A catalyst for liquid-phase Beckmann rearrangement, and its preparation method and application

Abstract

The present invention discloses a catalyst for liquid-phase Beckmann rearrangement, its preparation method, and application. The catalyst comprises a macrocyclic compound derivative formed by linking a catalytically active group to a macrocyclic compound having a delocalized macro-π system via a linker. The catalyst can be used to catalyze the Beckmann rearrangement of a ketoxime to obtain the corresponding amide compound, particularly a cyclic ketoxime to produce the corresponding lactam. The catalyst exhibits good catalytic activity, good selectivity, and is easily separable.

Description

Technical Field

[0001] The present invention belongs to the field of chemical industry and relates to a catalyst for liquid-phase Beckmann rearrangement, a preparation method and application thereof. The catalyst can be used to prepare corresponding amides through Beckmann rearrangement of ketoximes, in particular to prepare corresponding lactams through Beckmann rearrangement of cyclic ketoximes. Background Art

[0002] Among the methods for preparing amides, one of the most valuable and important methods is the Beckmann rearrangement. For example, the preparation of caprolactam from cyclohexanone oxime through the Beckmann rearrangement is the basis of the modern fiber industry. The conversion of cyclododecanone oxime into laurolactam through the Beckmann rearrangement is an important method for producing nylon 12 monomers.

[0003] Currently, the most commonly used catalyst for liquid-phase Beckmann rearrangement in industry is inorganic acid, such as sulfuric acid. However, there are problems such as large amount of sulfuric acid required, high viscosity of the reaction liquid, and by-production of ammonium sulfate, as shown in US6649757B2.

[0004] Sumitomo Chemical has developed a set of gas phase rearrangement without ammonium sulfate process to solve the above problems, this process is that cyclohexanone, under the catalysis of TS-1, reacts with ammonia and hydrogen peroxide to generate oxime, then realizes the Beckmann rearrangement of gas phase on a kind of high silicon-containing zeolite molecular sieve catalyst surface and obtains target product cyclohexanone oxime (Appl.Catal.A, 2004,262,137 etc.), and realizes industrialization in 2003.Similarly, CN101228122A discloses a kind of zeolite catalyst and is used for catalysis cyclododecanone oxime gas phase rearrangement and prepares laurolactam.But because the boiling point of cyclohexanone oxime and cyclododecanone oxime is higher, has reached 210 ℃ (normal pressure) and 140 ℃ (3mmHg) respectively, under higher reaction temperature, this type of catalyst surface is easy to coke, causes catalyst deactivation, and energy consumption is larger.Therefore, the liquid phase rearrangement of catalyst catalysis ketoxime under lower reaction temperature still has very large application value.

[0005] To this end, extensive research has been conducted on catalysts that catalyze the Beckmann rearrangement, focusing primarily on heteropolyacids, transition metal-containing Lewis acids, strong acid resins, and ionic liquids. For example, CN102658191A discloses a supported solid acid catalyst using a tungstophosphorus heteropoly acid as the active component and a mesoporous molecular sieve as the carrier. The catalyst achieves caprolactam yields and selectivities of 82.5% and 87.1%, respectively. The reaction system can be separated by filtration, and no products such as ammonium sulfate are generated during the process. Another example is CN108543548A, which discloses a silicon-containing composite resin catalyst that achieves a high caprolactam yield at a relatively low cost. For example, CN109503483A discloses impregnating metal salt solutions such as Fe(NO3)3, Zn(NO3)2, Cu(NO3)2, Cr(NO3)3, Mn(NO3)3, Co(NO3)2 on oxide supports such as SiO2, γ-Al2O3, TiO2, 4A molecular sieve, Y-type molecular sieve, kaolin, cordierite, etc., and activating them with trichloroacetic acid, methanesulfonic acid, aminosulfonic acid, picric acid, benzenesulfonic acid, toluenesulfonic acid, trifluorobenzenesulfonic acid, etc., to improve the stability and selectivity of the resin catalyst. For example, CN105289746A discloses a catalyst system that can be used for Beckmann rearrangement, prepared by preparing a silane-modified Lewis acid ionic liquid in two steps using imidazole or pyridine with 3-chloropropyltrialkoxysilane and zinc salt, and grafting it onto the surface of graphene oxide. The catalyst system has a conversion rate greater than 99% and a selectivity of over 90% in the catalytic reaction of acetophenone oxime. The catalyst was reused four times, and the selectivity and conversion rate fluctuated by approximately 2-3%, showing a certain degree of repeatability.

[0006] Progress has also been made in the study of organic catalysts. CN101547897A, US8163899B2, Takashi Kajitani et al. (J. Am. Chem. Soc., 2005, 127 (32), 1124-1125), and Ishii et al. (J. Org. Chem. 2008, 73, 2894-2897) used a series of small molecule catalysts to catalyze cyclic oximes to generate lactams, such as cyanuric chloride, hexachlorocyclotriphosphazene, bromosuccinimide, isocyanuric chloride, triphenylchlorosilane, etc., showing good application potential. However, compared with existing liquid phase and gas phase rearrangement technologies, there are still many shortcomings, such as high catalyst preparation cost, large dosage, low selectivity, and the need to use solvents such as hexafluoroisopropanol, which further increases cost and industrialization difficulty. Similarly, resin catalysts and supported molecular sieve catalysts also have problems such as insufficient strength and loss of active sites.

[0007] In view of this, the present invention is proposed. Summary of the Invention

[0008] In response to the problems existing in the above-mentioned prior art, the present invention has developed a class of macrocyclic compound derivatives containing calixarene and catalytic active sites, or a catalyst system in which calixarene and catalytic active sites are loaded on modified coke powder. The catalyst system is suitable for catalyzing the Beckmann rearrangement of ketone oxime to prepare the corresponding amide, especially the Beckmann rearrangement of cyclic ketone oxime to prepare the corresponding lactam, and has the advantages of high catalytic efficiency, easy separation, reusability, and no production of ammonium sulfate.

[0009] Therefore, it is an object of the present invention to provide a catalyst for liquid-phase Beckmann rearrangement.

[0010] Another object of the present invention is to provide a method for preparing the above catalyst.

[0011] Another object of the present invention is to provide the use of the above catalyst in catalyzing the Beckmann rearrangement of ketoxime to prepare the corresponding amide, especially the Beckmann rearrangement of cyclic ketoxime to prepare the corresponding lactam.

[0012] Specifically, the technical solution of the present invention to achieve the above-mentioned purpose is as follows:

[0013] In a first aspect of the present invention, a catalyst for liquid-phase Beckmann rearrangement is provided, comprising: a macrocyclic compound derivative formed by linking a catalytically active group to a macrocyclic compound having a delocalized macro-π system via a linker;

[0014] The linker is a structural fragment obtained by reacting a linker substance with a macrocyclic compound and a Beckmann rearrangement catalytic active component; the linker substance is selected from an amino acid, a diamine compound or an alcoholamine compound;

[0015] The catalytically active group is a group obtained by the reaction of the Beckmann rearrangement catalytically active component with the connecting arm substance. In some embodiments, the macrocyclic compound can be, for example, calixarene, pillararene or their derivatives. Among them, calixarene is a cavity-type molecule formed by connecting phenol units through methylene. In the present invention, the macrocyclic compound can be calix[4]arene, calix[5]arene, calix[6]arene, calix[7]arene, calix[8]arene, resorcinol calix[4]arene, etc. Pillararene is a columnar ring compound formed by cross-linking diphenol through methylene para-position. In the present invention, it can be pillar[5]arene, etc. Calixarene and pillararene have derivatization sites. In the present invention, the calixarene or pillararene derivative can be a calixarene or pillararene derivative in which the hydrogen of the phenolic hydroxyl group is replaced by -(CH2) m CH3, -(CH2CH2O) m H, -(CH2CH2) m OH, -(CH2) m Derivatives formed by substitution with COOH and other groups, wherein m is an integer of 1 to 6, preferably 1 to 3. From a comprehensive consideration of practical effect and cost, the present invention preferably uses calix[4]arene and its derivatives.

[0016] In some embodiments, the macrocyclic compound derivative containing a catalytically active group has a structure represented by formula (I):

[0017]

[0018] wherein n is 4, 5, 6, 7 or 8, corresponding to calix[4]arene, calix[5]arene, calix[6]arene, calix[7]arene, calix[8]arene or their derivatives, respectively; preferably, n is 4;

[0019] Each R1 is selected from H, -(CH2) m CH3, -(CH2CH2O) m H, and each R1 is not H at the same time; m is 1 or 2; preferably 1;

[0020] Each X is H or a structural fragment formed by the reaction of the linker material with the macrocyclic compound and the catalytically active component, and each X is not H at the same time. When X is H, R2 does not exist;

[0021] The linker material is selected from d-, l-, or racemic amino acids or esters thereof (e.g., glycine, alanine, valine, leucine, isoleucine, tryptophan, serine, tyrosine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine or fatty acid esters thereof (e.g., formate, acetate, propionate)), ethylenediamine, propylenediamine, diethyltriamine, 2,2′-oxybis(ethylamine), ethanolamine, etc.;

[0022] The reaction described varies depending on the reactive groups of the linker material. For example, when the linker material is a diamine compound, serine, serine methyl ester, threonine, threonine methyl ester, lysine, or lysine methyl ester, one amino group in the molecule can undergo a Mannich reaction with the benzene ring of the macrocyclic compound, and the other amino group or hydroxyl group can undergo a substitution reaction with the catalytically active component. When the linker material is another amino acid or amino acid ester, generally, a reaction is required on the benzyl ring of the macrocyclic compound to form benzyl alcohol, followed by a condensation reaction or transesterification reaction between the carboxyl group of the amino acid or its ester and the hydroxyl group of the alcohol, and then the amino group of the amino acid undergoes a substitution reaction with the catalytically active component. From the perspectives of simplifying industrial equipment, simplifying operations, and reducing costs, preferably, X is a structural fragment formed by a Mannich reaction between one amino group in lysine methyl ester, serine methyl ester, threonine methyl ester, etc. and the benzyl ring of the macrocyclic compound, and a substitution reaction between the other amino group or hydroxyl group and the catalytically active component. Preferably, X is selected from

[0023] Each R2 is independently a group formed by the reaction of a Beckmann rearrangement catalytic active component and a linker material; the Beckmann rearrangement catalytic active component is selected from one or a combination of cyanuric chloride and hexachlorocyclotriphosphazene; preferably, each R2 is independently selected from One of; preferably

[0024] In a specific embodiment, the catalyst for liquid-phase Beckmann rearrangement may further include modified coke powder, and the macrocyclic compound derivative is chemically modified on the surface of the modified coke powder.

