aforementioned.

[0097] In some embodiments, the reaction temperature is 60°C to 70°C. Specifically, the reaction temperature includes, but is not limited to, 60°C, 63°C, 65°C, 67°C, 70°C, or any range between the foregoing.

[0098] The reaction time can be monitored by observing the reaction solution to determine the reaction progress. Detection methods can include, for example, TLC, HPLC, or NMR. Generally, the reaction endpoint is defined as the disappearance of compound A or the cessation of the reaction. In some embodiments, the reaction time is 6 to 12 hours. Specifically, the reaction time includes, but is not limited to, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, or any range between the two.

[0099] Other embodiments of this application provide the use of naphthalene-containing carboxylic acid compounds or their salts as described above as extractants.

[0100] In some embodiments, the extractant is used to extract and separate metal ions. Understandably, the metal ions include target ions and ions to be separated. Further, the target ions include vanadium ions (V2). 5+ The ions to be separated include tungsten ions (W). 6+ ), molybdenum ions (Mo) 6+ ) and titanium ions (Ti 4+ One or more of the following.

[0101] In other embodiments of this application, an extraction composition is provided, comprising an extractant and a diluent, wherein the extractant comprises one or more of the naphthalene-containing carboxylic acid compounds and their salts as described above.

[0102] In some embodiments, the diluent is one or more selected from solvent oil, kerosene, hexane, heptane, and dodecane. Examples of solvent oils include, for example, one or more selected from solvent oil No. 200, solvent oil No. 260, and Escaid 110; examples of hexane include n-hexane; examples of heptane include n-heptane; and examples of dodecane include n-dodecane.

[0103] In some embodiments, the molar concentration of the extractant in the extraction composition is 0.1 mol / L to 1.5 mol / L. Specifically, the molar concentration includes, but is not limited to: 0.1 mol / L, 0.16 mol / L, 0.2 mol / L, 0.25 mol / L, 0.33 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.62 mol / L, 0.8 mol / L, 1 mol / L, 1.2 mol / L, 1.5 mol / L, or a range between any two of the foregoing.

[0104] Other embodiments of this application provide an extraction method, including the following steps:

[0105] The aqueous phase containing metal ions was extracted using the extraction composition described above, and the organic phase was collected.

[0106] Understandably, the metal ions contained in the aqueous phase include target ions and ions to be separated. In some embodiments, the target ions include vanadium ions, and the ions to be separated include one or more of tungsten ions, molybdenum ions, and titanium ions. After extraction, the target ions and ions to be separated are separated, wherein the target ions are selectively extracted and collected into the organic phase, while the ions to be separated mostly remain in the aqueous phase. By using the above-described extractant or extraction composition, vanadium ions can be separated from tungsten ions, molybdenum ions, and titanium ions with high selectivity, achieving selective recovery and utilization of vanadium ions.

[0107] In some embodiments, during the extraction process, vanadium ions (V... 5+ The saturation capacity is ≥30g / L.

[0108] Without limitation, the aqueous phase containing metal ions can be derived from the alkaline leaching solution of spent vanadium catalyst.

[0109] In some embodiments, the volume ratio of the extraction composition to the aqueous phase containing metal ions is 1:(1~10). Specifically, this volume ratio includes, but is not limited to: 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or any range between the foregoing. Further, the volume ratio of the extraction composition to the aqueous phase containing metal ions is 1:(1~5).

[0110] In some embodiments, the extraction pH (i.e., the pH of the mixture of the extraction composition and the aqueous phase containing the metal ions) is 7 to 13. Specifically, the extraction pH includes, but is not limited to, 7, 8, 9, 10, 11, 12, 13, or any range between the foregoing. Further, the extraction pH is 10 to 13, and even further, the extraction pH is 10 to 11.

[0111] Understandably, the pH of the extraction can be adjusted by saponifying the naphthalene-containing carboxylic acid compound, or by adjusting the molar ratio between the naphthalene-containing carboxylic acid compound and its salt. In some embodiments, the molar ratio of the naphthalene-containing carboxylic acid compound to its salt is (0.4–9):1. Specifically, this molar ratio includes, but is not limited to, 0.4:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or any range between the foregoing.

