A kind of preparation method of musk ketone

Abstract

The invention provides a method for preparing musk ketone, and belongs to the technical field of organic chemistry. Mg and methyl iodide are mixed for reaction, a catalyst is added, the mixed reaction is stirred, 2-cyclopentadecenone is added, the reaction is stirred, and the musk ketone is separated and purified to obtain the musk ketone. The method for preparing musk ketone of the invention is simple, the conditions are mild, the yield of the obtained musk ketone is high, the catalytic activity is high, the catalytic efficiency is high, the catalyst can react multiple times, and still maintains better catalytic activity, and has broad application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemistry, and in particular to a method for preparing musk ketone. Background Art

[0002] Musk is a very limited and expensive natural resource that is widely used in daily life, especially in medicine and perfume. Natural musk is mainly obtained by hunting musk deer, which is a first-class protected animal in my country. Killing musk deer for musk is not only illegal, but also seriously damages the ecological environment. As animal protection and ecological environment protection are increasingly valued, the significance of artificial musk is becoming more and more important.

[0003] The existing synthesis methods mainly include: bifunctional open-chain compound ring closing method, macrocyclic compound ring expansion method and methyl insertion method. Bifunctional open-chain compound ring closing method refers to the synthesis of musk ketone through intramolecular ring closing reactions such as aldol condensation, Dieckmann condensation, alcohol ketone condensation or Emmons-Horner olefination reaction.

[0004] In the process of obtaining 3-methylcyclopentadecenone by chloroacylation, carbonylation, ketohydrolysis and cyclization reaction with tetradecanedioic acid as raw material, and then obtaining musk ketone by catalytic hydrogenation reaction, the yield of the catalytic hydrogenation reaction has a great influence on the total yield and product quality of the whole route. Both C=O and C=C in 3-methylcyclopentadecenone can be hydrogenated, and its hydrogenation selectivity is affected by the stereo configuration of the catalyst and the electron cloud distribution of the active center. Therefore, the performance of the hydrogenation catalyst plays a key role in the hydrogenation process. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing musk ketone. The preparation method is simple, the conditions are mild, the yield of the prepared musk ketone is high, the catalytic activity is high, the catalytic efficiency is high, the catalyst can react multiple times and still maintain better catalytic activity, and the method has broad application prospects.

[0006] The technical solution of the present invention is achieved in this way:

[0007] The invention provides a method for preparing musk ketone, comprising the following steps: mixing Mg and methyl iodide for reaction, adding a catalyst, stirring the mixture for reaction, adding 2-cyclopentadecenone, stirring the reaction, separating and purifying to obtain musk ketone.

[0008] As a further improvement of the present invention, the mass volume ratio of Mg and methyl iodide is 2-3:0.5-1 g / mL, the temperature of the stirring and mixing reaction is 0-4°C, and the time is 0.5-1h. The mass volume ratio of 2-cyclopentadecenone and methyl iodide is 2-2.4:0.5-1 g / mL, the temperature of the stirring reaction is room temperature, and the time is 30-50 min.

[0009] As a further improvement of the present invention, the preparation method of the catalyst is as follows:

[0010] S1. Preparation of intercalated montmorillonite: adding montmorillonite powder to water, adding a surfactant, heating and stirring the reaction, filtering, washing, and drying to obtain intercalated montmorillonite;

[0011] S2. Preparation of magnetic intercalated montmorillonite: adding intercalated montmorillonite to water, adding ferric chloride and ferrous chloride, adding ammonia water dropwise under inert gas protection, heating and stirring the reaction, filtering, washing, drying, and calcining to obtain magnetic intercalated montmorillonite;

[0012] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite is placed in a tubular furnace insulation zone, heated under inert gas protection, n-hexane is introduced, the temperature is kept for reaction, and cooled to room temperature under inert gas protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0013] S4. Tannic acid modification: adding amorphous carbon / magnetic intercalated montmorillonite to a Tris-HCl solution, adding tannic acid, heating and stirring to react, separating with a magnet, washing, and drying to obtain modified amorphous carbon / magnetic intercalated montmorillonite;

[0014] S5. Fixation of Cu / Co: Add copper salt and cobalt salt into water, add modified amorphous carbon / magnetic intercalated montmorillonite, stir the reaction, separate with a magnet, wash, dry, and obtain a catalyst.

