A process for the synthesis of hydrogen peroxide pinane

Abstract

The present application relates to the technical field of organic peroxide, and particularly relates to a synthesis process of hydrogen peroxide pinane, which comprises the following steps: in the presence of hydrogen atmosphere and a catalyst, catalytic hydrogenation reaction is carried out on alpha-pinene to obtain a reaction mixture rich in cis-pinane; the catalyst is separated from the reaction mixture, and the remaining material is subjected to rectification to obtain cis-pinane; in the presence of an oxygen-containing gas atmosphere and an initiator, liquid phase oxidation reaction is carried out on the cis-pinane to obtain an oxidation liquid containing hydrogen peroxide pinane; the initiator is separated from the oxidation liquid, and the obtained organic phase is concentrated to obtain a product. The present application constructs a green process of continuous synthesis of hydrogen peroxide pinane through alpha-pinene hydrogenation-pinane oxidation, and provides a novel synthesis strategy which is efficient and safe, can be repeatedly used, and has no homogeneous initiator residue.

Description

Technical Field

[0001] This invention relates to the field of organic peroxide technology, and more particularly to a synthesis process for pinane hydroperoxide. Background Technology

[0002] Pinane hydrogen peroxide belongs to the cyclic terpenoid organic peroxide class. Its molecular structure contains peroxy bonds, giving it excellent oxidizing activity and selectivity, making it a mild yet highly efficient oxidizing agent. Pinane hydrogen peroxide is widely used as an initiator in organic polymerization reactions and as a resin curing agent. It is also a key intermediate in the synthesis of linalool and other terpenoid fragrances, as well as vitamin E, playing an indispensable role in fine chemicals, pharmaceutical intermediates, and fragrance synthesis. While α-pinene, the main component of turpentine oil, can be hydrogenated to produce pinane, pinane hydrogen peroxide is typically prepared from pinane through an oxidation reaction, mainly using batch and continuous methods.

[0003] Patent publication number CN102911102A discloses a method and apparatus for producing pinane hydroperoxide. In this method, pinane is fed into an oxidation tower from the bottom while compressed air is simultaneously introduced into the bottom of the tower, causing bubbling and ensuring sufficient contact between the air and pinane. After the reaction is complete, compressed air is introduced to pump the reaction fluid to a product storage tank, where it is purified by distillation to obtain high-concentration pinane hydroperoxide. This method features a short reaction time, excellent selectivity for pinane hydroperoxide, easy separation and purification of the reaction product, and a high recovery rate.

[0004] Currently used catalysts are mostly traditional single-metal catalysts or ordinary supported catalysts, which have few active sites and poor dispersion, making it difficult to efficiently activate the double bonds in α-pinene molecules. This results in hydrogenation reactions requiring harsh conditions such as high temperature and high pressure to proceed smoothly. Even under these conditions, the reaction rate remains slow, and the reaction cycle is significantly prolonged. This not only increases production energy consumption and equipment wear and tear but may also lead to feedstock decomposition and an increase in by-products due to excessively long reaction times. Furthermore, α-pinene molecules have multiple hydrogenation sites, and existing catalysts lack sufficient selectivity to precisely target the hydrogenation of specific double bonds in α-pinene. This often results in a low proportion of cis-pinene in the reaction products and a high content of trans-pinene and other hydrogenation by-products. The purity of cis-pinene directly affects the subsequent synthesis efficiency and product quality of pinane peroxide. The presence of by-products not only increases the difficulty and cost of subsequent separation and purification but also reduces the utilization rate of feedstocks. Summary of the Invention

[0005] To address the problems mentioned in the background section, this invention provides a process for synthesizing pinane peroxide.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A process for synthesizing pinane peroxide includes the following steps:

[0008] S1. In the presence of a hydrogen atmosphere and a catalyst, α-pinene is subjected to catalytic hydrogenation to obtain a reaction mixture rich in cis-pinene.

[0009] S2. Separate the catalyst from the reaction mixture and distill the remaining material to obtain cis-pinene;

[0010] S3. In the presence of an oxygen-containing gas atmosphere and an initiator, cis-pinene is subjected to a liquid-phase oxidation reaction to obtain an oxidized liquid containing pinane peroxide.

[0011] S4. Separate the initiator from the oxidation liquid and concentrate the resulting organic phase to obtain pinane peroxide product;

[0012] The catalyst is a supported amorphous alloy catalyst with Ni-Co-Mo-B as its active component, which is supported on a biochar carrier.

[0013] The initiator is a haloantimony oxide-based compound.

[0014] Further, the catalyst in step S1 is characterized by being prepared using the following steps:

[0015] A1. Biomass raw materials are pyrolyzed and carbonized under an inert atmosphere to obtain biochar carriers;

[0016] A2. Disperse the biochar carrier in a solvent, add compounds containing nickel, cobalt, and molybdenum metal salts in sequence, adjust the pH value, and impregnate.

[0017] A3. Cool the impregnated system, add an aqueous solution of boron-containing reducing agent under stirring to carry out a reduction reaction, generate a precipitate, separate the solid and liquid of the obtained product, and wash and dry the obtained solid to obtain the catalyst.

[0018] Furthermore, in step S1, the catalytic hydrogenation reaction is carried out under the conditions of pressure 1.0-2.0 MPa, temperature 60-70℃, and stirring speed 100-200 rpm; the amount of catalyst used is 0.8-2.0% of the mass of α-pinene; the mass concentration of α-pinene in the reaction system is 50%-80%, and the reaction time is 2-6 h.

[0019] Further, step S2 is characterized by comprising:

[0020] S21. Separate the catalyst from the reaction mixture rich in cis-pinene by centrifugation or magnetic separation; the centrifugation conditions are 3000-5000 rpm and 10-30 min; the magnetic separation is carried out using a permanent magnet with a magnetic field strength of 0.3-0.8 T and a separation time of 15-40 min; the separated catalyst can be reused 3-5 times, and needs to be dried at 100-120℃ for 2-3 h before reuse;

[0021] S22. The remaining material after catalyst separation is subjected to vacuum distillation. Under the conditions of absolute pressure not exceeding 5 kPa and reflux ratio of (1-3):1, the fraction with a top temperature of 65-72℃ is collected to obtain cis-pinene.

