Green and efficient method and apparatus for hydrating caryophyllene

Abstract

Provided in the present invention are a green and efficient method and apparatus for hydrating caryophyllene. The process comprises the following steps: mixing a solid acid catalyst with a heavy fraction of turpentine oil to obtain a mixed solution; adding water to the mixed solution, wherein a mass ratio of the water to the heavy fraction of turpentine oil is 100 : (10-15); after completing the reaction and / or filtering off the catalyst, obtaining a filtrate; and subjecting the filtrate to vacuum distillation and recrystallization to obtain the product. The preparation method is simple, can achieve a raw material conversion rate of 90-99%, and features mild reaction conditions, high product selectivity, few side reactions and easy operation. Meanwhile, the reaction efficiency is high, and the catalyst can be recycled after being filtered, which better conforms to the concept of green chemistry.

Description

A green and efficient method and apparatus for hydrating caryophyllene. Technical Field

[0001] This invention belongs to the field of chemical engineering and process technology, specifically to a green and efficient method and apparatus for hydrating caryophyllene. Background Technology

[0002] Resin distillation is an important process in forestry. It refers to the process of separating purified pine resin liquid using steam distillation or other methods to obtain rosin and turpentine. Pine resin is mainly composed of rosin and turpentine, which have different boiling points and can therefore be separated by distillation. During distillation, the pine resin is liquefied by heating, and then the turpentine (with a lower boiling point) evaporates first, while the rosin (with a higher boiling point) remains as a distillate. The heavier turpentine can be used as a raw material for the production of caryophyllene alcohol.

[0003] Caryophyllene alcohol is naturally found in the high-boiling fractions of peppermint oil or peppermint oil, possessing a unique aroma. It can be used to formulate various fragrances and cosmetics, and can also be used as a food additive. Caryophyllene alcohol also exhibits antibacterial and anti-inflammatory biological activities, and can be used to synthesize a new bronchodilator and antitussive drug with a long-lasting effect and low toxicity. Therefore, the preparation process of caryophyllene alcohol has received widespread attention. Current preparation methods involve using caryophyllene as a raw material and carrying out a hydration reaction under acid catalysis, such as using sulfuric acid, chloroacetic acid, p-toluenesulfonic acid, macroporous adsorption strongly acidic cation exchange resin, and molecular sieves as catalysts in different solvents, but none have yielded satisfactory results (see: Cao Yurong et al., *Journal of Chemical Research in Higher Education*, Vol. 20, No. 7, pp. 1086-1087, 1999). Other methods include reacting caryophyllene with optically active D- and L-camphorsulfonic acids to obtain optically active caryophyllene alcohol, or isolating high-purity caryophyllene alcohol from the residue of isophyllene. The above preparation methods all have intractable drawbacks: the catalysts and solvents used can cause some degree of pollution to the final product and the environment; the reaction products are complex and difficult to separate and purify; and the preparation conditions are difficult to implement for industrial production. Because food additives and pharmaceutical products must meet hygiene standards and specified purity requirements, finding a preparation process that meets the requirements for use as food additives and pharmaceuticals, while also being environmentally friendly and clean, is of paramount importance.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The primary objective of this invention is to provide a green and efficient method for hydrating caryophyllene. This preparation method is simple, achieves a raw material conversion rate of 90%-99%, has mild reaction conditions, high product selectivity, few side reactions, and is easy to operate in production. At the same time, the reaction efficiency is high, and the catalyst can be filtered and recycled, which is more in line with the concept of green chemistry.

[0006] The second objective of this invention is to provide an apparatus for the above-mentioned refined, green, and efficient caryophyllene hydration method, which utilizes a micro-interface enhancement device to effectively improve the mass transfer rate of the enhanced interface and greatly increase the reaction rate.

[0007] To achieve the above-mentioned objectives of this invention, the following technical solution is adopted: This invention provides a green and efficient method for hydrating caryophyllene, comprising the following steps: mixing a solid acid catalyst with a heavy fraction of turpentine to obtain a mixture; adding water at a mass ratio of 100:(10-15) to the heavy fraction of turpentine to the mixture; after the reaction is completed, and / or filtering off the catalyst to obtain a filtrate; and distilling the filtrate under reduced pressure and recrystallizing to obtain the final product.