[0025] The modified coke powder is obtained by surface activation and oxidation of coke powder, and its surface contains active groups such as hydroxyl groups;

[0026] The chemical modification can be covalently linking the macrocyclic compound to the modified coke powder surface through any known chemical reaction, for example, linking the macrocyclic compound to the modified coke powder surface (hydroxyl group, etc.) through the reaction of active reactive groups (such as amino groups, hydroxyl groups, etc.).

[0027] In the present invention, coke powder refers to small particles of coke powder produced during the coke production process of a coking enterprise. After screening, coke powder particles with a particle size of less than 5 mm are selected as raw materials. Preferably, the particle size of the coke powder particles in the present invention is 2-3 mm.

[0028] Modified coke powder is obtained after pretreatment (surface activation and surface oxidation) of coke powder.

[0029] Preferably, the coke powder surface can be activated (pore expansion and surface cleaning) using water vapor, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, followed by surface oxidation using an oxidizing agent (e.g., hydrogen peroxide, ozone, tert-butyl peroxide, m-chloroperbenzoic acid, potassium dichromate, etc.) in combination with an acidic compound (e.g., concentrated sulfuric acid, concentrated phosphoric acid, sulfamic acid, methanesulfonic acid, hydrofluoric acid, etc.). The surface of the modified coke powder is then modified with hydroxyl groups. Preferably, water vapor is used for surface activation, followed by surface oxidation modification using hydrogen peroxide and concentrated sulfuric acid.

[0030] In some embodiments, the modified coke fines are prepared by a method comprising the following steps:

[0031] The coke powder is calcined, and water vapor is introduced during the calcination process to activate it. After cooling, it is washed and dried to obtain surface-activated coke powder; the surface-activated coke powder is soaked in concentrated sulfuric acid and hydrogen peroxide to obtain oxidized coke powder; the oxidized coke powder is filtered, washed, and then dried to constant weight to obtain modified coke powder.

[0032] Preferably, the amount of water vapor introduced is 10-200% of the mass of the coke powder, preferably 20-50%, for example 30-50%;

[0033] Preferably, the mass concentration of hydrogen peroxide is 10-60%, preferably 30-50%; the amount of hydrogen peroxide used is 1-5% of the mass of the surface-activated coke powder, preferably 2-3%; the amount of concentrated sulfuric acid used is 1-10% of the mass of the surface-activated coke powder, preferably 4-6%;

[0034] Preferably, the soaking time is 1-24 hours, preferably 2-4 hours, and the soaking temperature is 20-80°C, preferably 25-45°C.

[0035] In some embodiments, the specific surface area of ​​the modified coke powder is 8.0-12.0 m 2 / g, carbon content is 80-90%, ash content is 10-12%, and bulk density is 400-480g / L.

[0036] In a second aspect of the present invention, a method (I) for preparing the catalyst for liquid-phase Beckmann rearrangement is provided, wherein the catalyst comprises the macrocyclic compound derivative, and the preparation method (I) comprises the following steps:

[0037] S01, chemically reacting the macrocyclic compound with the linker substance to obtain a linker-modified macrocyclic compound;

[0038] S02. Reactively connecting the linker-modified macrocyclic compound with a Beckmann rearrangement catalytic active component via the linker to obtain a macrocyclic compound derivative catalyst.

[0039] In the above-mentioned preparation method (I), the macrocyclic compound, the linker material, and the Beckmann rearrangement catalytic active component are as defined above. The active group (e.g., amino group, hydroxyl group) in the linker material can be connected to the structure (e.g., benzene ring) in the macrocyclic compound through any known chemical reaction; and the Beckmann rearrangement catalytic active component can be connected to another active group (e.g., hydroxyl group, amino group, etc.) in the above-mentioned linker material through any known chemical reaction.

[0040] In some embodiments, the preparation method (I) of the catalyst for liquid-phase Beckmann rearrangement comprises the following steps:

[0041] (1) mixing a calixarene derivative, an amino acid or its ester, a formaldehyde aqueous solution, acetic acid, and a solvent 1, reacting the mixture at room temperature for a period of time, removing the solvent 1, dissolving the residue with a solvent 2, washing, filtering, removing the solvent 2, and recrystallizing the mixture to obtain a calixarene derivative containing an amino acid linker arm;

[0042] (2) The calixarene derivative containing an amino acid linker arm is heated with cyanuric chloride, hexachlorocyclotriphosphazene, or a combination thereof, an acid-binding agent, and solvent 3 for a period of time, filtered, and the filtrate is freed from solvent 3. The residue is dissolved with solvent 4, washed, dried, filtered, and solvent 4 is removed. After recrystallization, the target catalyst is obtained.

[0043] In some embodiments, in step (1), the amino acid or its ester undergoes a Mannich reaction with a calixarene derivative, wherein:

[0044] The calixarene derivative is a phenolic hydroxyl group whose hydrogen is replaced by -(CH2) m CH3 or -(CH2CH2O) m H-substituted calixarene, selected from the following structures:

[0045]

[0046] The amino acids are d-, l-, or racemic serine, threonine, and lysine, and the amino acid esters are the aforementioned amino acid methyl esters or their methyl ester hydrochlorides. The molar ratio of the amino acid or its ester to the calixarene derivative is 0.5-3.0:1.0, preferably 1.5-2.5:1.0, for example 2.0:1. In this case, the amino acid is in excess, ensuring complete reaction of the calixarene derivative.

[0047] Preferably, the concentration of the formaldehyde aqueous solution is 1-40 wt%, preferably a commercially available 35-37 wt% formaldehyde aqueous solution is used, and the molar ratio of the added amino acid or its ester to formaldehyde is 0.8-10:1.0, preferably 0.8-1.0:1.0.

[0048] Preferably, the purpose of adding acetic acid is to ensure that the system maintains an acidic environment, and it can be added in an equimolar ratio with the amino acid or its ester; the acetic acid is preferably glacial acetic acid.

[0049] Preferably, solvent 1 is selected from one or more of tetrahydrofuran, methyltetrahydrofuran, acetone, methanol, ethanol, isopropanol, and tert-butanol, preferably tetrahydrofuran, methyltetrahydrofuran, or a combination thereof. The mass ratio of solvent 1 to the calixarene derivative is 5-15:1.0, preferably 5-10:1.0.

[0050] Preferably, solvent 2 is selected from one or more combinations of dichloromethane, chloroform, tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, and methyl tert-butyl ether, preferably dichloromethane.

[0051] Preferably, the washing is performed with deionized water.

[0052] Preferably, the recrystallization solvent is selected from one or more combinations of ethyl acetate-petroleum ether, ethyl acetate-n-hexane, ethyl acetate-n-heptane, ethyl acetate-cyclohexane, methyl acetate-n-hexane, methyl acetate-n-heptane, methyl acetate-cyclohexane, methyl acetate-petroleum ether, ethyl acetate-benzene or ethyl acetate-toluene, preferably ethyl acetate-petroleum ether.

[0053] In some embodiments, in step (2), cyanuric chloride, hexachlorocyclotriphosphazene, or a combination thereof undergoes a substitution reaction with a calixarene derivative containing an amino acid linker arm, wherein:

[0054] The molar ratio of cyanuric chloride, hexachlorocyclotriphosphazene, or a combination thereof to the calixarene derivative containing an amino acid linker arm is 1.0-10.0:1.0, preferably 4.0-6.0:1.0, for example 5.0:1.0. After the reaction is completed, the excess cyanuric chloride can be recovered and reused. In practice, cyanuric chloride has a strong mucosal irritation effect and should be used in a sealed environment or in a fume hood.

[0055] Preferably, the acid-binding agent is selected from one or more combinations of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine (TEA), diisopropylethylamine (DIPEA), and the like, preferably sodium carbonate or potassium carbonate. The molar ratio of the acid-binding agent to cyanuric chloride, hexachlorocyclotriphosphazene, or the combination thereof is 1-10:1.0, preferably 1.0-2.0:1.0.