[0022] Furthermore, the initiator in step S3 is prepared by the following steps:

[0023] Antimony-containing compounds and halogen-containing compounds are mixed and reacted in an alcohol solvent to form a suspension. The pH of the suspension is adjusted to 7.0-8.0 with an alkaline solution, followed by crystallization. The crystallized product is then subjected to solid-liquid separation. The obtained solid is washed and dried to obtain a haloantimony oxide-based compound. The reaction system for the liquid-phase oxidation reaction uses one or more solvents selected from n-hexane, cyclohexane, or petroleum ether, and the reaction time is 8-16 hours to obtain the SbOI initiator.

[0024] Furthermore, the liquid-phase oxidation reaction in step S3 is carried out at a temperature of 80-100℃ and a stirring speed of 200-400 rpm; the oxygen-containing gas is air, and its introduction rate is 0.3-0.8 m³ / min. 3 ·h -1 ·kg -1 Cis-pinene; the amount of initiator is 0.3-1.0% of the mass of cis-pinene; the liquid-phase oxidation reaction is carried out in a bubble-type reactor, and the air is introduced by bottom bubbling.

[0025] Furthermore, in step S4, the concentration is carried out under reduced pressure, with concentration conditions of absolute pressure 2-5 kPa and temperature 40-60℃, until the volume of the organic phase is 1 / 3-1 / 2 of the initial volume.

[0026] Further, the pyrolysis carbonization in step A1 includes: heating to 500-600℃ at a heating rate of 1-10℃ / min under an inert atmosphere, and maintaining this temperature for 1-4 hours; the biomass raw material includes, but is not limited to, one or more of bamboo, straw, rice husks, sawdust, or fruit shells; the inert gas is nitrogen or argon, and the gas flow rate is 0.5-1.0 m³ / min. 3 ·h -1 The pretreatment of biomass raw materials involves pulverizing them to a particle size of 20-80 mesh; the biochar carrier obtained after pyrolysis and carbonization needs to be pulverized to a particle size of 100-200 mesh.

[0027] Further, in step A2, the compounds containing nickel, cobalt, and molybdenum metal salts are nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and ammonium molybdate tetrahydrate, respectively; the pH value is adjusted to 7.5-9.0; impregnation is carried out at a temperature of 50-90℃ for 2-6 hours; the concentrations of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and ammonium molybdate tetrahydrate are 0.1-0.5 mol / L, 0.05-0.2 mol / L, and 0.02-0.1 mol / L, respectively; continuous stirring is carried out during impregnation at a stirring speed of 200-300 rpm; after impregnation, solid-liquid separation is performed by vacuum filtration to obtain the impregnated biochar carrier; the solvent is deionized water, and the dispersion concentration of the biochar carrier in the solvent is 10-30 g / L; the reagent used to adjust the pH value is one of ammonia water, sodium hydroxide solution, or sodium carbonate solution.

[0028] Furthermore, in step A3, the system is cooled at a temperature of 0-10℃; the stirring speed is 400-500 rpm; the boron-containing reducing agent is sodium borohydride or potassium borohydride; the reduction reaction is carried out under an inert atmosphere (nitrogen or argon); the temperature is controlled at 0-10℃ during the reaction; after the reaction is completed, the system is allowed to stand for 1-2 hours before solid-liquid separation.

[0029] Furthermore, in step A3, the reduction reaction time is 1-3 hours, the concentration of the boron-containing reducing agent aqueous solution is 0.5-2.0 mol / L, the washing solvent is deionized water and ethanol alternately, the drying temperature is 80-120℃, and the drying time is 4-8 hours.

[0030] Furthermore, the antimony-containing compound is antimony trichloride, the halogen-containing compound is potassium iodide, and the alcohol solvent is ethylene glycol; the crystallization treatment is carried out at 100-140℃ for 8-15 hours; the amount of ethylene glycol used is 5-10 times the mass of antimony trichloride; the crystallization treatment is carried out in a high-pressure reactor with a crystallization pressure of 0.1-0.3 MPa; after crystallization, the system is cooled to room temperature, and then solid-liquid separation is performed. The obtained solid is washed until the washing liquid is free of chloride ions (detected by silver nitrate solution) and then dried to obtain the initiator (SbOI).

[0031] The beneficial effects of this invention are:

[0032] 1. The preparation process of this invention relies on the inert atmosphere pyrolysis and carbonization of biomass raw materials, causing cellulose, hemicellulose, and lignin within the biomass to undergo thermal decomposition, dehydration, decarboxylation, and aromatization reactions, forming a biochar support with a hierarchical porous structure. The surface of this support is enriched with a large number of oxygen-containing functional groups and surface defect sites, providing stable anchoring points and mass transfer channels for the subsequent loading of active components. Subsequently, the biochar support is dispersed in a solvent, a polymetallic salt compound is added, and the pH of the system is adjusted. Through impregnation, polymetallic ions are uniformly dispersed and anchored on the surface and inside the pores of the biochar support via electrostatic adsorption and coordination complexation, avoiding localized enrichment of metal ions. Finally, through low-temperature cooling and co-reduction reaction with a boron-based reducing agent, the polymetallic ions are simultaneously reduced, and boron atoms are embedded in the interatomic spaces of the metal atoms, forming a short-range ordered, long-range disordered Ni-Co-Mo-B amorphous alloy structure, ultimately yielding a supported amorphous alloy catalyst. This preparation process relies on the green characteristics of biomass raw materials and solves the defects of existing technologies, such as high cost of catalyst carriers, poor environmental performance, complex preparation process, and uneven dispersion of active components.

[0033] 2. The hierarchical porous structure of biochar supports possesses a high specific surface area and excellent pore connectivity, enabling high dispersion of the amorphous alloy active components. This effectively limits the growth and aggregation of metal particles, exposing a large number of effective catalytic active sites on the catalyst surface. Simultaneously, a strong metal-support interaction forms between the biochar support and the amorphous alloy, further anchoring the active components and enhancing the catalyst's structural stability. The amorphous alloy structure differs from traditional crystalline catalysts, lacking fixed lattice boundaries and crystal orientations. Its surface contains numerous unsaturated coordinating atoms, atomic vacancies, and stepped active interfaces. Combined with interstitial doping and covalent bonding of boron atoms, this can induce electronic structure reconstruction of the active centers, optimizing the electron cloud distribution of the active sites. Furthermore, a significant electronic synergistic effect exists among the Ni-Co-Mo trimetallic compounds. The main active component, Ni, is responsible for adsorbing and activating hydrogen molecules; Co regulates the electron distribution of the active centers to lower the reaction energy barrier; and Mo optimizes the surface acid-base properties of the active sites to suppress side reactions.