[0112] In this application, "saponification" refers to the conversion of hydrogen ions in a naphthalene-containing carboxylic acid compound into alkali metal ions and / or NH4+ ions. 4+ (converted alkali metal ions and / or NH4+) 4+ Extraction is achieved by exchanging the extracted metal ions with the aqueous phase. The saponification step involves mixing the organic phase containing a naphthalene ring carboxylic acid compound with an aqueous solution of alkali. In some embodiments, the aqueous solution of alkali used for saponification can be an aqueous solution of sodium hydroxide, potassium hydroxide, or ammonia.

[0113] Saponification rate refers to the concentration of alkali metals and / or NH4+ in naphthalene ring carboxylic acid compounds. 4+ The proportion of hydrogen ions in the original body.

[0114] In some embodiments, the saponification rate of the naphthalene-containing carboxylic acid compound is 0% to 70%. Specifically, the saponification rate includes, but is not limited to, 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, or any range between the foregoing.

[0115] In some embodiments, the extraction temperature is 10°C to 50°C. Specifically, the extraction temperature includes, but is not limited to, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, or any range between the foregoing. Further, the extraction temperature is 25°C to 40°C.

[0116] In some embodiments, the extraction time is 5 min to 60 min. Specifically, the extraction time includes, but is not limited to: 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, or any range between the two for the foregoing.

[0117] Without limitation, extraction methods include one or more of shaking and stirring, primarily for mass transfer purposes, to ensure uniform mixing of the organic and aqueous phases.

[0118] In some embodiments, the extraction method further includes a step of back-extracting the organic phase.

[0119] Further, the organic phase is mixed with an aqueous solution of acid, and the aqueous phase containing the target ion is collected. After extracting the target ion using the above-mentioned extractant or extraction composition, the target ion can be easily and conveniently back-extracted into the aqueous phase using an aqueous solution of acid, with a small amount of acid required. Simultaneously, due to thorough back-extraction, the organic phase can be regenerated and reused.

[0120] Further, the molar concentration of the aqueous solution of the acid is 0.5 mol / L to 5 mol / L. Specifically, this molar concentration includes, but is not limited to: 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L, 5 mol / L, or any range between the foregoing. Even further, the molar concentration of the aqueous solution of the acid is 1 mol / L to 3 mol / L.

[0121] Furthermore, the acid in the aqueous solution is an inorganic acid. Specifically, the acid includes one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. Even further, the acid includes sulfuric acid.

[0122] Further, the volume ratio of the organic phase to the aqueous solution of the acid is (1~50):1. Specifically, this volume ratio includes, but is not limited to: 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, or any range between the foregoing. A further option is (10~20):1.

[0123] In some implementations, the single-step back-extraction rate is >99.5% during the back-extraction step.

[0124] For experimental parameters not specified in the following specific embodiments, please refer to the guidelines given in this application document first, or refer to experimental manuals or other experimental methods known in the art, or refer to the experimental conditions recommended by the manufacturer.

[0125] The raw materials and reagents involved in the following specific embodiments can be obtained commercially or prepared by those skilled in the art using known methods.

[0126] The test data used in the following specific embodiments are from a Bruker 400MHz nuclear magnetic resonance spectrometer and an Agilent 8890GC-5977C gas chromatography-mass spectrometry system.

[0127] Example 1

[0128] This embodiment provides compound WH001, whose preparation method is as follows:

[0129]

[0130] 83.1 g of isooctylnaphthol, 250 mL of tetrahydrofuran (THF), and 8.8 g of sodium granules were added to a three-necked flask. The temperature was raised to 60 °C, and 40 mL of a THF solution containing 8 mol / L 2-bromooctanoic acid was added dropwise. The reaction was continued at 60 °C for 6 h, resulting in the formation of a large amount of white solid with a small amount of sodium granules remaining. After cooling, the THF was removed by rotary evaporation. 200 mL of water and 200 mL of ethyl acetate (EA) were added to the concentrate, and the mixture was shaken to separate the layers. The aqueous layer was collected. The aqueous layer was acidified with hydrochloric acid to pH≈1, extracted with ethyl acetate, and the organic phase was washed twice with water. The product was then evaporated to dryness to obtain 88.3 g of a pale yellow product, designated as compound WH001 with a purity of 98%.