[0015] As a further improvement of the present invention, the mass ratio of the montmorillonite powder and the anionic surfactant in step S1 is 100:3-5, and the surfactant is selected from at least one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, sodium hexadecyl sulfonate, sodium hexadecyl sulfate, sodium hexadecylbenzene sulfonate, sodium octadecyl sulfate, sodium octadecyl sulfonate, sodium octadecylbenzene sulfonate, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and hexadecyldimethylbenzyl ammonium chloride, and the temperature of the heating and stirring reaction is 40-50°C, and the time is 1-2h.

[0016] As a further improvement of the present invention, the mass ratio of the intercalated montmorillonite, ferric chloride and ferrous chloride in step S2 is 10:3.2-3.3:1.2-1.3, the ammonia water is added dropwise until the pH value of the system is 7.5-8.5, the temperature of the heating and stirring reaction is 75-85°C, the time is 2-4h, and the calcination temperature is 400-500°C, and the time is 1-2h.

[0017] As a further improvement of the present invention, in step S3, the temperature is raised to 650-670° C., the ventilation rate of n-hexane is 0.3-0.5 mL / min, and the insulation reaction time is 20-40 min.

[0018] As a further improvement of the present invention, the pH value of the Tris-HCl solution in step S4 is 8.2-8.7, the mass ratio of the amorphous carbon / magnetic intercalated montmorillonite and tannic acid is 10:1-2, the temperature of the heating and stirring reaction is 35-45°C, and the time is 1-3h.

[0019] As a further improvement of the present invention, the mass ratio of the copper salt, the cobalt salt, and the modified amorphous carbon / magnetic intercalated montmorillonite in step S5 is 1-2:0.5-1.5:10, the copper salt is selected from at least one of copper chloride, copper sulfate, and copper nitrate, the cobalt salt is cobalt chloride or cobalt nitrate, and the stirring reaction time is 20-30 minutes.

[0020] The present invention further protects musk ketone prepared by the above preparation method.

[0021] The present invention further protects a catalyst, the preparation method of which comprises the following steps:

[0022] S1. Preparation of intercalated montmorillonite: 100 parts by weight of montmorillonite powder was added to water, 3-5 parts by weight of a surfactant was added, heated to 40-50 ° C, stirred for 1-2h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0023] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride, with a mass ratio of 3-5:2-4;

[0024] S2. Preparation of magnetic intercalated montmorillonite: 10 parts by weight of intercalated montmorillonite was added to water, 3.2-3.3 parts by weight of ferric chloride and 1.2-1.3 parts by weight of ferrous chloride were added, and under the protection of inert gas, aqueous ammonia was added dropwise until the pH value of the system was 7.5-8.5, heated to 75-85 ° C, stirred for 2-4h, filtered, washed, dried, and calcined at 400-500 ° C for 1-2h to obtain magnetic intercalated montmorillonite;

[0025] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite is placed in a tubular furnace insulation zone, heated to 650-670°C under inert gas protection, n-hexane is introduced at a flow rate of 0.3-0.5 mL / min, the reaction is kept warm for 20-40 min, and cooled to room temperature under inert gas protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0026] S4. Tannic acid modification: 10 parts by weight of amorphous carbon / magnetic intercalated montmorillonite was added to a Tris-HCl solution having a pH value of 8.2-8.7, 1-2 parts by weight of tannic acid was added, heated to 35-45°C, stirred for 1-3h, separated by a magnet, washed, and dried to obtain a modified amorphous carbon / magnetic intercalated montmorillonite;

[0027] S5. Fixation of Cu / Co: add 1-2 parts by weight of copper salt and 0.5-1.5 parts by weight of cobalt salt into water, add 10 parts by weight of modified amorphous carbon / magnetic intercalated montmorillonite, stir the reaction for 20-30 minutes, separate with a magnet, wash, and dry to obtain a catalyst.

[0028] The present invention has the following beneficial effects:

[0029] Montmorillonite is a layered silicate mineral with excellent expansion, adsorption and cation exchange properties, which enables it to undergo interlayer complexation or insertion reactions with a variety of guest substances. Under the synergistic action of anionic and cationic surfactants, the surfactants enter the montmorillonite interlayers to form a composite pillared structure. This composite action can significantly increase the interlayer spacing of organic montmorillonite, thereby significantly improving the specific surface area of ​​the composite material.