[0056] Preferably, solvent 3 is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, methyltetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, acetonitrile, and the like, preferably tetrahydrofuran, methyltetrahydrofuran, or acetonitrile. The amount of solvent 3 used is 15-40 times, preferably 20-30 times, the mass of the calixarene derivative containing the amino acid linker arm.

[0057] Preferably, the reaction temperature of the heating reaction is 30-80° C., preferably 60-65° C.; the reaction time is 0.5-5 h, preferably 1-3 h.

[0058] Preferably, solvent 4 is selected from one or more combinations of dichloromethane, acetonitrile, tetrahydrofuran, methyltetrahydrofuran, chloroform, and 1,4-dioxane, preferably dichloromethane.

[0059] Preferably, washing is washing with deionized water to remove residual sodium carbonate in the reaction system.

[0060] Preferably, the recrystallization solvent is selected from one or more combinations of ethyl acetate-petroleum ether, ethyl acetate-n-hexane, ethyl acetate-n-heptane, ethyl acetate-cyclohexane, methyl acetate-n-hexane, methyl acetate-n-heptane, methyl acetate-cyclohexane, methyl acetate-petroleum ether, ethyl acetate-benzene or ethyl acetate-toluene, preferably ethyl acetate-petroleum ether.

[0061] The present invention also provides a method (II) for preparing the above-mentioned catalyst for liquid-phase Beckmann rearrangement, wherein the macrocyclic compound derivative in the catalyst is chemically modified on the surface of the modified coke powder, and the preparation method (II) comprises the following steps:

[0062] S03, surface activating and oxidizing the coke powder to obtain modified coke powder;

[0063] S04, modifying the macrocyclic compound on the surface of the modified coke powder through a chemical reaction to obtain coke powder modified with the macrocyclic compound;

[0064] S05, chemically reacting the macrocyclic compound-modified char powder with a linker substance to obtain macrocyclic compound-modified char powder containing a linker;

[0065] S06. Reactively connecting the coke powder modified with the macrocyclic compound containing a connecting arm with the Beckmann rearrangement catalytic active component via the connecting arm to obtain the catalyst.

[0066] In the above method, in step S03, the coke powder surface is activated (pore expansion and surface cleaning) using water vapor, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate. Subsequently, an oxidizing agent (e.g., hydrogen peroxide, ozone, tert-butyl peroxide, m-chloroperbenzoic acid, potassium dichromate, etc.) is combined with an acidic compound (e.g., concentrated sulfuric acid, concentrated phosphoric acid, sulfamic acid, methanesulfonic acid, hydrofluoric acid, etc.) to oxidize the surface. After oxidation, the modified coke powder surface has hydroxyl groups. Preferably, water vapor is used for surface activation, followed by hydrogen peroxide and concentrated sulfuric acid for surface oxidation modification. The oxidized modified coke powder surface has hydroxyl groups, epoxy groups, carboxyl groups, and other groups, primarily hydroxyl groups.

[0067] In step S04, the macrocyclic compound is as defined above, and can be covalently linked to the surface of the modified coke powder (active groups (such as hydroxyl groups, amino groups) in the macrocyclic compound and hydroxyl groups on the surface of the modified coke powder) through any known chemical reaction.

[0068] In step S05, the linker material is as defined above, and the active groups (eg, amino groups, hydroxyl groups) in the linker material can be connected to the structure (eg, benzene ring) in the macrocyclic compound through any known chemical reaction.

[0069] In step S06, the Beckmann rearrangement catalytic active component is as defined above, and can be connected to another active group (such as hydroxyl group, amino group, etc.) of the linker arm through any known chemical reaction.

[0070] In some embodiments, the preparation method (II) of the catalyst for liquid-phase Beckmann rearrangement comprises the following steps:

[0071] (3) calcining the coke powder, introducing water vapor to activate it during the calcination process, cooling it, washing it, and drying it to obtain surface-activated coke powder; soaking the surface-activated coke powder in concentrated sulfuric acid and hydrogen peroxide to obtain oxidized coke powder; filtering and washing the oxidized coke powder, and then drying it to a constant weight to obtain modified coke powder;

[0072] (4) mixing the calixarene derivative with the modified coke powder and an organic solvent, adding a condensation reagent to react, filtering, washing with an organic solvent to remove by-products generated by the reaction, and drying to obtain calixarene-modified coke powder;

[0073] (5) mixing the calixarene-modified char powder, an amino acid or its ester, a formaldehyde aqueous solution, acetic acid, and a solvent, reacting the mixture at room temperature for a period of time by bubbling and stirring, and filtering, washing, and drying the mixture to obtain the calixarene-modified char powder containing an amino acid linker arm;

[0074] (6) The calixarene-modified char powder containing an amino acid linker arm is heated with one or a combination of cyanuric chloride, hexachlorocyclotriphosphazene, and a solvent for a period of time, and then filtered, washed, and dried to obtain the target catalyst.

[0075] In some embodiments, in step (3):

[0076] The coke powder is crushed and then sieved before calcining. After sieving, the particle size distribution of the coke powder is 1-5 mm, and the preferred particle size distribution is 2-3 mm.

[0077] Preferably, calcination can be carried out in a tubular furnace, and the calcination includes at least two stages: in the first stage, the temperature in the tubular furnace is raised from room temperature to 300-800°C, preferably 500-600°C; and kept warm for 1-24 hours, preferably 2-3 hours; in the second stage, the temperature is continued to be programmed to 700-1000°C, preferably 800-900°C, with a temperature increase gradient of 1-10°C / min, preferably 2-3°C / min, and kept warm for 1-24 hours, preferably 2-3 hours.

[0078] Preferably, in the second stage, water vapor is introduced for activation immediately after the temperature is raised to the highest point or during the heat preservation process; the amount of water vapor introduced is 10-200% of the mass of the coke powder, preferably 20-50%, preferably 30-50%, and is introduced all at once.

[0079] Preferably, the cooling is natural cooling.

[0080] Preferably, the calcined and cooled coke powder is soaked in 5% dilute hydrochloric acid for 30-60 minutes.

[0081] Preferably, the calcined, cooled, and preferably diluted hydrochloric acid-soaked coke powder is washed with desalted water until the pH of the filtrate reaches 5-6.

[0082] Preferably, the calcined, cooled, preferably soaked and washed coke powder is dried at 80° C. until the coke powder has a constant weight.

[0083] Preferably, the mass concentration of hydrogen peroxide is 10-60%, preferably 30-50%.

[0084] Preferably, the amount of hydrogen peroxide used is 1-6% of the mass of the surface-activated coke powder, such as 1-5% or 2-3%; the amount of concentrated sulfuric acid used is 1-10% of the mass of the surface-activated coke powder, such as 4-6% or 5-10%.

[0085] Preferably, the surface-activated coke powder is soaked in concentrated sulfuric acid and hydrogen peroxide for 1-24 hours, preferably 2-4 hours, at a soaking temperature of 20-80°C, preferably 25-45°C.

[0086] Preferably, the filtered oxidized coke powder is washed with desalted water to a pH of 4-6.

[0087] Preferably, the filtered and washed oxidized coke powder is dried at a temperature of 60-120°C, preferably 80-90°C.

[0088] In some embodiments, in step (4):

[0089] The calixarene derivative is a phenolic hydroxyl group whose hydrogen is replaced by -(CH2CH2O) m H-substituted calixarene, the structure of which is selected from the following structures:

[0090]

[0091] Preferably, the addition amount of the calixarene derivative is 0.1-10% of the mass of the modified coke powder, preferably 0.5-5%, more preferably 0.5-3%.

[0092] Preferably, the condensation reagents are azodicarbonate diester and triphenylphosphine; the azodicarbonate diester is one of diethyl azodicarbonate, diisopropyl azodicarbonate, di-tert-butyl azodicarboxylate, diphenyl azodicarboxylate, etc., or a combination thereof, preferably diethyl azodicarboxylate; the molar ratio of the azodicarbonate diester to the calixarene derivative is 0.1-10:1; preferably, the added amount of the azodicarbonate diester and the calixarene derivative is a molar ratio of 1:1; and the triphenylphosphine and the azodicarbonate diester are in an equimolar ratio.

[0093] Preferably, the organic solvent is one or more combinations selected from tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, dichloromethane, chloroform, benzene, toluene, xylene, ethyl acetate, acetonitrile, dimethyl sulfoxide, petroleum ether, etc.; preferably one or more combinations selected from tetrahydrofuran, methyltetrahydrofuran, and methyl tert-butyl ether, etc.; the amount of the organic solvent added is 10-400% of the mass of the modified coke powder, preferably 100-300%;

[0094] Preferably, the reaction temperature is 40-80°C, preferably 50-60°C; the reaction time is 0.5-5h, preferably 1-3h.

[0095] In some embodiments, in step (5), the amino acid or its ester undergoes a Mannich reaction with a calixarene derivative, wherein:

[0096] The amino acids are d-, l-, or racemic serine, threonine, and lysine, and the amino acid esters are the aforementioned amino acid methyl esters or their methyl ester hydrochlorides. The mass ratio of the amino acid or its ester to the calixarene-modified pyrolysis powder is 0.005-0.1:1.0, preferably 0.01-0.05:1.0, for example 0.02-0.04:1. At this point, the amino acid is in excess, ensuring complete reaction of the calixarene derivative.

[0097] Preferably, the concentration of the formaldehyde aqueous solution is 1-40 wt%, preferably a commercially available 35-37 wt% formaldehyde aqueous solution is used, and the molar ratio of the added amino acid or its ester to formaldehyde is 0.8-10:1.0, preferably 0.8-1.0:1.0.