[0131] 1 H NMR (400MHz, CDCl3) δ10.20(1H,br.);7.32(2H,t);6.68(2H,d);6.59(2H,d);4.84-4.81(1H,m);3.8(2H,m);2.6(2H,m);2.20-2.08(2H ,m); 1.66-1.56(3H,m); 1.46-1.38(12H,m); 0.99(3H,t,J=7.3,CH3); 0.93(3H,t,J=7.3,CH3); 0.90(3H,t,J=7.3,CH3).

[0132] 13 C NMR (101MHz, CDCl3) δ173.0, 153.4, 131.5, 129.6, 128.4, 125.5,125.4, 123.9, 123.6, 122.4, 121.9, 118.6, 118.5, 115.6 , 114.6, 90.0,41.1, 32.5, 29.3, 31.8, 27.5, 22.3, 14.2, 14.1, 13.9.

[0133] MS[MH] - 397.

[0134] Example 2

[0135] This embodiment provides compound WH002, whose preparation method is as follows:

[0136]

[0137] 87.7 g of nonylnaphthol, 250 mL of tetrahydrofuran (THF), and 8.8 g of sodium granules were added to a three-necked flask. The temperature was raised to 60 °C, and 40 mL of a THF solution containing 8 mol / L 2-bromohexanoic acid was added dropwise. The reaction was continued at 60 °C for 6 h, resulting in the formation of a large amount of white solid with a small amount of sodium granules remaining. After cooling, the THF was removed by rotary evaporation. 200 mL of water and 200 mL of ethyl acetate (EA) were added to the concentrate, and the mixture was shaken to separate the layers. The aqueous layer was collected and acidified with hydrochloric acid to pH ≈ 1. The aqueous layer was extracted with ethyl acetate, and the organic phase was washed twice with water. The product was then evaporated to dryness to obtain 85.2 g of a pale yellow product, designated as compound WH002 with a purity of 98%.

[0138] 1 H NMR (400MHz, CDCl3) δ10.20(1H,br.);7.32(2H,t);6.68(2H,d);6.59(2H,d);4.84-4.81(1H,m);3.8(2H,m);2.6(2H,m);2.20-2.08(2H ,m); 1.66-1.56(3H,m); 1.54-1.38(13H,m); 0.98(3H,t,J=7.3,CH3); 0.91(3H,t,J=7.3,CH3).

[0139] 13 C NMR (101MHz, CDCl3) δ169.8, 165.7, 162.9, 159.0, 153.4, 131.5, 129.6, 128.4, 125.4, 123.9, 123.6, 121.9, 118.6 , 118.5, 115.6, 114.6, 90.0, 41.1, 32.5, 29.3, 27.5, 22.3, 14.2, 14.1, 13.9.

[0140] MS[MH] - 383.

[0141] Example 3

[0142] This embodiment provides compound WH003, whose preparation method is as follows:

[0143]

[0144] 46.5 g of naphthol, 250 mL of tetrahydrofuran (THF), and 8.8 g of sodium granules were added to a three-necked flask. The mixture was heated to 60 °C, and 40 mL of a THF solution containing 8 mol / L 2-bromotetradecyl acid was added dropwise. The reaction was continued at 60 °C for 6 h, resulting in the formation of a large amount of white solid with a small amount of sodium granules remaining. After cooling, the THF was removed by rotary evaporation. 200 mL of water and 200 mL of ethyl acetate (EA) were added to the concentrate, and the mixture was shaken to separate the layers. The aqueous layer was collected and acidified with hydrochloric acid to pH ≈ 1. The aqueous layer was extracted with ethyl acetate, and the organic phase was washed twice with water. The product was then evaporated to dryness to obtain 82.1 g of a pale yellow product, designated as compound WH003 with a purity of 98%.