[0030] Under the premise of increasing the specific surface area, the obtained intercalated montmorillonite facilitates the deposition of magnetic ferroferric oxide. On the one hand, it increases the loading amount of magnetic substances and facilitates the magnetic separation of the catalyst. On the other hand, the loaded magnetic trivalent iron and divalent iron also have a good synergistic catalytic effect on the alkylation reaction, thereby improving the activity of the catalyst.

[0031] The invention loads amorphous carbon on the surface of the prepared magnetic intercalated montmorillonite by a chemical vapor deposition method, thereby greatly improving the specific surface area of ​​the catalyst and facilitating the subsequent loading of tannic acid. The structures of the carboxyl group, hydroxyl group and the like of the tannic acid are convenient for loading with metal ions such as copper ions and cobalt ions by forming complex bonds, thereby greatly improving the loading amount of the metal ions. Under the synergistic catalytic action of the copper ions and the cobalt ions, the alkylation catalytic performance of the catalyst is significantly improved. In addition, the dual functions of the metal and the acid center realize efficient synergistic catalysis, thereby greatly improving the catalytic activity of the catalyst, reducing the activation energy, and significantly improving the reaction efficiency of the reaction of catalyzing the alkylation reaction to obtain musk ketone, thereby greatly improving the yield of musk ketone.

[0032] The preparation method of musk ketone of the invention is simple and the conditions are mild. The prepared musk ketone has high yield, high catalytic activity and high catalytic efficiency. The catalyst can react multiple times and still maintain better catalytic activity, and has broad application prospects. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Montmorillonite powder, with a whiteness of 90% and an average grain size of 10±2 μm, was purchased from Shijiazhuang Fenghua Mineral Products Co., Ltd.

[0035] Preparation Example 1

[0036] A catalyst, the preparation method of which comprises the following steps:

[0037] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 3 g of a surfactant was added, heated to 40 ° C, stirred for 1 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0038] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride, with a mass ratio of 3:2;

[0039] S2. Preparation of magnetic intercalated montmorillonite: 10 g of intercalated montmorillonite was added to 200 mL of water, 3.2 g of ferric chloride and 1.2 g of ferrous chloride were added, and under nitrogen protection, aqueous ammonia was added dropwise until the pH value of the system was 7.5, heated to 75 ° C, stirred for 2 h, filtered, washed, dried, and calcined at 400 ° C for 1 h to obtain magnetic intercalated montmorillonite;

[0040] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite was placed in a tubular furnace insulation zone, heated to 650°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.3 mL / min, the reaction was kept warm for 20 min, and cooled to room temperature under nitrogen protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0041] S4. Tannic acid modification: 10 g of amorphous carbon / magnetic intercalated montmorillonite was added to 200 mL of Tris-HCl solution with a pH value of 8.2, 1 g of tannic acid was added, heated to 35°C, stirred for reaction for 1 h, separated by magnet, washed, and dried to obtain modified amorphous carbon / magnetic intercalated montmorillonite;

[0042] S5. Fixation of Cu / Co: Add 1 g of copper nitrate and 0.5 g of cobalt nitrate into 200 mL of water, add 10 g of modified amorphous carbon / magnetic intercalated montmorillonite, stir and react for 20 min, separate with a magnet, wash, and dry to obtain a catalyst.

[0043] Preparation Example 2

[0044] A catalyst, the preparation method of which comprises the following steps:

[0045] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 5 g of surfactant was added, heated to 50 ° C, stirred for 2 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0046] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride in a mass ratio of 5:4;

[0047] S2. Preparation of magnetic intercalated montmorillonite: 10 g of intercalated montmorillonite was added to 200 mL of water, 3.3 g of ferric chloride and 1.3 g of ferrous chloride were added, and under nitrogen protection, ammonia was added dropwise until the pH value of the system was 8.5, heated to 85 ° C, stirred for 4 h, filtered, washed, dried, and calcined at 500 ° C for 2 h to obtain magnetic intercalated montmorillonite;