[0008] In this invention, the content of turpentine heavy fraction and water is limited. At this mass ratio, the water content is slightly excessive. This setting ensures that the turpentine fully participates in the reaction while compensating for water losses during the reaction. Furthermore, this mass ratio promotes the forward reaction and accelerates the reaction process. If there is too little water, it is consumed prematurely, preventing the turpentine from further reacting and resulting in waste. Additionally, reactants and products mix, forming a difficult-to-separate mixture. Moreover, the reaction rate and efficiency decrease, failing to achieve the objectives of this invention. Conversely, excessive water content not only leads to unnecessary waste but also reduces reaction efficiency.

[0009] Preferably, as a further specific embodiment, the step of vacuum distillation includes the following steps: distilling the filtrate under vacuum at 90℃-110℃ / 4mmHg-5mmHg to obtain a mixture; and distilling the mixture a second fraction at 140℃-160℃ / 4mmHg-5mmHg.

[0010] In the present invention, based on the boiling point differences of liquids at different temperatures, the boiling points of impurities are reduced by reducing the pressure to 4 mmHg - 5 mmHg, and low-boiling impurities are efficiently separated under the low-temperature condition of 90°C - 110°C, and crude caryophyllene alcohol is extracted by distillation at a relatively high temperature of 140°C - 160°C. Therefore, in the present invention, the pressure cannot be easily changed, because the change of pressure will lead to the change of the boiling point of impurities. When the pressure is too low, although it will further reduce the boiling point of impurities and achieve a more energy-saving effect, it will also significantly reduce the separation efficiency of impurities; when the pressure increases, it will lead to a significant increase in the boiling point, and a large amount of energy is required for separation. Thus, in the present invention, it is necessary to limit the pressure during the pressure reduction process to play a role in limiting the temperature, further ensuring the separation of impurities more efficiently and energy-saving at a relatively reasonable temperature while ensuring the separation efficiency.

[0011] Preferably, as a further specific implementation manner, in the step of reacting the mixed solution with water, the reaction conditions are to react for 0.5 h - 4 h under the condition of 10°C - 80°C.

[0012] In the present invention, the reaction temperature and reaction time of the hydration reaction are limited. The reaction temperature of the present invention is significantly lower than that of general hydration reactions. The reasons are as follows: on the one hand, the method of the present invention combined with the reaction device can significantly reduce the energy required during the reaction process; on the other hand, through the screening and change of the reaction process, the reaction temperature can be significantly reduced while ensuring a relatively high reaction efficiency.

[0013] Preferably, as a further specific implementation manner, the mass ratio of the solid acid catalyst to water is 1:(1 - 3), and the sum of the mass of the solid acid catalyst and water is greater than or equal to 10% of the mass of the heavy fraction of turpentine itself.

[0014] The solid acid participates in the reaction as a catalyst, and in the present invention, the catalyst participating in the reaction can be recovered by filtration. There are acid centers on the solid acid catalyst, which can achieve the catalysis of the reaction. Therefore, different masses of the solid acid catalyst will affect its quantity, and ultimately affect the distribution intensity of the acid centers; in addition, the influence of the structure of the solid acid catalyst itself on the reaction itself also needs to be considered. It can be seen that in the reaction of the present invention, the strength range of the effective catalyst needs to be controlled within -3 < H0 < +1.5. Therefore, it is necessary to limit the mass ratio of it to water within the range of 1:(1 - 3), and the sum of the mass of the solid acid catalyst and water is greater than or equal to 10% of the mass of the heavy fraction of turpentine itself to ensure the strength of the reaction. When the content of the solid acid catalyst is too small, the catalytic strength is too low, reducing the reaction efficiency; when the content of the solid acid catalyst is too large, the catalyst is prone to aggregation and sedimentation, reducing the total specific surface area of the catalyst and the effective contact area, thus reducing the reaction rate.

[0015] Preferably, as a further specific embodiment, the reagent used for recrystallization is any one or more of alkane reagents, ethanol, or petroleum ether; preferably, the alkane reagent is n-heptane.