[0145] 1 H NMR (400MHz, CDCl3) δ10.20(1H,br.);7.32-7.10(2H,t);6.68(2H,d);6.59(2H,d);4.88-4.81(1H,m);3.8(2H,m);2.6(2H ,m); 2.20-2.08(2H,m); 1.66-1.56(3H,m); 1.49-1.32(14H,m); 0.92(3H,t,J=7.3,CH3).

[0146] 13 C NMR (101MHz, CDCl3) δ171.6, 153.5, 131.6, 128.6, 126.4, 125.6,125.3, 124.9, 123.6, 122.3, 121.8, 118.7, 115.8, 114.7, 90.1, 41.3, 32.6, 29.4, 31.7, 27.5, 22.6, 14.3, 14.1, 13.6.

[0147] MS[MH] - 369.

[0148] Example 4

[0149] This embodiment provides compound WH004, whose preparation method is as follows:

[0150]

[0151] 101.4 g of dodecylnaphthol, 250 mL of tetrahydrofuran (THF), and 8.8 g of sodium granules were added to a three-necked flask. The temperature was raised to 60 °C, and 40 mL of a THF solution containing 8 mol / L 2-bromotetradecyl acid was added dropwise. The reaction was continued at 60 °C for 6 h, resulting in the formation of a large amount of white solid with a small amount of sodium granules remaining. After cooling, the THF was removed by rotary evaporation. 200 mL of water and 200 mL of ethyl acetate (EA) were added to the concentrate, and the mixture was shaken to separate the layers. The aqueous layer was collected and acidified with hydrochloric acid to pH ≈ 1. The aqueous layer was extracted with ethyl acetate, and the organic phase was washed twice with water. The product was then evaporated to dryness to obtain 119.4 g of a pale yellow product, designated as compound WH004 with a purity of 98%.

[0152] 1 H NMR (400MHz, CDCl3) δ10.20(1H,br.);7.32-7.10(2H,t);6.68(2H,d);6.59(2H,d);4.83-4.80(2H,m);2.6(2H,m);2.20-2.08(2H ,m); 1.66-1.56(3H,m); 1.49-1.32(18H,m); 1.30-1.02(18H,m); 0.96(3H,t,J=7.3,CH3); 0.92(3H,t,J=7.3,CH3).

[0153] 13 C NMR (101MHz, CDCl3) δ174.6, 157.4, 155.9, 153.1, 149.3, 148.9,148.4, 142.7, 140.0, 137.6, 137.0, 136.5, 136.4, 136.1, 134.3, 133.8, 132.6,131.5, 129.6, 125.5, 123.9, 123.6, 121.9, 118.6, 118.5, 114.6, 90.0,41.1, 32.5, 29.3, 31.8, 27.5, 22.3, 14.2, 14.1, 13.9.

[0154] MS[MH] - :537.

[0155] Comparative Example 1

[0156] This comparative example demonstrates the preparation method of compound D1, and the steps are as follows:

[0157]

[0158] 83.1 g of isooctylphenol, 225 mL of tetrahydrofuran (THF), and 8.8 g of 60% sodium hydride (dispersed in mineral oil) were added to a three-necked flask. The mixture was heated to 60 °C, and 40 mL of 8 mol / L 2-bromooctanoic acid in THF solution was added dropwise. The reaction was continued at 60 °C for 4 h, resulting in the formation of a large amount of white solid. After cooling, THF was removed by rotary evaporation. 200 mL of water and 200 mL of ethyl acetate (EA) were added to the concentrate, and the mixture was shaken to separate the layers. The aqueous layer was collected. The aqueous layer was acidified with hydrochloric acid to pH≈1, extracted with ethyl acetate, and the organic phase was washed twice with water. The product was then evaporated to dryness to obtain 81.6 g of a pale yellow product, namely compound D1, with a purity of 98%.

[0159] 1 H NMR (400MHz, CDCl3) δ10.20 (1H,br.); 8.60(2H,t); 7.30(2H,t); 6.66(2H,d); 4.83-4.81(1H,m); 2.57(2H,m); 2.17-2.04(2H,m); 1.62-1.53(3H,m); 1.42-1.34(12H,m); 0.99(3H,t,J=7.3,CH3); 0.93(3H,t,J=7.3,CH3); 0.90(3H,t,J=7.3,CH3).