[0048] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite was placed in a tubular furnace insulation zone, heated to 670°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.5 mL / min, the reaction was kept warm for 40 min, and cooled to room temperature under nitrogen protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0049] S4. Tannic acid modification: 10 g of amorphous carbon / magnetic intercalated montmorillonite was added to 200 mL of Tris-HCl solution with a pH value of 8.7, 2 g of tannic acid was added, heated to 45°C, stirred for reaction for 3 h, separated by magnet, washed, and dried to obtain modified amorphous carbon / magnetic intercalated montmorillonite;

[0050] S5. Fixation of Cu / Co: Add 2 g of copper sulfate and 1.5 g of cobalt chloride into 200 mL of water, add 10 g of modified amorphous carbon / magnetic intercalated montmorillonite, stir and react for 30 min, separate with a magnet, wash, and dry to obtain a catalyst.

[0051] Preparation Example 3

[0052] A catalyst, the preparation method of which comprises the following steps:

[0053] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 4 g of a surfactant was added, heated to 45 ° C, stirred for 1.5 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0054] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride in a mass ratio of 4:3;

[0055] S2. Preparation of magnetic intercalated montmorillonite: 10 g of intercalated montmorillonite was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, and under nitrogen protection, aqueous ammonia was added dropwise until the pH value of the system was 8, heated to 80 ° C, stirred for 3 h, filtered, washed, dried, and calcined at 450 ° C for 1.5 h to obtain magnetic intercalated montmorillonite;

[0056] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite was placed in a tubular furnace insulation zone, heated to 660°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.4 mL / min, and the reaction was kept warm for 30 min, and cooled to room temperature under nitrogen protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0057] S4. Tannic acid modification: 10 g of amorphous carbon / magnetic intercalated montmorillonite was added to 200 mL of Tris-HCl solution with a pH value of 8.5, 1.5 g of tannic acid was added, heated to 40°C, stirred for reaction for 2 h, separated by magnet, washed, and dried to obtain modified amorphous carbon / magnetic intercalated montmorillonite;

[0058] S5. Fixation of Cu / Co: Add 1.5 g of copper chloride and 1 g of cobalt chloride into 200 mL of water, add 10 g of modified amorphous carbon / magnetic intercalated montmorillonite, stir and react for 25 min, separate with a magnet, wash, and dry to obtain a catalyst.

[0059] Comparative Preparation Example 1

[0060] Compared with Preparation Example 3, the difference is that step S1 is not performed.

[0061] The details are as follows:

[0062] S1. Preparation of magnetic intercalated montmorillonite: 10 g of montmorillonite powder was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, and under nitrogen protection, ammonia water was added dropwise until the pH value of the system was 8, heated to 80 ° C, stirred for 3 h, filtered, washed, dried, and calcined at 450 ° C for 1.5 h to obtain magnetic intercalated montmorillonite;

[0063] S2. Amorphous carbon deposition: The magnetic montmorillonite was placed in a tubular furnace insulation zone, heated to 660°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.4 mL / min, and the reaction was kept warm for 30 min. The amorphous carbon / magnetic montmorillonite was obtained by cooling to room temperature under nitrogen protection;

[0064] S3. Tannic acid modification: 10 g of amorphous carbon / magnetic montmorillonite was added to 200 mL of Tris-HCl solution with a pH value of 8.5, 1.5 g of tannic acid was added, heated to 40°C, stirred for reaction for 2 h, separated by a magnet, washed, and dried to obtain modified amorphous carbon / magnetic montmorillonite;

[0065] S4. Fixation of Cu / Co: Add 1.5 g of copper chloride and 1 g of cobalt chloride into 200 mL of water, add 10 g of modified amorphous carbon / magnetic montmorillonite, stir and react for 25 min, separate with a magnet, wash, and dry to obtain a catalyst.

[0066] Comparative Preparation Example 2

[0067] Compared with Preparation Example 3, the difference is that step S2 is not performed.