[0034] 3. The catalyst prepared in this invention has a large number of exposed effective active sites and a synergistic effect of multiple metals, which can effectively reduce the activation energy of the hydrogenation reaction of α-pinene carbon-carbon double bonds. It eliminates the need for harsh reaction conditions of high temperature and high pressure, achieving efficient hydrogenation conversion of α-pinene under mild operating conditions, significantly reducing production energy consumption and equipment wear, and solving the defects of harsh hydrogenation reaction conditions and high energy consumption in existing technologies. Secondly, the microstructure of the amorphous alloy and the directional catalytic effect of multiple metals target and activate carbon-carbon double bonds at specific positions, effectively suppressing side reactions such as ring opening, excessive hydrogenation, and isomerization, significantly improving the directional selectivity of cis-pinene, reducing by-product formation, improving raw material utilization, and reducing the difficulty of subsequent separation and purification, solving the problems of difficult efficient preparation of cis-pinene-rich products and excessive by-products in existing technologies. Attached Figure Description

[0035] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0036] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] like Figure 1 The diagram illustrates a process flow chart for the synthesis of pinane peroxide, comprising: S1 Catalytic hydrogenation: α-pinene undergoes hydrogenation under the action of a Ni-Co-Mo-B / BC catalyst and hydrogen; S2 Separation and distillation: the reaction mixture undergoes solid-liquid separation to recover the catalyst, and high-purity cis-pinane is obtained by liquid-phase vacuum distillation; S3 Liquid-phase oxidation: cis-pinane undergoes oxidation under the action of an SbOI initiator and air; S4 Separation and concentration: the initiator is recovered by filtration, and the organic phase is concentrated under vacuum to obtain the final product, pinane peroxide. The core advantages of this process are: the hydrogenation catalyst is recyclable, the oxidation initiator is a multiphase system that can be recovered, and there is no homogeneous initiator residue throughout the process, combining high efficiency with environmental friendliness.

[0038] The following detailed description is provided through examples and comparative examples. In the following examples and comparative examples, α-pinene was industrial grade with a purity ≥95.0 wt%; bamboo powder, straw powder, rice husk powder, wood chip powder, and fruit shell powder were all obtained from agricultural and forestry waste through drying, crushing, and sieving, with a moisture content ≤8.0 wt%; nickel nitrate hexahydrate (CAS No.: 13478-00-7), cobalt nitrate hexahydrate (CAS No.: 10026-22-9), and ammonium molybdate tetrahydrate (CAS No.: 12054-85-2) were all analytical grade with a purity ≥99.0%; sodium borohydride (CAS No.: 16940-66-2) and potassium borohydride (CAS No.: 13762-51-1) were both analytical grade with a purity ≥98.0%; and antimony trichloride (CAS No.: 10025-91-9) and potassium iodide (CAS No.: 7681-11-0) were both analytical grade with a purity ≥99.0%.

[0039] Example 1

[0040] The preparation of the catalyst includes the following steps:

[0041] A1. Take 50g of bamboo powder pulverized to 20 mesh, introduce nitrogen gas, heat to 500℃ at a heating rate of 1℃ / min, and maintain at this temperature for 1h for pyrolysis carbonization. Pulverize the resulting biochar carrier to 100 mesh for later use.

[0042] A2. Disperse 10g of biochar carrier in 1000mL of deionized water, and add 29.08g of nickel nitrate hexahydrate (0.1mol / L), 14.55g of cobalt nitrate hexahydrate (0.05mol / L), and 5.24g of ammonium molybdate tetrahydrate (0.02mol / L) in sequence. Adjust the pH to 7.5 with ammonia water, and impregnate for 2h at 50℃ and 200rpm. After impregnation, separate by vacuum filtration to obtain the impregnated biochar carrier.

[0043] A3. Cool the impregnated system to 0℃, and slowly add 20g of 0.5mol / L sodium borohydride aqueous solution while stirring at 400rpm. Carry out the reduction reaction for 1h under nitrogen protection and 0℃. After the reaction is completed, let it stand for 1h. After solid-liquid separation, wash with deionized water and ethanol three times each, and dry at 80℃ for 4h to obtain the catalyst.

[0044] A process for synthesizing pinane peroxide includes the following steps:

[0045] S1. Under a hydrogen atmosphere, 100g of α-pinene and 100mL of deionized water were added to the reactor, along with 0.8g of the catalyst prepared above. The reaction was carried out for 2 hours under the conditions of 1.0MPa pressure, 60℃ temperature and 100rpm stirring speed to obtain a reaction mixture rich in cis-pinene.

[0046] S21. Place the above reaction mixture into a centrifuge tube and centrifuge at 3000 rpm for 10 min to separate the catalyst. The separated catalyst can be reused after drying at 100°C for 2 h.

[0047] S22. The remaining material is subjected to vacuum distillation. Under the conditions of absolute pressure of 5 kPa and reflux ratio of 1:1, the fraction with a top temperature of 65-72℃ is collected to obtain cis-pinene.

[0048] S3. Take 10g of antimony trichloride and 21.81g of potassium iodide, add 50mL of ethylene glycol, mix and stir to form a suspension, adjust the pH to 7.0 with alkaline solution, put it into a high-pressure reactor, crystallize at 100℃ and 0.1MPa for 8h, cool to room temperature and separate solid and liquid, wash with deionized water until the washing liquid is free of chloride ions, dry to obtain antimony halide-based initiator; add 100mL of n-hexane as solvent to a bubbling reactor, add 50g of cis-pinene and 0.15g of the initiator prepared above, control the temperature at 80℃ and the stirring speed at 200rpm, bubble air from the bottom, react for 8h to obtain an oxidized liquid containing pinane peroxide;

[0049] S4. Filter and separate the initiator from the oxidation liquid. Concentrate the obtained organic phase under reduced pressure at 2 kPa and 40 °C until the volume of the organic phase is 1 / 3 of the initial volume to obtain the hydrogen peroxide pinane product.