[0098] Preferably, the purpose of adding acetic acid is to ensure that the system maintains an acidic environment, and it can be added in an equimolar ratio with the amino acid or its ester; the acetic acid is preferably glacial acetic acid.

[0099] Preferably, the solvent is selected from one or more of tetrahydrofuran, methyltetrahydrofuran, acetone, methanol, ethanol, isopropanol, and tert-butanol, preferably tetrahydrofuran and methyltetrahydrofuran. The mass ratio of the solvent to the calixarene-modified char powder is 0.5-10:1.0, preferably 1.5-2.0:1.0.

[0100] In some embodiments, in step (6), cyanuric chloride, hexachlorocyclotriphosphazene, or a combination thereof, undergoes a substitution reaction with calixarene-modified pyrochlore containing an amino acid linker arm, wherein:

[0101] The mass ratio of cyanuric chloride, hexachlorocyclotriphosphazene, or a combination thereof to the calixarene-modified char powder containing an amino acid linker is 0.01-0.1:1, preferably 0.01-0.04:1.0, for example 0.02:1.0. After the reaction, excess cyanuric chloride can be recycled. In practice, cyanuric chloride is a strong mucosal irritant and should be used in a sealed environment or in a fume hood.

[0102] Preferably, the acid-binding agent is selected from one or more combinations of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine (TEA), diisopropylethylamine (DIPEA), and the like, preferably sodium carbonate or potassium carbonate. The molar ratio of the acid-binding agent to cyanuric chloride, hexachlorocyclotriphosphazene, or the combination thereof is 1-10:1.0, preferably 1.0-2.0:1.0.

[0103] Preferably, the solvent is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, methyltetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, and acetonitrile, preferably tetrahydrofuran, methyltetrahydrofuran, or acetonitrile. The amount of solvent used is 10-400% by weight of the calixarene-modified char powder containing an amino acid linker arm, preferably 100-300%.

[0104] Preferably, the reaction temperature of the heating reaction is 30-80° C., preferably 60-65° C.; the reaction time is 0.5-5 h, preferably 1-3 h.

[0105] Preferably, deionized water is used for washing to remove residual sodium carbonate in the reaction system.

[0106] Preferably, drying is carried out at 50-60°C under nitrogen purge.

[0107] The third aspect of the present invention provides the use of the above catalyst for liquid-phase Beckmann rearrangement or the catalyst prepared by the above preparation method in a liquid-phase Beckmann rearrangement reaction.

[0108] In some embodiments, the liquid-phase Beckmann rearrangement reaction uses a ketoxime as a raw material to prepare the corresponding amide. The ketoxime includes cyclic ketoximes and aliphatic ketoximes. The cyclic ketoximes include, for example, cyclopentanone oxime, cyclohexanone oxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanone oxime, cyclodecanone oxime, cycloundecanone oxime, and cyclododecanone oxime; the aliphatic ketoximes include, for example, acetone oxime, butanone oxime, and heptanone oxime. In particular, the liquid-phase Beckmann rearrangement reaction of the present invention uses a cyclic ketoxime as a raw material.

[0109] In some embodiments of the above applications, the catalyst is activated in a cobalt naphthenate solution before use to provide metal ions to ensure the smooth progress of the Beckmann rearrangement. Preferably, the ratio of cobalt naphthenate to catalyst is 0.01-0.2 mol: 300-500 g, preferably 0.01-0.05 mol: 360 g (when the catalyst is a macrocyclic compound derivative alone) or 0.08-0.12 mol: 400 g (when the catalyst is a macrocyclic compound derivative chemically modified on the surface of modified coke powder), for example 0.1 mol: 400 g. The solvent for the cobalt naphthenate solution can be a solvent for the liquid-phase Beckmann reaction, such as one or more of acetonitrile, tetrahydrofuran, and methyltetrahydrofuran.

[0110] In the above application, in the liquid-phase Beckmann rearrangement reaction, the mass ratio of catalyst to ketoxime is 0.2-20:1.0, preferably 0.2-0.5:1.0 (when the catalyst is a single macrocyclic compound derivative) or 3.0-5.0:1.0 (when the catalyst is a macrocyclic compound derivative chemically modified on the surface of the modified coke powder).

[0111] Preferably, the reaction temperature of the liquid-phase Beckmann rearrangement reaction is 70-160° C., preferably 70-90° C.; the reaction pressure is 0.1-5.0 MPa, preferably 0.1-0.3 MPa; and the reaction time is 0.1-10 h, preferably 2-4 h.

[0112] Compared with the prior art, the catalyst for liquid-phase Beckmann rearrangement and the preparation method thereof of the present invention have the following advantages:

[0113] The catalyst of the present invention combines catalytically active substances such as cyanuric chloride with calixarene, increasing the catalyst's tolerance. Furthermore, the addition of coke powder as a carrier not only facilitates the coke's loading function but also promotes the aggregation of reaction substrates on the catalyst surface, accelerating the reaction and improving conversion. Consequently, the catalyst of the present invention exhibits high conversion and selectivity, mild reaction conditions, no ammonium sulfate byproduct, and is easily separable and reusable.

[0114] 2. The catalyst of the present invention is suitable for catalyzing the rearrangement of cyclic ketoximes, especially macrocyclic ketoximes, such as cyclododecanone oxime to laurolactam.

[0115] 3. The catalyst preparation method of the present invention has simple steps. The raw material coke powder is connected with the coking enterprise. The preparation of calixarene is connected with the crude benzene and coal tar industries. Amino acids are easily purchased and available. The scale is controllable and easy to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS

[0116] Figure 1The following is a schematic diagram of the reactor used for the coupling of the calix[4]arene derivative (II) with the modified coke powder in step (2) of Examples 1-3. In particular, 1 is the reactor; 2 is the jacket; 3 is the upper air inlet; 4 is the feed port; 5 is the lower air inlet; 6 is the lower discharge port; and 7 is the sieve plate.

[0117] Figure 2 This is a schematic diagram of the reactor used in Examples 4-7. In particular, 1 - reactor; 2 - jacket; 3 - lower inlet / outlet; 4 - upper inlet / outlet; 5 - temperature measuring point 1; 6 - temperature measuring point 2; 7 - check valve; 8 - feed pump; 9 - storage tank; 10 - upper inlet / outlet of storage tank; 11 - sampling port; 12 - lower inlet / outlet of storage tank; 13 - thermal oil inlet; 14 - thermal oil outlet; 15 - thermal oil heater; 16 - thermal oil pump; 17 - upper air inlet; 18 - side outlet; 19 - side sampling port of storage tank. DETAILED DESCRIPTION

[0118] The following examples are only used to illustrate the technical solution of the present invention more clearly, and are not intended to limit the scope of protection of the present invention.

[0119] Reagents and sources:

[0120] During the experiments, various organic solvents, including calixarene, cobalt naphthenate, amino acids and their methyl ester hydrochlorides, and polyamines, were purchased from Aladdin Reagent Company and MacLean Reagent Company and used without further treatment. Hydrogen peroxide and coke powder were sourced from Hebei Xuyang New Energy Co., Ltd. and Cangzhou Xuyang Chemical Co., Ltd., subsidiaries of Xuyang Group.

[0121] Example 1 Preparation of Calixarene Derivative Catalyst 1

[0122]

[0123] (1) Preparation of 1,3-diethyl-calix[4]arene:

[0124] Under nitrogen protection, a solution of calix[4]arene (42.5 g, 0.1 mol), ethyl bromide (27.3 g, 0.25 mol), and Na2CO3 (26.5 g, 0.25 mol) in acetonitrile (200 L) was refluxed for 24 h. The solution was filtered and the acetonitrile was removed by distillation under reduced pressure. 250 mL of dichloromethane was added to the residue to fully dissolve it, followed by 300 mL of deionized water. After phase separation, the organic phase was washed with 10% dilute hydrochloric acid solution (200 mL × 1) and deionized water (200 mL × 2), dried over anhydrous magnesium sulfate, and the dichloromethane was evaporated under reduced pressure. The crude product was purified by silica gel column chromatography (eluent: petroleum ether-ethyl acetate = 4:1, v / v) to obtain 1,3-diethyl-calix[4]arene (39.7 g, 82.6%).

[0125] (2) Preparation of 1,3-diethyl-calix[4]arene modified with serine methyl ester:

[0126] In a 250 mL reactor, 80 mL of tetrahydrofuran was added at room temperature, followed by 6.2 g (40.0 mmol) of serine methyl ester hydrochloride, 3.40 g of formaldehyde aqueous solution (35%, 40.0 mmol), 2.4 g (40.0 mmol) of glacial acetic acid and 9.60 g (20 mmol) of 1,3-diethyl-calix[4]arene. Stirring was started and the reaction was carried out at room temperature for 24 hours. The reaction was monitored by TLC until the raw material 1,3-diethyl-calix[4]arene completely disappeared. The tetrahydrofuran was removed in vacuo, and the residue was dissolved in dichloromethane (150 mL) and washed with deionized water (100 mL×3). The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated to dryness. The crude product was recrystallized using ethyl acetate-petroleum ether (volume ratio of 1:5) to obtain serine methyl ester-modified calix[4]-1,3-crown ether (7.2 g, 48.1%).