[0068] The details are as follows:

[0069] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 4 g of a surfactant was added, heated to 45 ° C, stirred for 1.5 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0070] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride in a mass ratio of 4:3;

[0071] S2. Amorphous carbon deposition: The intercalated montmorillonite was placed in a tubular furnace insulation zone, heated to 660°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.4 mL / min, and the reaction was kept warm for 30 min, and cooled to room temperature under nitrogen protection to obtain amorphous carbon / intercalated montmorillonite;

[0072] S3. Tannic acid modification: 10 g of amorphous carbon / intercalated montmorillonite was added to 200 mL of Tris-HCl solution with a pH value of 8.5, 1.5 g of tannic acid was added, heated to 40°C, stirred for reaction for 2 h, separated by a magnet, washed, and dried to obtain modified amorphous carbon / intercalated montmorillonite;

[0073] S4. Fixation of Cu / Co: Add 1.5 g of copper chloride and 1 g of cobalt chloride into 200 mL of water, add 10 g of modified amorphous carbon / intercalated montmorillonite, stir and react for 25 min, separate with a magnet, wash, and dry to obtain a catalyst.

[0074] Comparative Preparation Example 3

[0075] Compared with Preparation Example 3, the difference is that step S3 is not performed.

[0076] The details are as follows:

[0077] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 4 g of a surfactant was added, heated to 45 ° C, stirred for 1.5 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0078] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride in a mass ratio of 4:3;

[0079] S2. Preparation of magnetic intercalated montmorillonite: 10 g of intercalated montmorillonite was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, and under nitrogen protection, aqueous ammonia was added dropwise until the pH value of the system was 8, heated to 80 ° C, stirred for 3 h, filtered, washed, dried, and calcined at 450 ° C for 1.5 h to obtain magnetic intercalated montmorillonite;

[0080] S3. Tannic acid modification: 10 g of magnetic intercalated montmorillonite was added to 200 mL of Tris-HCl solution with a pH value of 8.5, 1.5 g of tannic acid was added, heated to 40 ° C, stirred for 2 h, separated by magnet, washed, and dried to obtain modified magnetic intercalated montmorillonite;

[0081] S4. Fixation of Cu / Co: Add 1.5 g of copper chloride and 1 g of cobalt chloride into 200 mL of water, add 10 g of modified magnetic intercalated montmorillonite, stir and react for 25 min, separate with a magnet, wash, and dry to obtain a catalyst.

[0082] Comparative Preparation Example 4

[0083] Compared with Preparation Example 3, the difference is that step S4 is not performed.

[0084] The details are as follows:

[0085] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 4 g of a surfactant was added, heated to 45 ° C, stirred for 1.5 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0086] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride in a mass ratio of 4:3;

[0087] S2. Preparation of magnetic intercalated montmorillonite: 10 g of intercalated montmorillonite was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, and under nitrogen protection, aqueous ammonia was added dropwise until the pH value of the system was 8, heated to 80 ° C, stirred for 3 h, filtered, washed, dried, and calcined at 450 ° C for 1.5 h to obtain magnetic intercalated montmorillonite;

[0088] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite was placed in a tubular furnace insulation zone, heated to 660°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.4 mL / min, and the reaction was kept warm for 30 min, and cooled to room temperature under nitrogen protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0089] S4. Fixation of Cu / Co: Add 1.5 g of copper chloride and 1 g of cobalt chloride into 200 mL of water, add 10 g of amorphous carbon / magnetic intercalated montmorillonite, stir and react for 25 min, separate with a magnet, wash, and dry to obtain a catalyst.

[0090] Comparative Preparation Example 5

[0091] Compared with Preparation Example 3, the difference is that copper chloride is not added in step S5.

[0092] The details are as follows:

[0093] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 4 g of a surfactant was added, heated to 45 ° C, stirred for 1.5 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0094] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride in a mass ratio of 4:3;

[0095] S2. Preparation of magnetic intercalated montmorillonite: 10 g of intercalated montmorillonite was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, and under nitrogen protection, aqueous ammonia was added dropwise until the pH value of the system was 8, heated to 80 ° C, stirred for 3 h, filtered, washed, dried, and calcined at 450 ° C for 1.5 h to obtain magnetic intercalated montmorillonite;

[0096] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite was placed in a tubular furnace insulation zone, heated to 660°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.4 mL / min, and the reaction was kept warm for 30 min, and cooled to room temperature under nitrogen protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0097] S4. Tannic acid modification: 10 g of amorphous carbon / magnetic intercalated montmorillonite was added to 200 mL of Tris-HCl solution with a pH value of 8.5, 1.5 g of tannic acid was added, heated to 40°C, stirred for reaction for 2 h, separated by magnet, washed, and dried to obtain modified amorphous carbon / magnetic intercalated montmorillonite;

[0098] S5. Fixation of Co: 2.5 g of cobalt chloride was added to 200 mL of water, and 10 g of modified amorphous carbon / magnetic intercalated montmorillonite was added. The reaction was stirred for 25 min, separated by a magnet, washed, and dried to obtain a catalyst.