[0160] 13 C NMR (101MHz, CDCl3) δ173.0, 153.4, 131.5, 129.6, 128.4, 125.5, 125.1, 119.6, 118.9, 116.3, 115.6, 90.0, 41.1, 32.5, 29.3, 31.8, 14.2, 14.1, 13.9.

[0161] MS[MH] - 347.

[0162] Comparative Example 2

[0163] This comparative example demonstrates the preparation method of compound D2, and the steps are as follows:

[0164]

[0165] 92.9 g of (4-isooctyl)naphthylmethylene magnesium bromide (Gernristor's reagent), 225 mL of tetrahydrofuran (THF), and 10.6 g of palladium powder were added to a three-necked flask. The temperature was raised to 60 °C, and 40 mL of 8 mol / L 2-bromooctanoic acid in THF solution was added dropwise. The reaction was continued at 60 °C for 16 h. After cooling, THF was removed by rotary evaporation. 200 mL of water and 200 mL of ethyl acetate (EA) were added to the concentrate. The mixture was shaken to separate the layers, and the aqueous layer was collected. The aqueous layer was acidified with hydrochloric acid to pH≈1, extracted with ethyl acetate, and the organic phase was washed twice with water. The solution was then evaporated to dryness to obtain 90.8 g of white powder, namely compound D2, with a purity of 98%.

[0166] 1 H NMR (400MHz, CDCl3) δ10.20(1H,br.);7.83(2H,t);7.32(2H,t);6.68(2H,d);4.84-4.81(1H,m);2.6(2H,m);2.20-2.08(3H ,m); 1.66-1.56(6H,m); 1.46-1.38(12H,m); 0.99(3H,t,J=7.3,CH3); 0.93(3H,t,J=7.3,CH3); 0.90(3H,t,J=7.3,CH3).

[0167] 13 C NMR (101MHz, CDCl3) δ173.0, 153.4, 131.5, 129.6, 128.4, 125.5,125.4, 123.9, 123.6, 122.4, 121.9, 118.6, 118.5, 115.6 , 114.6, 90.0,41.1, 32.5, 29.3, 31.8, 27.5, 22.3, 14.2, 14.1, 13.9.

[0168] MS[MH] - 395.

[0169] Test Example 1

[0170] Extraction method:

[0171] Compound WH001 was dissolved in No. 260 solvent oil to prepare a 0.1 mol / L organic phase. The filtrate after alkaline leaching and pressure filtration in the waste vanadium catalyst recovery process (from Wanhua Chemical Group Co., Ltd.) was used as the aqueous phase. The ionic composition is shown in Table 1.

[0172] Table 1

[0173]

[0174] The organic phase was first saponified with 11 mol / L sodium hydroxide aqueous solution, with or without saponification rate ranging from 0% to 70%, and the pH of the organic phase was adjusted accordingly. The initial pH of the aqueous phase was kept constant at 10. The organic phase and aqueous phase were extracted at a volume ratio of 1:1 after different degrees of saponification (i.e., corresponding to different pH values ​​of the extraction system equilibrium). The equilibrium time was 15 min and the temperature was 25℃.

[0175] After extraction, the extraction rate was plotted against equilibrium pH to obtain the extraction rate E%-pH curves of compound WH001 for each ion. The results are as follows: Figure 1 As shown in Table 2.

[0176] Table 2 Extraction rates (E%) of compounds for each ion

[0177]

[0178] Compounds WH002~WH004 and compounds D1~D2 were dissolved in solvent oil No. 260 to prepare 0.1 mol / L organic phases. The aqueous phase was the same as in Example 1, with the saponification rate varied to ensure an equilibrium pH of 10. The aqueous phase was extracted at a volume ratio of 1:1 (organic phase to aqueous phase) for 15 min at 25°C. A comparison with WH001 is shown in Table 3 below.