[0127] (3) Preparation of Catalyst 1

[0128] Close the nitrogen valve, add 50 mL of anhydrous acetonitrile to the reactor, add 1.5 g (2.0 mmol) of the intermediate obtained in the previous step, add 0.53 g (5.0 mmol) of finely ground anhydrous sodium carbonate powder, add 0.922 g (5.0 mmol) of cyanuric chloride, close the reactor, stir at 60°C under nitrogen protection for 2-3 hours, remove the solid by filter press, remove the acetonitrile in vacuo, dissolve the residue with dichloromethane (50 mL), wash with deionized water (25 mL×3), separate the liquids, dry the organic phase with anhydrous sodium sulfate, filter, remove the solvent in vacuo, and recrystallize the crude product from ethyl acetate-petroleum ether to obtain catalyst 1 (1.89 g, 90%).

[0129] Example 2 Preparation of Catalyst 2 Using Modified Coke Powder as Support

[0130]

[0131] (1) Modification of coke powder

[0132] The coke powder was crushed and sieved using 10-mesh and 5-mesh sieves to select coke powder particles with a particle size of 2-3mm. 500g of the sieved coke powder was weighed and placed in a tube furnace. The atmosphere was replaced with nitrogen. The temperature was raised from 25°C to 500°C at a rate of 2°C / min, held for 2 hours, and then raised from 500°C to 900°C at a rate of 2°C / min. When the temperature reached 900°C, 150g of water vapor was introduced into the tube furnace at once and held for 2 hours. After the holding time was reached, the mixture was naturally cooled to room temperature. The tube furnace was opened and the coke powder was removed. At this point, the coke powder was partially agglomerated and some parts of the surface were white. The weight was approximately 400-450g. The above was crushed and sieved to retain coke powder particles with a particle size of 2-3 mm, suspended in 100 mL of 5% dilute hydrochloric acid and soaked for 30 minutes, filtered, and the filter cake was washed with desalted water until the pH of the filtrate was 5-6. Subsequently, the filter cake was dried at 80°C to constant weight to obtain about 300 g of surface-activated coke powder.

[0133] In a shake flask, add 200g of the surface-activated scorch powder and 6g of 30% hydrogen peroxide. After shaking for 5 minutes, add 10g of concentrated sulfuric acid and shake thoroughly for 120 minutes to prepare oxidized scorch powder. At this point, a small amount of black flocculent or filamentous adherent material may be observed on the wall of the shake flask. After the reaction is completed, add 100mL of deionized water and soak for 2-3 hours. A small amount of black flocculent or flaky material may be observed floating on the liquid surface. Decant the floating material and the remaining solids. Wash the remaining solids repeatedly with deionized water to a pH of 5-6. Dry the solids at 80°C to constant weight. Approximately 180-200g of modified scorch powder is obtained.

[0134] The properties of the coke powder before and after modification are shown in Table 1.

[0135] Table 1.

[0136]

[0137] (2) Preparation of 1,3-dihydroxyethyl-calix[4]arene:

[0138] 1,3-Dihydroxyethyl-calix[4]arene is prepared by reacting calix[4]arene with iodoethanol, as described in Angewandte Chemie-International Edition, 2010, 49, 40, 7222-7224. The method is as follows: calix[4]arene (15 g, 35 mmol) and finely ground anhydrous potassium carbonate (9.75 g, 71.8 mmol) are added to acetonitrile (250 ml), followed by the addition of 2-iodoethanol (10 ml, 0.125 mol). The reaction mixture is stirred at reflux temperature for 24 hours under nitrogen protection. The reaction mixture is cooled, and most of the acetonitrile is removed by distillation under reduced pressure. The residue is fully dissolved in water (150 ml), and the aqueous phase is extracted with dichloromethane (50 ml x 3). The organic phases are combined, dried over anhydrous magnesium sulfate, and the dichloromethane solvent is removed by distillation under reduced pressure. The obtained crude product was purified by recrystallization from dichloromethane-methanol (v / v 1:5) to give colorless crystals (15 g, yield 80%).

[0139] (3) Coupling of 1,3-dihydroxyethyl-calix[4]arene with modified coke powder

[0140] In the attached Figure 1 In the reactor shown, 100 g of the modified coke powder prepared in the above step (1) was added, 200 mL of anhydrous tetrahydrofuran was added, and then 2.36 g (4.6 mmol) of 1,3-dihydroxyethyl-calix[4]arene and 0.8 g of diethyl azodicarbonate (4.6 mmol) were added. The nitrogen valve at the bottom of the reactor was opened with a nitrogen flow rate of 5 L / min. Under sufficient bubbling, 1.2 g (4.6 mmol) of triphenylphosphine (TPP) solid was slowly added. Subsequently, hot water was introduced into the jacket until the internal temperature of the reaction solution rose to 60°C and stirring was continued for 2 hours. After the reaction is completed, stop the nitrogen flow at the lower port, open the nitrogen valve at the upper port of the reactor, remove the excess reactants and by-products such as triphenylphosphine together with the solvent by filter pressing, turn off the nitrogen, add 100 mL of anhydrous tetrahydrofuran, open the nitrogen valve at the lower port, bubble wash for 10 minutes, close the nitrogen valve at the lower port, open the nitrogen valve at the upper port, filter out the liquid by filter pressing, close the nitrogen valve at the upper port, open the nitrogen valve at the lower port again, and let the resulting product dry at 60°C with nitrogen boiling for 2 hours to obtain 1,3-dihydroxyethyl-calix[4]arene-coke powder condensate, which is directly prepared in the next step.

[0141] (4) Preparation of 1,3-dihydroxyethyl-calix[4]arene-coke powder condensate modified with serine methyl ester:

[0142] In the above-mentioned reactor, 200 mL of tetrahydrofuran was added at room temperature, 3.1 g (20.0 mmol) of serine methyl ester hydrochloride was added, 1.70 g of formaldehyde aqueous solution (35%, 20.0 mmol) was added, and 1.2 g (20.0 mmol) of glacial acetic acid was added. The nitrogen valve at the lower part of the reactor was opened at a nitrogen flow rate of 5 L / min, and the reaction was fully bubbling overnight. After the reaction was completed, the nitrogen at the lower port was stopped, the nitrogen valve at the upper port of the reactor was opened, and the excess amino acid, acetic acid, etc. were removed together with the solvent by pressure filtration. Hot water was passed through the jacket, and the lower nitrogen valve was opened again. The resulting product was purged with nitrogen at 60° C. and boiled to dryness for 2 hours before being directly processed into the next step of preparation.

[0143] (5) Preparation of Catalyst 2

[0144] The nitrogen valve was closed, and 200 mL of anhydrous acetonitrile, 2.0 g (18.9 mmol) of finely ground anhydrous sodium carbonate powder, and 2.0 g (11.0 mol) of cyanuric chloride were added to the reactor. The reactor was closed and hot water was passed through the jacket. The reactor was heated to 60°C. At the same time, the nitrogen valve at the bottom of the reactor was opened, and the nitrogen flow rate was 5 L / min. The reaction was fully bubbled for 2 hours. After the reaction was completed, the temperature was lowered to room temperature, the nitrogen flow at the bottom was stopped, and the nitrogen valve at the top of the reactor was opened. The excess cyanuric chloride and the solvent were removed by pressure filtration. This part of the cyanuric chloride tetrahydrofuran solution can be directly used. Subsequently, 100 mL of deionized water was added to the reactor, and nitrogen bubbling and washing were carried out from the bottom. The upper nitrogen pressure filtration was repeated three times to remove the residual sodium carbonate in the system. Finally, hot water was passed through the jacket, and the resulting product was dried at 60°C under nitrogen purge and boiling for 2-4 hours to obtain catalyst 2.

[0145] By comparing the weights before and after the reaction, the loading amount of the active component of Catalyst 2 is about 700-900 ppm, depending on the preparation batch, that is, the active component contained in every 100 g of Catalyst 2 is about 0.07-0.09 g.

[0146] Example 3 Preparation of Catalyst 3 Using Modified Coke Powder as Support

[0147]

[0148] Catalyst 3 was prepared in the same manner as in Example 2, except that threonine methyl ester hydrochloride was added in an amount of 3.3 g (20.0 mmol) instead of serine methyl ester hydrochloride in step (4). All other conditions remained unchanged. Similarly, by comparing the weights before and after the reaction, the loading of the active component in Catalyst 3 was approximately 700-900 ppm, depending on the preparation batch.

[0149] Example 4 Preparation of Catalyst 4 Using Modified Coke Powder as Support

[0150] Catalyst 4 was prepared in the same manner as in Example 2, except that lysine methyl ester hydrochloride was added in an amount of 4.7 g (20.0 mmol) instead of serine methyl ester hydrochloride in step (3). All other conditions remained unchanged. Similarly, comparison of pre- and post-reaction weights revealed that the active component loading of Catalyst 3 was approximately 800-1000 ppm, depending on the preparation batch.

[0151] It should be pointed out here that since lysine contains two amino groups in its structure, a mixture of a series of products is actually obtained through the Mannich reaction. The structural schematic is shown below:

[0152]

[0153] Test Example 1 Catalyst 1 is used to prepare laurolactam from cyclododecanone oxime

[0154] In three 2000 mL reactors, 100 g of cyclododecanone oxime and 1000 mL of acetonitrile were added, followed by 0.36 g of Catalyst 1, 0.15 g of cyanuric chloride or 0.20 g of calix[4]arene (the amount of cyanuric chloride or calix[4]arene being substantially the same as that in Catalyst 1), and 0.5 mL of a 0.05 mol / L cobalt naphthenate solution. The reaction was stirred at 80°C for 2-3 hours. The conversion of cyclododecanone oxime and the selectivity for laurolactam were analyzed by GC chromatography. The results are shown in Table 2.