[0099] Comparative Preparation Example 6

[0100] Compared with Preparation Example 3, the difference is that cobalt chloride is not added in step S5.

[0101] The details are as follows:

[0102] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 4 g of a surfactant was added, heated to 45 ° C, stirred for 1.5 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0103] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride in a mass ratio of 4:3;

[0104] S2. Preparation of magnetic intercalated montmorillonite: 10 g of intercalated montmorillonite was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, and under nitrogen protection, aqueous ammonia was added dropwise until the pH value of the system was 8, heated to 80 ° C, stirred for 3 h, filtered, washed, dried, and calcined at 450 ° C for 1.5 h to obtain magnetic intercalated montmorillonite;

[0105] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite was placed in a tubular furnace insulation zone, heated to 660°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.4 mL / min, and the reaction was kept warm for 30 min, and cooled to room temperature under nitrogen protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0106] S4. Tannic acid modification: 10 g of amorphous carbon / magnetic intercalated montmorillonite was added to 200 mL of Tris-HCl solution with a pH value of 8.5, 1.5 g of tannic acid was added, heated to 40°C, stirred for reaction for 2 h, separated by magnet, washed, and dried to obtain modified amorphous carbon / magnetic intercalated montmorillonite;

[0107] S5. Fixation of Cu: Add 2.5 g of copper chloride into 200 mL of water, add 10 g of modified amorphous carbon / magnetic intercalated montmorillonite, stir and react for 25 min, separate with a magnet, wash, and dry to obtain a catalyst.

[0108] Comparative Preparation Example 7

[0109] Compared with Preparation Example 3, the difference is that step S5 is not performed.

[0110] The details are as follows:

[0111] S1. Preparation of intercalated montmorillonite: 100 g of montmorillonite powder was added to 500 mL of water, 4 g of a surfactant was added, heated to 45 ° C, stirred for 1.5 h, filtered, washed, and dried to obtain intercalated montmorillonite;

[0112] The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride in a mass ratio of 4:3;

[0113] S2. Preparation of magnetic intercalated montmorillonite: 10 g of intercalated montmorillonite was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, and under nitrogen protection, aqueous ammonia was added dropwise until the pH value of the system was 8, heated to 80 ° C, stirred for 3 h, filtered, washed, dried, and calcined at 450 ° C for 1.5 h to obtain magnetic intercalated montmorillonite;

[0114] S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite was placed in a tubular furnace insulation zone, heated to 660°C under nitrogen protection, n-hexane was introduced at a flow rate of 0.4 mL / min, and the reaction was kept warm for 30 min, and cooled to room temperature under nitrogen protection to obtain amorphous carbon / magnetic intercalated montmorillonite;

[0115] S4. Tannic acid modification: add 10 g amorphous carbon / magnetic intercalated montmorillonite into 200 mL Tris-HCl solution with a pH value of 8.5, add 1.5 g tannic acid, heat to 40°C, stir and react for 2 h, separate with a magnet, wash, and dry to obtain modified amorphous carbon / magnetic intercalated montmorillonite, which is the catalyst.

[0116] Test Example 1

[0117] The specific surface areas of the catalysts prepared in Preparation Examples 1-3 and Comparative Preparation Examples 1-7 were measured using a high-throughput gas adsorption instrument. The results are shown in Table 1.

[0118] Table 1

[0119]

[0120]

[0121] It can be seen from the above table that the catalysts prepared in Preparation Examples 1-3 of the present invention have a relatively high specific surface area.