[0050] Example 2

[0051] The preparation of the catalyst includes the following steps:

[0052] A1. Take 60g of straw powder pulverized to 50 mesh, introduce nitrogen gas, heat to 550℃ at a heating rate of 5℃ / min, and maintain at this temperature for 2.5h for pyrolysis carbonization. Pulverize the resulting biochar carrier to 150 mesh for later use.

[0053] A2. Disperse 20g of biochar carrier in 1000mL of deionized water, and add 87.24g of nickel nitrate hexahydrate (0.3mol / L), 36.38g of cobalt nitrate hexahydrate (0.125mol / L), and 15.72g of ammonium molybdate tetrahydrate (0.06mol / L) in sequence. Adjust the pH to 8.2 with sodium hydroxide solution, and impregnate for 4h at 70℃ and 250rpm. After impregnation, separate by vacuum filtration to obtain the impregnated biochar carrier.

[0054] A3. Cool the impregnated system to 5°C, and slowly add 62.5g of 1.25mol / L potassium borohydride aqueous solution while stirring at 450rpm. Carry out the reduction reaction for 2h under argon protection and at 5°C. After the reaction is completed, let it stand for 1.5h. After solid-liquid separation, wash with deionized water and ethanol three times each, and dry at 100°C for 6h to obtain the catalyst.

[0055] A process for synthesizing pinane peroxide includes the following steps:

[0056] S1. Under a hydrogen atmosphere, 130g of α-pinene and 70mL of deionized water were added to the reactor, along with 1.82g of the catalyst prepared above. The reaction was carried out for 4h under the conditions of 1.5MPa pressure, 65℃ temperature and 150rpm stirring speed to obtain a reaction mixture rich in cis-pinene.

[0057] S21. Place the above reaction mixture into a magnetic separation device and use a permanent magnet with a magnetic field strength of 0.55T for magnetic separation. The separation time is 27.5 min. The separated catalyst can be reused after drying at 110℃ for 2.5 h.

[0058] S22. The remaining material is subjected to vacuum distillation. Under the conditions of absolute pressure of 3 kPa and reflux ratio of 2:1, the fraction with a top temperature of 65-72℃ is collected to obtain cis-pinene.

[0059] S3. Take 15g of antimony trichloride and 32.72g of potassium iodide, add 112.5mL of ethylene glycol, mix and stir to form a suspension, adjust the pH to 7.5 with alkaline solution, put it into a high-pressure reactor, crystallize at 120℃ and 0.2MPa for 11.5h, cool to room temperature and separate the solid and liquid, wash with deionized water until the washing liquid is free of chloride ions, dry to obtain antimony halide-based initiator; add 120mL of cyclohexane as solvent to a bubbling reactor, add 60g of cis-pinene and 0.39g of the initiator prepared above, control the temperature at 90℃ and the stirring speed at 300rpm, bubble air from the bottom, react for 12h to obtain an oxidized liquid containing pinane peroxide;

[0060] S4. The initiator is separated by filtration from the oxidation liquid. The resulting organic phase is concentrated under reduced pressure at 3.5 kPa and 50 °C until the volume of the organic phase is 5 / 12 of the initial volume, thus obtaining the pinane peroxide product.

[0061] Example 3

[0062] The preparation of the catalyst includes the following steps:

[0063] A1. Take 70g of rice husk powder pulverized to 80 mesh, introduce nitrogen gas, heat to 600℃ at a heating rate of 10℃ / min, and maintain at this temperature for 4h for pyrolysis carbonization. Pulverize the resulting biochar carrier to 200 mesh for later use.

[0064] A2. Disperse 30g of biochar carrier in 1000mL of deionized water, and add 145.40g of nickel nitrate hexahydrate (0.5mol / L), 58.21g of cobalt nitrate hexahydrate (0.2mol / L), and 26.20g of ammonium molybdate tetrahydrate (0.1mol / L) in sequence. Adjust the pH to 9.0 with sodium carbonate solution, and impregnate for 6h at 90℃ and 300rpm. After impregnation, separate by vacuum filtration to obtain the impregnated biochar carrier.

[0065] A3. Cool the impregnated system to 10°C, and slowly add 80g of 2.0mol / L sodium borohydride aqueous solution while stirring at 500rpm. Carry out the reduction reaction for 3h under nitrogen protection and at 10°C. After the reaction is completed, let it stand for 2h. After solid-liquid separation, wash it 3 times each with deionized water and ethanol, and dry it at 120°C for 8h to obtain the catalyst.

[0066] A process for synthesizing pinane peroxide includes the following steps:

[0067] S1. Under a hydrogen atmosphere, 160g of α-pinene and 40mL of deionized water were added to the reactor, along with 3.2g of the catalyst prepared above. The reaction was carried out for 6h under the conditions of 2.0MPa pressure, 70℃ temperature and 200rpm stirring speed to obtain a reaction mixture rich in cis-pinene.

[0068] S21. Place the above reaction mixture into a centrifuge tube and centrifuge at 5000 rpm for 30 min to separate the catalyst. The separated catalyst can be reused after drying at 120°C for 3 h.

[0069] S22. The remaining material is subjected to vacuum distillation. Under the conditions of absolute pressure of 4 kPa and reflux ratio of 3:1, the fraction with a top temperature of 65-72℃ is collected to obtain cis-pinene.

[0070] S3. Take 20g of antimony trichloride and 43.62g of potassium iodide, add 180mL of ethylene glycol, mix and stir to form a suspension, adjust the pH to 8.0 with alkaline solution, put it into a high-pressure reactor, crystallize at 140℃ and 0.3MPa for 15h, cool to room temperature and separate solid and liquid, wash with deionized water until the washing liquid is free of chloride ions, dry to obtain antimony halide-based initiator; add 150mL of petroleum ether as solvent to a bubbling reactor, add 70g of cis-pinene and 0.7g of the initiator prepared above, control the temperature at 100℃ and the stirring speed at 400rpm, bubble air from the bottom, react for 16h to obtain an oxidized liquid containing pinane peroxide;

[0071] S4. Filter and separate the initiator from the oxidation liquid. Concentrate the obtained organic phase under reduced pressure of 5 kPa and 60 °C until the volume of the organic phase is 1 / 2 of the initial volume to obtain the hydrogen peroxide pinane product.