[0155] Table 2.

[0156] Catalyst 1 Cyanuric chloride Calix[4]arene Conversion rate (%) 65.0 2.2 Almost no reaction Selectivity (%) 99.0 75 -

[0157] The results show that calix[4]arene has almost no catalytic effect on the preparation of laurolactam from cyclododecanone oxime. The reaction using only cyanuric chloride as a catalyst has a poor reaction effect. This is because the present invention uses acetonitrile as a solvent, which is significantly different from the perfluoroisopropanol generally used in the literature. As a result, the catalytic effect of cyanuric chloride alone is poor. However, the conversion rate and selectivity of catalyst 1, which combines cyanuric chloride with calixarene, are greatly improved. It is said that by combining catalytically active substances such as cyanuric chloride with calixarene, it helps it adapt to a wider range of operating conditions and has better tolerance.

[0158] Test Example 2 Catalysts 2-4 are used to prepare laurolactam from cyclododecanone oxime

[0159] The above catalysts 2-4 are loaded as Figure 2 Reactions and evaluations were carried out in the reactor shown.

[0160] Figure 2The device shown is an intermittent or semi-continuous operation mode. In addition, the side sampling port of the material storage tank of the system can be connected to the sampling of the gas chromatograph to realize real-time analysis, monitor the reaction process, and determine the reaction end point. After the reaction is completed, the product is directly extracted without the need for neutralization, filtration or other treatments or steps to separate the catalyst, which has the dual purpose of improving evaluation efficiency and convenient product preparation. In addition, studies have shown that ketone oxime is easily oxidized, and the product lactam is also easily oxidized and yellowed by oxygen in the air, affecting downstream applications. Usually, nitrogen or argon is required for protection during the reaction process to isolate the air. In this device, the material is transported in a closed manner and is not in contact with the air throughout the process. While avoiding yellowing of the material, it saves the consumption of nitrogen, argon, etc. Compared with a stirred tank reactor, it can avoid the breakage and pulverization of the catalyst due to disordered collisions.

[0161] It should be noted that in the present invention, the amount of the catalyst loaded in the reaction tube that can process ketoxime in a single time is determined by experiment. The specific experimental method is to add an equal amount of catalyst in a glass round-bottom flask at a disposable basis, followed by adding an acetonitrile solution of ketoxime, react at the same temperature, monitor the reaction and complete within 2-3 hours (ketoxime conversion> 99%), and fine-tune based on this to optimize the amount of the catalyst that can process ketoxime in a single time. The reaction time is optimized to 2-3 hours to avoid the product staying in the reactor for a long time and causing side reactions; under the above-mentioned reaction conditions, the feed rate is 0.01-20L / min, preferably 0.02-0.03L / min during the reaction.

[0162] Specifically, the steps of applying catalyst 2-4 to cyclododecanone oxime to prepare laurolactam are as follows:

[0163] (1) Catalyst activation

[0164] Xiang Fu Figure 2 400g of catalyst 2-4 (about 0.9L, bulk density of about 530g / L) was added to the reactor 1 shown, the reactor was closed, 2000mL of 0.05mol / L cobalt naphthenate in acetonitrile solution was added through the upper inlet / discharge port 10 of the storage tank, the feed pump 8 was turned on, and at room temperature, the cobalt naphthenate in acetonitrile solution was pumped into the reactor 1 at a flow rate of 0.02L / min and circulated for 2-3 hours. The feed pump 8 and the feed port valve 3 were closed, the side discharge port 18 below the reactor was opened, and the nitrogen inlet 17 above the reactor 1 was opened to drain the liquid in the reactor to obtain the activated catalyst.

[0165] (2) Preparation of laurolactam from cyclododecanone oxime

[0166] Thermal oil is passed into chuck 2, and thermal oil heater 15, thermal oil pump 16 are opened, temperature is raised to 80 ℃ by measuring temperature point 5 and 6, then the acetonitrile solution (containing cyclododecanone oxime 100g, acetonitrile 1000g) containing cyclododecanone oxime is added in storage tank 9. Open feed pump 8, with the flow velocity of 0.02L / min, material is pumped into reactor 1, circulates 2-3 hour, by gas chromatography monitoring reaction process. When reaction finishes, feed pump 8 and feed port valve are closed, the side discharge port 18 below reactor 1 is opened, the nitrogen inlet 17 above reactor is opened, the liquid in reactor is discharged and mixed with the liquid in storage tank 9, the product solution obtained, the finished product uses the transformation efficiency of the cyclododecanone oxime of GC chromatographic analysis and the selectivity of laurolactam.Analysis results are shown in Table 3.

[0167] (3) Recycling of Catalyst 2

[0168] The operation method was the same as (1)-(2) in this test example. This operation was repeated 6 times to analyze the effect of the catalyst recycling 6 times. The content of metal ion Co in the product was determined by ICP method. The analysis results are shown in Table 3.

[0169] Table 3.

[0170]

[0171]

[0172] Comparing the data in Tables 2 and 3, it can be seen that Catalyst 2, using coke powder as a carrier, achieves a significantly higher conversion rate than Catalyst 1, which does not contain coke powder. This indicates that the coke powder not only serves as a carrier but also promotes the aggregation of reaction substrates on its surface, accelerating the reaction and improving conversion. This also demonstrates that in the catalyst system of the present invention, the combination of active centers, calixarene, and coke powder is not a simple stacking of structures, but rather imparts new functions and effects to each, achieving a 1+1+1>3 effect.

[0173] Furthermore, the catalyst system of the present invention exhibits good conversion and selectivity for the Beckmann rearrangement of cyclododecanone oxime to laurolactam. Compared to conventional preparation methods, the catalyst system of the present invention exhibits excellent recycling effectiveness, with no significant change in catalyst activity after six reuses. Furthermore, the residual Co ions in Recycle 1 were caused by the failure to wash the catalyst after activation. With increasing cycles, the Co residual gradually became undetectable, returning to normal levels.

[0174] It should be noted that the above embodiments can be adapted to adjust the structure of the coke powder and macrocyclic compound, as well as the distribution of the coke powder particles, as needed. The foregoing description only illustrates some embodiments of the present invention. It should be noted that those skilled in the art will be able to make various modifications without departing from the principles of the present invention, and such modifications are considered within the scope of protection of the present invention.

Claims

1. A catalyst for liquid-phase Beckmann rearrangement, comprising: A macrocyclic compound derivative formed by connecting a catalytically active group to a macrocyclic compound having a delocalized macro-π system via a connecting arm, and a modified coke powder, wherein the macrocyclic compound derivative is chemically modified on the surface of the modified coke powder; in, The macrocyclic compound is one or more of calixarene, pillararene or their derivatives; The linker is a structural fragment obtained by reacting a linker substance with a macrocyclic compound and a Beckmann rearrangement catalytic active component; the linker substance is selected from D-, L-, or racemic amino acids or amino acid esters, ethylenediamine, propylenediamine, diethyltriamine, 2,2'-oxybis(ethylamine), and ethanolamine; The catalytically active group is a group obtained by the reaction of the Beckmann rearrangement catalytically active component and the linker material; The Beckmann rearrangement catalytic active component is selected from one of cyanuric chloride and hexachlorocyclotriphosphazene or a combination thereof.

2. The catalyst according to claim 1, characterized in that The calixarene is one or more selected from calix[4]arene, calix[5]arene, calix[6]arene, calix[7]arene, calix[8]arene, and resorcinol calix[4]arene; The pillar aromatic hydrocarbon is pillar[5] aromatic hydrocarbon; The derivative of the calixarene or pillararene is that the hydrogen in the phenolic hydroxyl group of the calixarene or pillararene is replaced by -(CH2) m CH3, -(CH2CH2O) m H, -(CH2CH2) m OH or -(CH2) m The derivatives are formed by COOH substitution, wherein m is an integer of 1-6.

3. The catalyst according to claim 2, characterized in that m is an integer from 1 to 3.

4. The catalyst according to claim 2, characterized in that The macrocyclic compound is one or more of calix[4]arene and its derivatives.

5. The catalyst according to claim 1, characterized in that The amino acids are one or more selected from glycine, alanine, valine, leucine, isoleucine, tryptophan, serine, tyrosine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, and histidine.

6. The catalyst according to claim 1, characterized in that The macrocyclic compound derivative containing a catalytically active group has a structure shown in formula (I): （I） Wherein, n is 4, 5, 6, 7 or 8; Each R1 is selected from H, -(CH2) m CH3, -(CH2CH2O) m H, and each R1 is not H at the same time; m is 1 or 2; Each X is H or a structural fragment formed by the reaction of the linker material with the macrocyclic compound and the catalytically active component, and each X is not H at the same time. When X is H, R2 does not exist; Each R2 is independently a group formed after the Beckmann rearrangement catalytic active component reacts with the linker material.

7. The catalyst according to claim 6, characterized in that n is 4 and m is 1.

8. The catalyst according to claim 6, characterized in that X is a structural fragment formed by a Mannich reaction between one amino group in lysine methyl ester, serine methyl ester or threonine methyl ester and the benzene ring of the macrocyclic compound, and a substitution reaction between the other amino group or hydroxyl group and the catalytic active component.