[0179] Table 3 Comparison of the extraction efficiency (E%) of each compound for ions

[0180]

[0181] Extraction results:

[0182] Compounds WH001~WH004 all affect V 5+ The extraction exhibits excellent selectivity, with the extraction order for each ion being V. 5+ W 6+ Mo 6+ Ti 4+ When the equilibrium pH of the aqueous phase is 10, compounds WH001~WH004 all affect V. 5+ It exhibits excellent extraction selectivity and can achieve good separation of vanadium / molybdenum, vanadium / tungsten, and vanadium / titanium at this equilibrium pH.

[0183] Compound D1 on V 5+ The extraction exhibits a certain degree of selectivity, with the extraction order for each ion being V. 5+ W 6+ Mo 6 + Ti 4+ But for V 5+The selective extraction effect of compound D2 was significantly worse than that of the compounds in the examples; however, the selectivity of compound D2 showed a large difference, preferentially extracting Ti. 4+ The extraction order for each ion is Ti 4+ V 5+ W 6+ Mo 6+ .

[0184] Test Example 2

[0185] The compound WH001 was used for extraction, and the extraction method was the same as that in Test Example 1. The main difference was the different ionic composition of the aqueous phase, as shown in Table 4.

[0186] Table 4

[0187]

[0188] The extraction results are shown in Table 5.

[0189] Table 5 Extraction rates (E%) of compounds for each ion

[0190]

[0191] It can be seen that compound WH001 affects V 5+ The extraction rate is still approximately 99.7% for W. 6+ Mo 6+ Ti 4+ The extraction rate is between 12.3% and 22.4%, with good selectivity.

[0192] Test Example 3

[0193] The compound WH001 was used for extraction, and the extraction method was the same as that in Test Example 1. The main difference was the different ionic composition of the aqueous phase, as shown in Table 6.

[0194] Table 6

[0195]

[0196] The extraction results are shown in Table 7.

[0197] Table 7 Extraction rates (E%) of compounds for each ion

[0198]

[0199] It can be seen that compound WH001 affects V 5+ The extraction rate is still approximately 99.7% for W. 6+ Mo 6+ Ti 4+ The extraction rate is between 12.3% and 22.8%, with good selectivity.

[0200] Test Example 4

[0201] This test case examines the back-extraction performance of compound WH001 after loading metal ions.

[0202] Compound WH001 was dissolved in n-dodecane to prepare a 0.62 mol / L organic phase. The aqueous phase was a sulfate solution containing 0.05 mol / L vanadium ions. The organic phase was saponified with 9 mol / L ammonia solution at a saponification ratio of 50%. The saponified organic phase was then extracted with the aqueous phase at a volume ratio of 1:3 for 15 min at 25 °C. This yielded a vanadium-loaded organic phase. 5+ The content is 0.15 mol / L.

[0203] The vanadium-loaded organic phase was back-extracted using a 2 mol / L sulfuric acid aqueous solution. During back-extraction, the volume ratio of the vanadium-loaded organic phase to the sulfuric acid aqueous solution was 10:1, and the back-extraction rate was >99.5%.

[0204] The same steps were performed, but with P507 replacing compound WH001. The resulting vanadium-loaded organic phase was back-extracted using a 4 mol / L sulfuric acid aqueous solution, achieving a single-pass back-extraction rate of approximately 85%. This demonstrates that the naphthalene-containing carboxylic acid compound of this application can achieve a high back-extraction rate even with relatively low back-extraction acidity when used for metal ion extraction.

[0205] Test Example 5

[0206] This test case examines the saturation capacity test of vanadium extraction by compound WH001.

[0207] Compound WH001 was dissolved in n-dodecane to prepare a 0.6 mol / L organic phase. A 50 g / L solution containing V was prepared. 5+ The aqueous solution is used as the aqueous phase.

[0208] Take a 100 mL separatory funnel, add 15 mL of organic phase, and saponify it with 10 mol / L NaOH aqueous solution. The saponification ratio is 60%. After saponification, the organic phase does not need to be separated. Directly add 15 mL of aqueous phase and shake to mix for 15 min. Separate the aqueous phase, then add 15 mL of fresh 50 g / L NiSO4 aqueous solution and shake to mix for 15 min. Repeat the above operation until the ion concentration in the aqueous phase no longer changes. At this point, the metal concentration in the organic phase is the saturation capacity of the extractant. Back-extracting the organic phase yields compound WH001, which has a saturation capacity of 30.6 g / L for vanadium extraction.