[0072] Example 4

[0073] The preparation of the catalyst includes the following steps:

[0074] A1. Take 55g of wood chips pulverized to 30 mesh, introduce nitrogen gas, heat to 520℃ at a heating rate of 3℃ / min, and maintain at this temperature for 2h for pyrolysis carbonization. Pulverize the resulting biochar carrier to 120 mesh for later use.

[0075] A2. Disperse 15g of biochar carrier in 1000mL of deionized water, and add 43.62g of nickel nitrate hexahydrate (0.15mol / L), 21.83g of cobalt nitrate hexahydrate (0.075mol / L), and 7.86g of ammonium molybdate tetrahydrate (0.03mol / L) in sequence. Adjust the pH to 7.8 with ammonia water, and impregnate for 3h at 60℃ and 220rpm. After impregnation, separate by vacuum filtration to obtain the impregnated biochar carrier.

[0076] A3. Cool the impregnated system to 3°C, and slowly add 35g of 0.8mol / L sodium borohydride aqueous solution while stirring at 420rpm. Carry out the reduction reaction for 1.5h under nitrogen protection and at 3°C. After the reaction is completed, let it stand for 1.2h. After solid-liquid separation, wash with deionized water and ethanol three times each, and dry at 90°C for 5h to obtain the catalyst.

[0077] A process for synthesizing pinane peroxide includes the following steps:

[0078] S1. Under a hydrogen atmosphere, 110g of α-pinene and 90mL of deionized water were added to the reactor, along with 1.1g of the catalyst prepared above. The reaction was carried out for 3h under the conditions of 1.2MPa pressure, 62℃ temperature and 120rpm stirring speed to obtain a reaction mixture rich in cis-pinene.

[0079] S21. Place the above reaction mixture into a magnetic separation device and use a permanent magnet with a magnetic field strength of 0.4T for magnetic separation. The separation time is 20 minutes. The separated catalyst can be reused after drying at 105℃ for 2.2 hours.

[0080] S22. The remaining material is subjected to vacuum distillation. Under the conditions of absolute pressure of 4.5 kPa and reflux ratio of 1.5:1, the fraction with a top temperature of 65-72℃ is collected to obtain cis-pinene.

[0081] S3. Take 12g of antimony trichloride and 26.17g of potassium iodide, add 72mL of ethylene glycol, mix and stir to form a suspension, adjust the pH to 7.2 with alkaline solution, put it into a high-pressure reactor, crystallize at 110℃ and 0.15MPa for 10h, cool to room temperature and separate solid and liquid, wash with deionized water until the washing liquid is free of chloride ions, dry to obtain antimony halide-based initiator; add 110mL of n-hexane as solvent to a bubbling reactor, add 55g of cis-pinene and 0.22g of the initiator prepared above, control the temperature at 85℃ and the stirring speed at 250rpm, bubble air from the bottom, react for 10h to obtain an oxidized liquid containing pinane peroxide;

[0082] S4. The initiator is separated by filtration from the oxidation liquid. The resulting organic phase is concentrated under reduced pressure at 2.5 kPa and 45 °C until the volume of the organic phase is 7 / 20 of the initial volume, thus obtaining the pinane peroxide product.

[0083] Example 5

[0084] The preparation of the catalyst includes the following steps:

[0085] A1. Take 65g of fruit shell powder crushed to 60 mesh, introduce argon gas, heat to 570℃ at a heating rate of 7℃ / min, and maintain at this temperature for 3h for pyrolysis carbonization. Crush the resulting biochar carrier to 180 mesh for later use.

[0086] A2. Disperse 25g of biochar carrier in 1000mL of deionized water, and add 116.32g of nickel nitrate hexahydrate (0.4mol / L), 45.81g of cobalt nitrate hexahydrate (0.16mol / L), and 20.96g of ammonium molybdate tetrahydrate (0.08mol / L) in sequence. Adjust the pH to 8.5 with sodium hydroxide solution, and impregnate for 5h at 80℃ and 280rpm. After impregnation, separate by vacuum filtration to obtain the impregnated biochar carrier.

[0087] A3. Cool the impregnated system to 8°C, and slowly add 70g of 1.6mol / L potassium borohydride aqueous solution while stirring at 480rpm. Carry out the reduction reaction for 2.5h under argon protection and at 8°C. After the reaction is completed, let it stand for 1.8h. After solid-liquid separation, wash with deionized water and ethanol three times each, and dry at 110°C for 7h to obtain the catalyst.

[0088] A process for synthesizing pinane peroxide includes the following steps:

[0089] S1. Under a hydrogen atmosphere, 145g of α-pinene and 55mL of deionized water were added to the reactor, along with 2.47g of the catalyst prepared above. The reaction was carried out for 5h under the conditions of 1.7MPa pressure, 67℃ temperature and 180rpm stirring speed to obtain a reaction mixture rich in cis-pinene.

[0090] S21. Place the above reaction mixture into a centrifuge tube and centrifuge at 4000 rpm for 22 min to separate the catalyst. The separated catalyst can be reused after drying at 115°C for 2.8 h.

[0091] S22. The remaining material is subjected to vacuum distillation. Under the conditions of absolute pressure of 3.5 kPa and reflux ratio of 2.5:1, the fraction with a top temperature of 65-72℃ is collected to obtain cis-pinene.

[0092] S3. Take 18g of antimony trichloride and 39.26g of potassium iodide, add 153mL of ethylene glycol, mix and stir to form a suspension, adjust the pH to 7.8 with alkaline solution, put it into a high-pressure reactor, crystallize at 130℃ and 0.25MPa for 13h, cool to room temperature and separate solid and liquid, wash with deionized water until the washing liquid is free of chloride ions, dry to obtain antimony halide-based initiator; add 135mL of cyclohexane as solvent to a bubbling reactor, add 65g of cis-pinene and 0.52g of the initiator prepared above, control the temperature at 95℃ and the stirring speed at 350rpm, bubble air from the bottom, react for 14h to obtain an oxidized liquid containing pinane peroxide;

[0093] S4. Filter and separate the initiator from the oxidation liquid. Concentrate the obtained organic phase under reduced pressure at 4 kPa and 55 °C until the volume of the organic phase is 3 / 8 of the initial volume to obtain the pinane peroxide product.