[0122] Preparation method of 2-cyclopentadecenone References: Liu Jinyu, Hu Yanru, Yang Fengke, et al. Synthesis and optimization of musk ketone [J], Journal of Qingdao University of Science and Technology (Natural Science Edition), 2016, 37(6): 609-612, 618. Article number: 1672-6987(2016)06-0609-04; DOI: 10.16351 / j.1672-6987.2016.06.004.

[0123] Example 1

[0124] The present embodiment provides a method for preparing musk ketone, comprising the following steps: mixing 2 g of Mg and 0.5 mL of iodomethane for reaction, adding the catalyst prepared in Preparation Example 1 in an amount of 1 wt% of the total mass of the system, stirring and mixing at 0° C. for reaction for 1 h, adding 2 g of 2-cyclopentadecenone, stirring and reacting at room temperature for 50 min, separating and purifying to obtain musk ketone.

[0125] Example 2

[0126] The present embodiment provides a method for preparing musk ketone, comprising the following steps: mixing 3 g of Mg and 1 mL of methyl iodide for reaction, adding the catalyst prepared in Preparation Example 2 in an amount of 1 wt% of the total mass of the system, stirring and mixing at 4° C. for reaction for 0.5 h, adding 2.4 g of 2-cyclopentadecenone, stirring and reacting at room temperature for 30 min, separating and purifying, and preparing musk ketone.

[0127] Example 3

[0128] The present embodiment provides a method for preparing musk ketone, comprising the following steps: mixing 2.5 g of Mg and 0.7 mL of iodomethane for reaction, adding the catalyst prepared in Preparation Example 3 in an amount of 1 wt % of the total mass of the system, stirring and mixing at 2° C. for reaction for 1 h, adding 2.2 g of 2-cyclopentadecenone, stirring and reacting at room temperature for 40 min, separating and purifying to obtain musk ketone.

[0129] Comparative Example 1

[0130] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 1.

[0131] Comparative Example 2

[0132] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 2.

[0133] Comparative Example 3

[0134] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 3.

[0135] Comparative Example 4

[0136] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 4.

[0137] Comparative Example 5

[0138] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 5.

[0139] Comparative Example 6

[0140] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 6.

[0141] Comparative Example 7

[0142] Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 7.

[0143] Test Example 1

[0144] The methods in Examples 1-3 and Comparative Examples 1-5 were evaluated, and the results are shown in Table 2.

[0145] Table 2

[0146] Group Yield of musk ketone (%) Example 1 88.9 Example 2 90.2 Example 3 91.1 Comparative Example 1 81.2 Comparative Example 2 82.7 Comparative Example 3 76.8 Comparative Example 4 70.4 Comparative Example 5 74.5 Comparative Example 6 75.1 Comparative Example 7 69.6

[0147] It can be seen from the above table that the yield of musk ketone obtained by the method in Examples 1-3 of the present invention is higher.

[0148] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing musk ketone, characterized in that: The method comprises the following steps: mixing Mg and methyl iodide for reaction, adding a catalyst, stirring the mixture for reaction, adding 2-cyclopentadecenone, stirring the mixture for reaction, separating and purifying to obtain musk ketone; The preparation method of the catalyst is as follows: S1. Preparation of intercalated montmorillonite: adding montmorillonite powder to water, adding a surfactant, heating and stirring the reaction, filtering, washing, and drying to obtain intercalated montmorillonite; The surfactant is sodium lauryl sulfate and hexadecyltrimethylammonium chloride; S2. Preparation of magnetic intercalated montmorillonite: adding intercalated montmorillonite to water, adding ferric chloride and ferrous chloride, adding ammonia water dropwise under inert gas protection, heating and stirring the reaction, filtering, washing, drying, and calcining to obtain magnetic intercalated montmorillonite; S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite is placed in a tubular furnace insulation zone, heated under inert gas protection, n-hexane is introduced, the temperature is kept for reaction, and cooled to room temperature under inert gas protection to obtain amorphous carbon / magnetic intercalated montmorillonite; S4. Tannic acid modification: adding amorphous carbon / magnetic intercalated montmorillonite to a Tris-HCl solution, adding tannic acid, heating and stirring to react, separating with a magnet, washing, and drying to obtain modified amorphous carbon / magnetic intercalated montmorillonite; S5. Fixation of Cu / Co: Add copper salt and cobalt salt into water, add modified amorphous carbon / magnetic intercalated montmorillonite, stir the reaction, separate with a magnet, wash, dry, and obtain a catalyst.