[0209] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0210] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. Naphthyl ring carboxylic acid compounds or their salts having the structural features shown in formula (I): （I）， R1 is a C3~C12 alkyl group; R2 is an H or C1~C12 base.

2. The naphthalene-containing carboxylic acid compound or its salt according to claim 1, characterized in that, R1 is a C3-C12 straight-chain alkyl group, optionally a C4-C6 straight-chain alkyl group; and / or, R2 is a C7 to C10 alkyl group.

3. The naphthalene-containing carboxylic acid compound or its salt according to claim 1, characterized in that, The naphthalene-containing carboxylic acid compound has the structural features shown in formula (II): (II)。 4. The naphthalene-containing carboxylic acid compound or its salt according to any one of claims 1 to 3, characterized in that, The naphthalene-containing carboxylic acid compound is one or more of the following compounds: 、 、 、 、 and .

5. The method for preparing the naphthalene-containing carboxylic acid compound or its salt according to any one of claims 1 to 4, characterized in that, Includes the following steps: Compound A and compound B are reacted; Compound A has the following structural features: X is a halogen; Compound B has the following structural features: 。 6. The method for preparing naphthalene-containing carboxylic acid compounds or their salts according to claim 5, characterized in that, It has one or more of the following characteristics: (1) The reaction is carried out in the presence of a solvent and a base; Optionally, the solvent includes ether solvents, and more preferably tetrahydrofuran; Optionally, the volume-to-mass ratio of the solvent to compound B is (1~8) mL:1 g; Optionally, the alkali includes one or more of alkali metals and alkali metal hydrides, and is further optionally one or more of sodium metal and sodium hydride; Optionally, the molar ratio of the base to compound A is (1~1.5):1; (2) The molar ratio of compound A to compound B is 1: (1~1.5); (3) The reaction temperature is 60℃~70℃; (4) The reaction time is 6h~12h.

7. The use of the naphthalene-containing carboxylic acid compound or its salt as described in any one of claims 1 to 4 as an extractant; Optionally, the extractant is used to extract and separate metal ions; Further optionally, the metal ions include target ions and ions to be separated, wherein the target ions include vanadium ions, and the ions to be separated include one or more of tungsten ions, molybdenum ions, and titanium ions.

8. An extraction composition, characterized in that, It includes an extractant and a diluent, wherein the extractant includes one or more of the naphthalene-containing carboxylic acid compounds and their salts as described in any one of claims 1 to 4; Optionally, the diluent is one or more selected from solvent oil, kerosene, hexane, heptane, and dodecane; Optionally, in the extraction composition, the molar concentration of the extractant is 0.1 mol / L to 1.5 mol / L.

9. An extraction method, characterized in that, Includes the following steps: The extraction composition according to claim 8 is used to extract the aqueous phase containing metal ions, and the organic phase is collected. Optionally, the volume ratio of the extraction composition to the aqueous phase containing metal ions is 1:(1~10); Optionally, the extraction pH is 7-13, further preferably 10-13, and even more preferably 10-11; Optionally, the extraction temperature is 10℃~50℃; Optionally, the extraction time is 5 min to 60 min; Optionally, the extraction method includes shaking; Optionally, the metal ions include target ions and ions to be separated, wherein the target ions include vanadium ions, and the ions to be separated include one or more of tungsten ions, molybdenum ions, and titanium ions.

10. The extraction method according to claim 9, characterized in that, It also includes the step of back-extracting the organic phase: The organic phase is mixed with an aqueous solution of acid, and the aqueous phase containing the target ion is collected. Optionally, the molar concentration of the aqueous solution of the acid is 0.5 mol / L to 5 mol / L; Optionally, the acid in the aqueous solution of the acid is an inorganic acid, which may include one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. Optionally, the volume ratio of the organic phase to the aqueous solution of the acid is (1~50):1, and more preferably (10~20):1.

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