[0094] Example 6

[0095] The preparation of the catalyst includes the following steps:

[0096] A1. Take 52g of bamboo material and straw mixed powder (mass ratio 1:1) crushed to 25 mesh, introduce nitrogen gas, heat to 510℃ at a heating rate of 2℃ / min, and maintain at this temperature for 1.5h for pyrolysis carbonization. Crush the resulting biochar carrier to 110 mesh for later use.

[0097] A2. Disperse 12g of biochar carrier in 1000mL of deionized water, and add 34.89g of nickel nitrate hexahydrate (0.12mol / L), 17.46g of cobalt nitrate hexahydrate (0.06mol / L), and 6.29g of ammonium molybdate tetrahydrate (0.024mol / L) in sequence. Adjust the pH to 7.6 with sodium carbonate solution, and impregnate for 2.5h at 55℃ and 210rpm. After impregnation, separate by vacuum filtration to obtain the impregnated biochar carrier.

[0098] A3. Cool the impregnated system to 2°C, and slowly add 28g of 0.6mol / L sodium borohydride aqueous solution while stirring at 410rpm. Carry out the reduction reaction for 1.2h under nitrogen protection and at 2°C. After the reaction is completed, let it stand for 1.1h. After solid-liquid separation, wash with deionized water and ethanol three times each, and dry at 85°C for 4.5h to obtain the catalyst.

[0099] A process for synthesizing pinane peroxide includes the following steps:

[0100] S1. Under a hydrogen atmosphere, 105g of α-pinene and 105mL of deionized water were added to the reactor, along with 0.95g of the catalyst prepared above. The reaction was carried out for 2.5h under the conditions of 1.1MPa pressure, 61℃ temperature and 110rpm stirring speed to obtain a reaction mixture rich in cis-pinene.

[0101] S21. Place the above reaction mixture into a magnetic separation device and perform magnetic separation using a permanent magnet with a magnetic field strength of 0.35T. The separation time is 18 minutes. The separated catalyst can be reused after drying at 102℃ for 2.1 hours.

[0102] S22. The remaining material is subjected to vacuum distillation. Under the conditions of absolute pressure 4.8 kPa and reflux ratio 1.2:1, the fraction with a top temperature of 65-72℃ is collected to obtain cis-pinene.

[0103] S3. Take 11g of antimony trichloride and 23.99g of potassium iodide, add 55mL of ethylene glycol, mix and stir to form a suspension, adjust the pH to 7.1 with alkaline solution, put it into a high-pressure reactor, crystallize at 105℃ and 0.12MPa for 9h, cool to room temperature and separate solid and liquid, wash with deionized water until the washing liquid is free of chloride ions, dry to obtain antimony halide-based initiator; add 105mL of petroleum ether as solvent to a bubbling reactor, add 52g of cis-pinene and 0.18g of the initiator prepared above, control the temperature at 82℃ and the stirring speed at 220rpm, bubble air from the bottom, react for 9h to obtain an oxidized liquid containing pinane peroxide;

[0104] S4. The initiator is separated by filtration from the oxidation liquid. The resulting organic phase is concentrated under reduced pressure at 2.2 kPa and 42 °C until the volume of the organic phase is 2 / 7 of the initial volume, thus obtaining the pinane peroxide product.

[0105] Comparative Example 1

[0106] The difference between this comparative example and Example 1 is that the biochar support for the catalyst is replaced with an equal mass of activated carbon, while the remaining steps and parameters are exactly the same as in Example 1.

[0107] Comparative Example 2

[0108] The difference between this comparative example and Example 2 is that ammonium molybdate tetrahydrate was omitted in the catalyst preparation, and only nickel nitrate hexahydrate and cobalt nitrate hexahydrate were added. The remaining steps and parameters are exactly the same as in Example 2.

[0109] Comparative Example 3

[0110] The difference between this comparative example and Example 3 is that the antimony halooxide-based initiator is replaced with an equal mass of azobisisobutyronitrile, while the remaining steps and parameters are exactly the same as in Example 3.

[0111] Comparative Example 4

[0112] The difference between this comparative example and Example 4 is that cobalt nitrate hexahydrate was omitted in the catalyst preparation, and only nickel nitrate hexahydrate and ammonium molybdate tetrahydrate were added. The remaining steps and parameters are exactly the same as in Example 4.

[0113] Comparative Example 5

[0114] The difference between this comparative example and Example 5 is that nickel nitrate hexahydrate was omitted in the catalyst preparation, and only cobalt nitrate hexahydrate and ammonium molybdate tetrahydrate were added. The remaining steps and parameters are exactly the same as in Example 5.

[0115] A gas chromatograph (HP-5 capillary column, 30 m long, 0.32 mm inner diameter, 0.25 μm film thickness) was used. The column temperature program was set as follows: initial temperature 80 °C, hold for 2 min, increase to 180 °C at a rate of 5 °C / min, hold for 5 min. Detector temperature 250 °C, injection port temperature 220 °C, nitrogen as carrier gas, carrier gas flow rate 1.0 mL / min, split ratio 10:1, injection volume 1 μL. 1.0 mL of the reaction mixture from each of Examples 1-6 and Comparative Examples 1-5 after the S1 reaction was completed was accurately measured, diluted with 4.0 mL of anhydrous ethanol, shaken well, and allowed to stand for 5 min. The supernatant was then injected for analysis, and the remaining α-pinene mass was calculated using a standard curve. Conversion rate calculation formula: Conversion rate = (Initial α-pinene mass - Remaining α-pinene mass) / Initial α-pinene mass × 100%, where the initial α-pinene mass is calculated based on the actual mass of α-pinene added in each scheme S1. The results are shown in Table 1:

[0116] Table 1. α-Pinene conversion test results of different examples and comparative examples

[0117]

[0118] The gas chromatograph described above was used, and the detection parameters were consistent with those for the α-pinene conversion detection. 1.0 mL of the cis-pinene fraction collected in S22 of each scheme was accurately measured, diluted with 4.0 mL of anhydrous ethanol, shaken well, and allowed to stand for 5 min. The supernatant was then injected for analysis. The peak areas of cis-pinene and other pinane isomers (trans-pinene) were recorded. The purity of cis-pinene and the total pinane mass were calculated using the peak area normalization method. The selectivity calculation formula was: Selectivity = (mass of cis-pinene / mass of total pinane produced) × 100%, where total pinane mass = (mass of cis-pinene + mass of other pinane isomers). The results are shown in Table 2.