9. The catalyst according to claim 6, characterized in that X is selected from 、 、 、 .

10. The catalyst according to claim 6, characterized in that Each R2 is independently selected from 、 One of them.

11. The catalyst according to claim 6, characterized in that R2 is .

12. The catalyst according to any one of claims 1 to 11, characterized in that The modified coke powder is obtained by surface activation and oxidation of coke powder, and the surface of the modified coke powder contains hydroxyl groups.

13. The catalyst according to claim 12, characterized in that The particle size of the coke powder is less than 5 mm.

14. The catalyst according to claim 13, characterized in that The particle size of the coke powder is 2-3 mm.

15. The catalyst according to claim 12, characterized in that The modified coke powder is prepared by a method comprising the following steps: The coke powder is calcined, and water vapor is introduced during the calcination process to activate it. After cooling, it is washed and dried to obtain surface-activated coke powder; the surface-activated coke powder is soaked in concentrated sulfuric acid and hydrogen peroxide to obtain oxidized coke powder; the oxidized coke powder is filtered, washed, and then dried to constant weight to obtain modified coke powder.

16. The catalyst according to claim 15, characterized in that The amount of water vapor introduced is 10-200% of the mass of the coke powder; and / or The mass concentration of the hydrogen peroxide is 10-60%; the amount of hydrogen peroxide used is 1-5% of the mass of the surface-activated coke powder; the amount of concentrated sulfuric acid used is 1-10% of the mass of the surface-activated coke powder; and / or The soaking time is 1-24 hours, and the soaking temperature is 20-80°C.

17. The catalyst according to claim 16, characterized in that The amount of water vapor introduced is 20-50% of the mass of the coke powder; and / or The mass concentration of the hydrogen peroxide is 30-50%; and / or The amount of hydrogen peroxide used is 2-3% of the mass of the surface-activated coke powder; and / or The amount of concentrated sulfuric acid used is 4-6% of the mass of the surface-activated coke powder; and / or The soaking time is 2-4 hours, and / or the soaking temperature is 25-45°C.

18. The catalyst according to claim 16, characterized in that The amount of water vapor introduced is 30-50% of the mass of the coke powder.

19. The catalyst according to claim 12, characterized in that The specific surface area of ​​the modified coke powder is 8.0-12.0m 2 / g, carbon content is 80-90%, ash content is 10-12%, and bulk density is 400-480g / L.

20. The method for preparing the catalyst according to claim 1, comprising the steps of: (1) activating and oxidizing the surface of the coke powder to obtain modified coke powder; wherein the surface of the modified coke powder after oxidation has hydroxyl groups; (2) modifying the macrocyclic compound on the surface of the modified coke powder by chemical reaction to obtain modified coke powder modified with the macrocyclic compound; wherein the macrocyclic compound is covalently linked to the surface of the modified coke powder by chemical reaction; (3) chemically reacting the modified coke powder modified with the macrocyclic compound with a linker substance to obtain a modified coke powder modified with the macrocyclic compound containing a linker; wherein the active group in the linker substance is connected to the structure in the macrocyclic compound through a chemical reaction; (4) The modified coke powder modified with a macrocyclic compound containing a connecting arm is reacted and connected with a Beckmann rearrangement catalytic active component through the connecting arm to obtain the catalyst; wherein the Beckmann rearrangement catalytic active component is connected with another active group of the connecting arm through a chemical reaction.

21. The preparation method according to claim 20, characterized in that In step (1), water vapor, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate is used to activate the surface of the coke powder, and then an oxidant is used in combination with an acidic compound to oxidize the surface.

22. The preparation method according to claim 21, characterized in that The oxidant is one or more selected from hydrogen peroxide, ozone, tert-butyl peroxide, m-chloroperbenzoic acid, and potassium dichromate; The acidic compound is one or more selected from concentrated sulfuric acid, concentrated phosphoric acid, aminosulfonic acid, methanesulfonic acid, and hydrofluoric acid.

23. The preparation method according to claim 21, characterized in that The surface of the coke powder was activated by water vapor, and then the surface of the coke powder was oxidized and modified by hydrogen peroxide and concentrated sulfuric acid.

24. The preparation method according to claim 20, characterized in that The preparation method comprises the following steps: (1) calcining the coke powder, introducing water vapor to activate it during the calcination process, cooling it, washing it, and drying it to obtain surface-activated coke powder; soaking the surface-activated coke powder in concentrated sulfuric acid and hydrogen peroxide to obtain oxidized coke powder; filtering and washing the oxidized coke powder, and then drying it to a constant weight to obtain modified coke powder; (2) mixing the calixarene derivative with the modified coke powder and an organic solvent, adding a condensation reagent to react, filtering, washing with an organic solvent to remove by-products generated by the reaction, and drying to obtain the calixarene-modified modified coke powder; (3) mixing the calixarene-modified modified char powder, amino acid or amino acid ester, formaldehyde aqueous solution, acetic acid and solvent, reacting at room temperature for a period of time by bubbling and stirring, and obtaining the calixarene-modified modified char powder containing an amino acid linker arm after filtering, washing and drying; (4) The modified coke powder modified with the calixarene containing an amino acid linker arm is heated to react for a period of time with one or a combination of cyanuric chloride, hexachlorocyclotriphosphazene, an acid-binding agent, and a solvent, and then filtered, washed, and dried to obtain the target catalyst.

25. The preparation method according to claim 24, characterized in that In step (1): The coke powder is crushed and then sieved before calcination, and the particle size distribution of the coke powder after sieving is 1-5 mm; and / or The calcination is carried out in a tube furnace and includes two stages: in the first stage, the temperature in the tube furnace is raised from room temperature to 300-800°C and kept at this temperature for 1-24 hours; in the second stage, the temperature is continuously raised to 700-1000°C with a temperature increase gradient of 1-10°C / min and kept at this temperature for 1-24 hours; and / or During the second stage, water vapor is introduced immediately after the temperature reaches the highest point or during the heat preservation process for activation; the amount of water vapor introduced is 10-200% of the mass of the coke powder, and is introduced all at once; and / or Cooling is natural cooling; and / or Soak the calcined and cooled coke powder in 5% dilute hydrochloric acid for 30-60 minutes; Wash the calcined, cooled, and diluted hydrochloric acid-soaked coke powder with desalted water until the filtrate has a pH of 5-6; Drying the calcined, cooled, soaked and washed coke powder at 80°C until the coke powder has a constant weight; and / or The mass concentration of hydrogen peroxide is 10-60%; and / or The amount of hydrogen peroxide used is 1-6% of the mass of the surface-activated coke powder; the amount of concentrated sulfuric acid used is 1-10% of the mass of the surface-activated coke powder; and / or Soaking the surface-activated coke powder in concentrated sulfuric acid and hydrogen peroxide for 1-24 hours at a temperature of 20-80° C.; and / or Wash the filtered oxidized coke powder with desalted water to a pH of 4-6; The filtered and washed oxidized coke powder is dried at a temperature of 60-120°C.

26. The preparation method according to claim 25, characterized in that After screening, the particle size distribution of coke powder is 2-3 mm; and / or During the first stage of calcination, the temperature in the tube furnace is raised from room temperature to 500-600°C and kept at this temperature for 2-3 hours; during the second stage, the temperature is continued to be raised to 800-900°C at a temperature increase gradient of 2-3°C / min and kept at this temperature for 2-3 hours; and / or During the second stage, the amount of water vapor introduced is 20-50% of the mass of the coke powder; and / or The mass concentration of hydrogen peroxide is 30-50%; and / or The amount of hydrogen peroxide used is 1-5% of the mass of the surface-activated coke powder; and / or The amount of concentrated sulfuric acid used is 4-6% of the mass of the surface-activated coke powder; and / or The surface activated coke powder is soaked in concentrated sulfuric acid and hydrogen peroxide for 2-4 hours and / or the soaking temperature is 25-45° C.; and / or The filtered and washed oxidized coke powder is dried at a temperature of 80-90°C.

27. The preparation method according to claim 25, characterized in that During the second stage of calcination, the amount of water vapor introduced is 30-50% of the mass of the coke powder; and / or The amount of hydrogen peroxide used is 2-3% of the mass of the surface-activated coke powder; and / or The amount of concentrated sulfuric acid used is 5-10% of the mass of the surface-activated coke powder.

28. The preparation method according to claim 24, characterized in that In step (2): The calixarene derivative is a phenolic hydroxyl group whose hydrogen is replaced by -(CH2CH2O) m H-substituted calixarene, selected from the following structures: and / or The amount of the calixarene derivative added is 0.1-10% of the mass of the modified coke powder; and / or The condensation reagents are azodicarbonate diester and triphenylphosphine; the molar ratio of the azodicarbonate diester to the calixarene derivative is 0.1-10:1; the molar ratio of triphenylphosphine to the azodicarbonate diester is equimolar; and / or The organic solvent is one or more selected from tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, dichloromethane, chloroform, benzene, toluene, xylene, ethyl acetate, acetonitrile, dimethyl sulfoxide, and petroleum ether; the amount of the organic solvent added is 10-400% of the mass of the modified coke powder; and / or The reaction temperature is 40-80°C; the reaction time is 0.5-5h.