2. The preparation method according to claim 1, characterized in that: The mass volume ratio of Mg and methyl iodide is 2-3:0.5-1 g / mL, the temperature of the stirring and mixing reaction is 0-4°C, and the time is 0.5-1h. The mass volume ratio of 2-cyclopentadecenone and methyl iodide is 2-2.4:0.5-1 g / mL, the temperature of the stirring reaction is room temperature, and the time is 30-50 min.

3. The preparation method according to claim 1, characterized in that: The temperature of the heating and stirring reaction in step S1 is 40-50° C. and the time is 1-2 h.

4. The preparation method according to claim 1, characterized in that: In step S2, the mass ratio of intercalated montmorillonite, ferric chloride and ferrous chloride is 10:3.2-3.3:1.2-1.3, ammonia water is added dropwise until the pH value of the system is 7.5-8.5, the temperature of the heating and stirring reaction is 75-85°C, the time is 2-4h, and the calcination temperature is 400-500°C, and the time is 1-2h.

5. The preparation method according to claim 1, characterized in that: In step S3, the temperature is raised to 650-670° C., the ventilation rate of n-hexane is 0.3-0.5 mL / min, and the insulation reaction time is 20-40 min.

6. The preparation method according to claim 1, characterized in that: The pH value of the Tris-HCl solution in step S4 is 8.2-8.7, the mass ratio of the amorphous carbon / magnetic intercalated montmorillonite and tannic acid is 10:1-2, the temperature of the heating and stirring reaction is 35-45° C., and the time is 1-3 hours.

7. The preparation method according to claim 1, characterized in that: In step S5, the mass ratio of the copper salt, the cobalt salt, and the modified amorphous carbon / magnetic intercalated montmorillonite is 1-2:0.5-1.5:10, the copper salt is selected from at least one of copper chloride, copper sulfate, and copper nitrate, the cobalt salt is cobalt chloride or cobalt nitrate, and the stirring reaction time is 20-30 minutes.

8. A catalyst, characterized in that The preparation method comprises the following steps: S1. Preparation of intercalated montmorillonite: 100 parts by weight of montmorillonite powder was added to water, 3-5 parts by weight of a surfactant was added, heated to 40-50 ° C, stirred for 1-2h, filtered, washed, and dried to obtain intercalated montmorillonite; The surfactant is sodium dodecyl sulfate and hexadecyl trimethyl ammonium chloride, with a mass ratio of 3-5:2-4; S2. Preparation of magnetic intercalated montmorillonite: 10 parts by weight of intercalated montmorillonite was added to water, 3.2-3.3 parts by weight of ferric chloride and 1.2-1.3 parts by weight of ferrous chloride were added, and under the protection of inert gas, aqueous ammonia was added dropwise until the pH value of the system was 7.5-8.5, heated to 75-85 ° C, stirred for 2-4h, filtered, washed, dried, and calcined at 400-500 ° C for 1-2h to obtain magnetic intercalated montmorillonite; S3. Amorphous carbon deposition: The magnetic intercalated montmorillonite is placed in a tubular furnace insulation zone, heated to 650-670°C under inert gas protection, n-hexane is introduced at a flow rate of 0.3-0.5 mL / min, the reaction is kept warm for 20-40 min, and cooled to room temperature under inert gas protection to obtain amorphous carbon / magnetic intercalated montmorillonite; S4. Tannic acid modification: 10 parts by weight of amorphous carbon / magnetic intercalated montmorillonite was added to a Tris-HCl solution having a pH value of 8.2-8.7, 1-2 parts by weight of tannic acid was added, heated to 35-45°C, stirred for 1-3h, separated by a magnet, washed, and dried to obtain a modified amorphous carbon / magnetic intercalated montmorillonite; S5. Fixation of Cu / Co: add 1-2 parts by weight of copper salt and 0.5-1.5 parts by weight of cobalt salt into water, add 10 parts by weight of modified amorphous carbon / magnetic intercalated montmorillonite, stir the reaction for 20-30 minutes, separate with a magnet, wash, and dry to obtain a catalyst.

Images