[0119] Table 2. Results of cis-pinene selectivity tests in different examples and comparative examples

[0120]

[0121] Using the gas chromatograph described above, the detection parameters were adjusted as follows: column temperature program: initial temperature 100℃, hold for 3 min, increase to 200℃ at a rate of 4℃ / min, hold for 6 min; detector temperature 260℃, injection port temperature 230℃, carrier gas flow rate 1.2 mL / min, split ratio 5:1, injection volume 1 μL. 1.0 mL of the final product from each S4 scheme was accurately measured, diluted with 4.0 mL of anhydrous ethanol, shaken well, and allowed to stand for 5 min. The supernatant was then injected for analysis. The purity of pinane peroxide was calculated using the peak area normalization method, and the peak area of ​​impurities was also measured to ensure that the total impurity content was below 0.5% (the content of a single impurity was below 0.1%). Each batch of samples was analyzed in triplicate, and the average value was taken as the final purity. The results are shown in Table 3.

[0122] Table 3. Purity test results of pinane hydroperoxide products from different examples and comparative examples.

[0123]

[0124] The catalysts separated in S21 of each scheme were dried to constant weight according to the drying conditions of S21 in the corresponding scheme. The mass of the catalyst was accurately weighed and reused in the α-pinene hydrogenation reaction (S1 step) of the corresponding scheme, and reused three times consecutively. The reaction parameters were completely consistent with the corresponding scheme each time. After each reaction, the α-pinene conversion rate was detected and calculated according to the above-mentioned α-pinene conversion rate detection procedure. The retention rate of the third reaction was calculated based on the conversion rate of the first reaction. The retention rate calculation formula is: Retention rate = (Third conversion rate / First conversion rate) × 100%. The results are shown in Table 4:

[0125] Table 4. α-pinene conversion retention rate after 3 catalyst recycling cycles

[0126]

[0127] As shown in Table 1, the α-pinene conversion rates in Examples 1-6 were all relatively high, ranging from 90.2% to 99.3%. The supported amorphous alloy catalyst prepared in this invention utilizes a biochar support with a hierarchical porous structure, enabling high dispersion of the amorphous alloy active components. This effectively limits the growth and aggregation of metal particles, exposing a large number of effective catalytic active sites on the catalyst surface. Simultaneously, the amorphous alloy structure surface contains numerous unsaturated coordinating atoms, which, combined with interstitial doping and covalent bonding of boron atoms, induce electronic structure reconstruction of the active centers, optimizing the electron cloud distribution of the active sites. Furthermore, a significant electronic synergistic effect exists among the Ni-Co-Mo trimetallic compounds. The main active component, Ni, is responsible for adsorbing and activating hydrogen molecules; Co regulates the electron distribution of the active centers to lower the reaction energy barrier; and Mo optimizes the acid-base properties of the active site surface to suppress side reactions. This effectively reduces the activation energy of the α-pinene carbon-carbon double bond hydrogenation reaction, achieving efficient hydrogenation conversion under mild operating conditions.

[0128] In Comparative Example 1, replacing the biochar support with an equal mass of activated carbon resulted in a conversion rate of only 76.2%. Biochar supports, leveraging the green characteristics of biomass feedstock, possess a hierarchical porous structure with a high specific surface area and good pore connectivity. Furthermore, their surface is enriched with numerous oxygen-containing functional groups and surface defect sites, providing stable anchoring points and mass transfer channels for the subsequent loading of active components. Activated carbon, on the other hand, may not provide such a favorable support environment, leading to uneven dispersion of active components, a reduction in effective catalytic active sites, and a decrease in reaction conversion rate.

[0129] Comparative Example 2, by omitting ammonium molybdate tetrahydrate, and Comparative Example 4, by omitting cobalt nitrate hexahydrate, achieved conversion rates of 89.5% and 86.7%, respectively, lower than the examples. This indicates that the electronic synergistic effect among the Ni-Co-Mo trimetallic compounds has a significant impact on the reaction conversion rate. The absence of one of the metals weakens the electronic synergistic effect, reduces the reactivity, and leads to a decrease in conversion rate.

[0130] Comparative Example 5, with the removal of nickel nitrate hexahydrate, showed a conversion rate of only 2.3%. This is because Ni is the main active component, responsible for adsorbing and activating hydrogen molecules. Without Ni, the reaction cannot proceed effectively, resulting in an extremely low conversion rate.

[0131] As shown in Table 2, the selectivity of cis-pinene in Examples 1-6 ranged from 92.6% to 96.1%. Due to the microstructure of the amorphous alloy and the directional catalytic effect of the multi-metal, the carbon-carbon double bond at a specific position is activated, effectively suppressing side reactions such as ring opening, excessive hydrogenation, and isomerization, thus significantly improving the directional selectivity of cis-pinene.

[0132] Comparative Example 1, using an activated carbon support, showed a cis-pinene selectivity of 85.7%. The unique structure and properties of biochar support facilitate the dispersion and stability of the active components, as well as the formation of strong metal-support interactions, further enhancing the structural stability and selectivity of the catalyst. Activated carbon support, however, cannot achieve the same effect, resulting in reduced selectivity.

[0133] Comparative Examples 2 and 4, lacking molybdenum and cobalt respectively, showed cis-pinene selectivities of 90.1% and 89.4%, respectively. The synergistic effect of the Ni-Co-Mo trimetallic compounds is crucial for suppressing side reactions and improving cis-pinene selectivity. The absence of any one of these metals weakens the synergistic effect, increases side reactions, and decreases selectivity.

[0134] In Comparative Example 5, the selectivity for cis-pinene was 78.9% even without nickel. Nickel, as the main active component, plays a crucial role in directed catalytic reactions, and its absence affects the selectivity of the reaction.

[0135] Table 3 shows that the purity of pinane hydroperoxide in Examples 1-6 is between 99.2% and 99.6%, while the purity of comparative examples 1-5 is between 98.2% and 99.1%. This indicates that the synthesis process of the present invention is relatively stable overall and can produce high-purity pinane hydroperoxide products. Although the comparative examples differ from the examples in some aspects (such as the carrier or metal composition), the impact on the purity of the final product is relatively small, possibly because the subsequent purification steps such as distillation and concentration play a certain role in ensuring the purity of the product.