29. The preparation method according to claim 28, characterized in that The amount of the calixarene derivative added is 0.5-5% of the mass of the modified coke powder; and / or The azodicarbonate diester is one of diethyl azodicarbonate, diisopropyl azodicarbonate, di-tert-butyl azodicarboxylate, and diphenyl azodicarboxylate, or a combination thereof; and / or The amount of the azodicarbonate diester added is in a molar ratio of 1:1 to the calixarene derivative; and / or The organic solvent is one or more combinations selected from tetrahydrofuran, methyltetrahydrofuran and methyl tert-butyl ether; and / or The amount of organic solvent added is 100-300% of the mass of the modified coke powder; and / or The reaction temperature is 50-60°C; and / or The reaction time is 1-3h.

30. The preparation method according to claim 29, wherein The amount of the calixarene derivative added is 0.5-3% of the mass of the modified coke powder; and / or The azodicarbonate diester is diethyl azodicarboxylate.

31. The preparation method according to claim 24, characterized in that In step (3), an amino acid or an amino acid ester undergoes a Mannich reaction with a calixarene derivative, wherein: The amino acid is D-, L-, or racemic serine, threonine, and lysine; the amino acid ester is amino acid methyl ester of serine, threonine, and lysine, or their methyl ester hydrochloride; the mass ratio of the amino acid or amino acid ester to the calixarene-modified modified char powder is 0.005-0.1:1.0; The concentration of the formaldehyde aqueous solution is 1-40 wt %, and the molar ratio of the added amino acid or amino acid ester to formaldehyde is 0.8-10:1.0; and / or acetic acid and amino acid or amino acid ester are added in equal molar ratios; and or The solvent is selected from one or more combinations of tetrahydrofuran, methyltetrahydrofuran, acetone, methanol, ethanol, isopropanol, and tert-butanol; the mass ratio of the solvent to the modified char powder modified by calixarene is 0.5-10:1.

0.

32. The preparation method according to claim 31, wherein The mass ratio of the amino acid or amino acid ester to the modified char powder modified by calixarene is 0.01-0.05:1.0; and / or The concentration of the formaldehyde solution is 35-37 wt%; and / or The molar ratio of the added amino acid or amino acid ester to formaldehyde is 0.8-1.0:1.0; and / or Acetic acid is glacial acetic acid; and or The solvent is selected from tetrahydrofuran and methyltetrahydrofuran; the mass ratio of the solvent to the modified coke powder modified by calixarene is 1.5-2.0:1.

0.

33. The preparation method according to claim 31, wherein The mass ratio of the amino acid or amino acid ester to the modified char powder modified with calixarene is 0.02-0.04:

1.

34. The preparation method according to claim 24, wherein In step (4), cyanuric chloride, hexachlorocyclotriphosphazene or a combination thereof undergoes a substitution reaction with the modified coke powder modified with a calixarene containing an amino acid linker arm, wherein: The mass ratio of cyanuric chloride, hexachlorocyclotriphosphazene or a combination thereof to the modified char powder modified with a calixarene containing an amino acid linker arm is 0.01-0.1:1; and / or The acid binding agent is selected from one or more combinations of potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine, and diisopropylethylamine; the molar ratio of the acid binding agent to cyanuric chloride, hexachlorocyclotriphosphazene, or a combination thereof is 1-10:1.0; and / or The solvent is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, methyltetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, and acetonitrile; the amount of the solvent is 10-400% of the mass of the modified char powder modified with calixarene containing an amino acid linker arm; and / or The reaction temperature of the heating reaction is 30-80°C; the reaction time is 0.5-5h; and / or Washing with deionized water to remove residual sodium carbonate in the reaction system; and / or Drying was carried out at 50-60°C under nitrogen purge.

35. The preparation method according to claim 34, wherein The mass ratio of cyanuric chloride, hexachlorocyclotriphosphazene or a combination thereof to the modified char powder modified with a calixarene containing an amino acid linker arm is 0.01-0.04:1.0; and / or The acid binding agent is sodium carbonate or potassium carbonate; and / or The molar ratio of the acid binding agent to cyanuric chloride, hexachlorocyclotriphosphazene or a combination thereof is 1.0-2.0:1.0; and / or The solvent is tetrahydrofuran, methyltetrahydrofuran or acetonitrile; and / or The amount of the solvent used is 100-300% of the mass of the modified char powder modified with calixarene containing an amino acid linker arm; and / or The reaction temperature of the heating reaction is 60-65° C.; and / or the reaction time is 1-3 h.

36. The preparation method according to claim 35, wherein The mass ratio of cyanuric chloride, hexachlorocyclotriphosphazene or a combination thereof to the modified char powder modified with calixarene containing an amino acid linker arm is 0.02:1.

0.

37. Use of the catalyst according to any one of claims 1 to 19 in a liquid-phase Beckmann rearrangement reaction.

38. Use of a catalyst in a liquid phase Beckmann rearrangement reaction, characterized in that: The catalyst comprises: a macrocyclic compound derivative formed by connecting a catalytically active group to a macrocyclic compound having a delocalized macro-π system via a connecting arm, wherein The macrocyclic compound is one or more of calixarene, pillararene or their derivatives; The linker is a structural fragment obtained by reacting a linker substance with a macrocyclic compound and a Beckmann rearrangement catalytic active component; the linker substance is selected from D-, L-, or racemic amino acids or amino acid esters, ethylenediamine, propylenediamine, diethyltriamine, 2,2'-oxybis(ethylamine), and ethanolamine; The catalytically active group is a group obtained by the reaction of the Beckmann rearrangement catalytically active component and the linker material; The Beckmann rearrangement catalytic active component is selected from one of cyanuric chloride and hexachlorocyclotriphosphazene or a combination thereof.

39. The use according to claim 38, characterized in that The calixarene is one or more selected from calix[4]arene, calix[5]arene, calix[6]arene, calix[7]arene, calix[8]arene, and resorcinol calix[4]arene; The pillar aromatic hydrocarbon is pillar[5] aromatic hydrocarbon; The derivative of the calixarene or pillararene is that the hydrogen in the phenolic hydroxyl group of the calixarene or pillararene is replaced by -(CH2) m CH3, -(CH2CH2O) m H, -(CH2CH2) m OH or -(CH2) m The derivatives are formed by COOH substitution, wherein m is an integer of 1-6.

40. The use according to claim 39, characterized in that m is an integer from 1 to 3.

41. The use according to claim 39, characterized in that The macrocyclic compound is one or more of calix[4]arene and its derivatives.

42. The use according to claim 38, characterized in that The amino acids are one or more selected from glycine, alanine, valine, leucine, isoleucine, tryptophan, serine, tyrosine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, and histidine.

43. The use according to claim 38, wherein The macrocyclic compound derivative containing a catalytically active group has a structure shown in formula (I): （I） Wherein, n is 4, 5, 6, 7 or 8; Each R1 is selected from H, -(CH2) m CH3, -(CH2CH2O) m H, and each R1 is not H at the same time; m is 1 or 2; Each X is H or a structural fragment formed by the reaction of the linker material with the macrocyclic compound and the catalytically active component, and each X is not H at the same time. When X is H, R2 does not exist; Each R2 is independently a group formed after the Beckmann rearrangement catalytic active component reacts with the linker material.

44. The use according to claim 43, wherein n is 4 and m is 1.

45. The use according to claim 43, characterized in that X is a structural fragment formed by a Mannich reaction between one amino group in lysine methyl ester, serine methyl ester or threonine methyl ester and the benzene ring of the macrocyclic compound, and a substitution reaction between the other amino group or hydroxyl group and the catalytic active component.

46. ​​The use according to claim 43, characterized in that X is selected from 、 、 、 .

47. The use according to claim 43, characterized in that Each R2 is independently selected from 、 One of them.

48. The use according to claim 43, characterized in that R2 is .

49. The use according to claim 37 or 38, characterized in that The liquid-phase Beckmann rearrangement reaction uses ketoxime as a raw material to prepare the corresponding amide; The ketoxime includes cyclic ketoxime and aliphatic ketoxime; and / or The catalyst is activated in a cobalt naphthenate solution before use; the ratio of cobalt naphthenate to catalyst is 0.08-0.12 mol: 400 g; the solvent of the cobalt naphthenate solution is a solvent for a liquid-phase Beckmann reaction; and / or In the liquid-phase Beckmann rearrangement reaction, the mass ratio of the catalyst to the ketoxime is 3.0-5.0:1.0; and / or The reaction temperature of the liquid-phase Beckmann rearrangement reaction is 70-160° C.; the reaction pressure is 0.1-5.0 MPa; and the reaction time is 0.1-10 h.

50. The use according to claim 49, wherein The cyclic ketone oxime is one or more selected from cyclopentanone oxime, cyclohexanone oxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanone oxime, cyclodecanone oxime, cycloundecanone oxime, and cyclododecanone oxime; the aliphatic ketone oxime is one or more selected from acetone oxime, butanone oxime, and heptanone oxime; and / or The solvent of the cobalt naphthenate solution is one or more of acetonitrile, tetrahydrofuran, and methyltetrahydrofuran; and / or The reaction temperature of the liquid-phase Beckmann rearrangement reaction is 70-90° C.; and / or the reaction pressure is 0.1-0.3 MPa; and / or the reaction time is 2-4 h.

51. The use according to claim 49, characterized in that The ketoxime is a cyclic ketoxime.

52. The use according to claim 49, characterized in that The ketoxime is cyclododecanone oxime.

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