[0136] As shown in Table 4, the conversion retention rates of Examples 1-6 were between 92.4% and 95.9%. This indicates that the catalyst prepared by this invention has good structural stability, and a strong metal-support interaction is formed between the biochar support and the amorphous alloy, further anchoring the active components. During multiple cycles of use, the active components are not easily lost or agglomerated, and can maintain high catalytic activity.

[0137] Comparative Example 1, using an activated carbon support, showed a conversion retention rate of only 67.5%. The interaction between the activated carbon support and the active components was weak, and the active components were prone to loss and aggregation during repeated cycles, leading to a decrease in catalytic activity and a reduction in conversion retention rate.

[0138] Comparative Examples 2 and 4, lacking molybdenum and cobalt respectively, showed conversion retention rates of 89.6% and 88.6%, respectively. The synergistic effect of the Ni-Co-Mo trimetallic compounds not only affects the initial activity of the reaction but also has a certain impact on the stability of the catalyst. The lack of any one of the metals reduces the stability of the catalyst during recycling and lowers the conversion retention rate.

[0139] Comparative Example 5, lacking nickel, achieved a conversion retention rate of 82.6%, but due to its extremely low initial conversion, its overall catalytic effect was poor. This indicates that nickel plays a crucial role in both the activity and stability of the catalyst.

[0140] In summary, this invention constructs a green process for the continuous synthesis of pinane from α-pinene hydrogenation to pinane oxidation using a biochar-supported Ni-Co-Mo-B amorphous alloy catalyst, providing a novel synthetic strategy that is efficient, safe, reusable, and leaves no homogeneous initiator residue.

[0141] In the description of this specification, the reference to terms such as "embodiment," "various embodiments," etc., indicates that a specific feature, structure, material, or characteristic described in connection with that embodiment or preparation example is included in at least one embodiment of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments.

[0142] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A process for synthesizing pinane hydroperoxide, characterized in that, Includes the following steps: S1. In the presence of a hydrogen atmosphere and a catalyst, α-pinene is subjected to catalytic hydrogenation to obtain a reaction mixture rich in cis-pinene. S2. Separate the catalyst from the reaction mixture and distill the remaining material to obtain cis-pinene; S3. In the presence of an oxygen-containing gas atmosphere and an initiator, cis-pinene is subjected to a liquid-phase oxidation reaction to obtain an oxidized liquid containing pinane peroxide. S4. Separate the initiator from the oxidation liquid and concentrate the resulting organic phase to obtain pinane peroxide product; The catalyst is a supported amorphous alloy catalyst with Ni-Co-Mo-B as its active component, which is supported on a biochar carrier. The initiator is a haloantimony oxide-based compound.

2. The synthesis process of pinane hydroperoxide according to claim 1, characterized in that, The catalyst in step S1 is prepared by the following steps: A1. Biomass raw materials are pyrolyzed and carbonized under an inert atmosphere to obtain biochar carriers; A2. Disperse the biochar carrier in a solvent, add compounds containing nickel, cobalt, and molybdenum metal salts in sequence, adjust the pH value, and impregnate. A3. Cool the impregnated system, add an aqueous solution of boron-containing reducing agent under stirring to carry out a reduction reaction, generate a precipitate, separate the solid and liquid of the obtained product, and wash and dry the obtained solid to obtain the catalyst.

3. The synthesis process of pinane hydroperoxide according to claim 1, characterized in that, In step S1, the catalytic hydrogenation reaction is carried out under the conditions of pressure 1.0-2.0 MPa, temperature 60-70℃, and stirring speed 100-200 rpm; the amount of catalyst used is 0.8-2.0% of the mass of α-pinene.

4. The synthesis process of pinane hydroperoxide according to claim 1, characterized in that, Step S2 includes: S21. The catalyst is separated from the reaction mixture rich in cis-pinene by centrifugation or magnetic separation. S22. The remaining material after catalyst separation is subjected to vacuum distillation. Under the conditions of absolute pressure not exceeding 5 kPa and reflux ratio of (1-3):1, the fraction with a top temperature of 65-72℃ is collected to obtain cis-pinene.

5. The synthesis process of pinane hydroperoxide according to claim 1, characterized in that, The initiator in step S3 is prepared by the following steps: Antimony-containing compounds and halogen-containing compounds are mixed and reacted in an alcohol solvent to generate a suspension. The pH of the suspension is adjusted to 7.0-8.0 with an alkaline solution, and then crystallization is performed. The crystallized product is separated into solid and liquid components. The obtained solid is washed and dried to obtain a haloantimony oxide-based compound.

6. The synthesis process of pinane hydroperoxide according to claim 1, characterized in that, In step S3, the liquid-phase oxidation reaction is carried out at a temperature of 80-100℃ and a stirring speed of 200-400 rpm; the oxygen-containing gas is air, and its introduction rate is 0.3-0.8 m³ / min. 3 ·h -1 ·kg -1 Cis-pinene; the amount of initiator is 0.3-1.0% of the mass of cis-pinene.

7. The synthesis process of pinane hydroperoxide according to claim 2, characterized in that, The pyrolysis carbonization in step A1 includes: heating to 500-600℃ at a heating rate of 1-10℃ / min under an inert atmosphere and maintaining at this temperature for 1-4 hours; the biomass raw materials include, but are not limited to, one or more of bamboo, straw, rice husk, sawdust or fruit shells.

8. The synthesis process of pinane hydroperoxide according to claim 2, characterized in that, In step A2, the compounds containing nickel, cobalt, and molybdenum metal salts are nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and ammonium molybdate tetrahydrate, respectively; the pH value is adjusted to 7.5-9.0; and the immersion is carried out at a temperature of 50-90℃ for 2-6 hours.

9. The synthesis process of pinane hydroperoxide according to claim 2, characterized in that, In step A3, the system is cooled to a temperature of 0-10℃; the stirring speed is 400-500 rpm; and the boron-containing reducing agent is sodium borohydride or potassium borohydride.

10. The synthesis process of pinane hydroperoxide according to claim 5, characterized in that, The antimony-containing compound is antimony trichloride, the halogen-containing compound is potassium iodide, and the alcohol solvent is ethylene glycol; the crystallization treatment is carried out at 100-140℃ for 8-15 hours.

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