[0016] This selection method ensures that caryophyllene alcohol dissolves first in the selected recrystallization reagent, while impurities remain undissolved, thus yielding caryophyllene alcohol with higher purity.

[0017] The present invention also provides an apparatus for a green and efficient method for hydrating caryophyllene, comprising: a slurry bed reaction tower or a fixed bed reaction tower, wherein the slurry bed reaction tower or the fixed bed reaction tower is directly connected to the middle of a distillation tower, and a micro-interface enhancement unit is provided at the bottom of the slurry bed reaction tower / solid bed reaction tower.

[0018] When combined with the device, the method of this invention can enhance the mass transfer rate of the interface by using a micro-interface enhancement unit, thereby enabling the mass transfer interface to reach several times or even tens of times that of the traditional macro-interface, and thus increasing the reaction rate exponentially.

[0019] Preferably, as a further specific embodiment, the inlet of the slurry bed reaction tower is directly connected to a filter, and the bottom outlet of the filter is directly connected to a vacuum distillation tower; a condenser is provided at the top of the vacuum distillation tower, a reboiler is provided at the bottom of the vacuum distillation tower, and the condenser is directly connected to a recrystallization tower.

[0020] Preferably, as a further specific embodiment, the solid reaction tower is directly connected to the middle inlet of the vacuum distillation tower, the top of the vacuum distillation tower is provided with a condenser, and the bottom of the vacuum distillation tower is provided with a reboiler; the condenser is directly connected to the recrystallization tower.

[0021] In this invention, the catalyst in the fixed-bed reactor is installed on a fixed bed, so there is no need to set up an additional filter to filter the catalyst; while in the slurry-bed reactor, the catalyst is mixed into the reactants, so an additional filter is required to filter the catalyst.

[0022] Preferably, as a further specific embodiment, the bottom outlet of the recrystallization tower is connected to a circulation pipeline, the inlet of which is connected to the top of the recrystallization tower; a delivery pump and a condenser are provided on the circulation pipeline, and a material outlet is provided on the condenser.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) By optimizing the preparation method of caryophyllene alcohol, the present invention can achieve a conversion rate of 90%-99% of the raw materials, and no acidic by-products or acidic substances are generated in the reaction products. There is no need for neutralization, water washing and other operations. The process is simple and can effectively improve the reaction efficiency. At the same time, there are few side reactions and the reaction purity is high.

[0024] (2) The reaction apparatus was designed to increase the reaction rate several times over while reducing the energy consumption of the reaction, making it more environmentally friendly and in line with the requirements of green chemistry. Attached Figure Description

[0025] Figure 1: Schematic diagram of solid-state bed micro-interface enhanced reaction device; Figure 2: Schematic diagram of slurry bed micro-interface enhanced reaction device.

[0026] 1-Rosin inlet, 2-Distillation column, 3-Reboiler, 4-Micro-interface enhancement unit, 5-Heavy turpentine inlet, 6-Fixed bed, 7-Condenser, 8-Fixed bed reaction column, 9-Vacuum distillation column, 10-Recrystallization solvent inlet, 11-Recrystallization column, 12-Condenser, 13-Condenser, 14-Circulating pump, 15-Reboiler, 16-Reboiler outlet, 17-Reboiler outlet; 1'-Rosin inlet, 2'-Distillation column, 3'-Reboiler, 4'-Micro-interface enhancement unit, 5'-Heavy turpentine inlet, 6'-Solid acid catalyst inlet pipeline, 7'-Condenser, 8'-Slurry bed reaction tower, 9'-Filter, 10'-Vacuum distillation tower, 11'-Recrystallization solvent inlet, 12'-Recrystallization tower, 13'-Condenser, 14'-Circulation pump, 15'-Reboiler, 16'-Condenser, 17'-Reboiler outlet, 18'-Reboiler outlet. Detailed Implementation

[0027] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. 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. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0028] Example 1 This example uses a solid-bed reactor for the reaction.

[0029] The specific connection method is shown in Figure 1. The top of the distillation column 2 is equipped with an outlet connected in parallel with the condenser 7. The condenser 7 also has an outlet, from which the turpentine oil obtained from the reaction flows out. The bottom of the distillation column 2 is equipped with a rosin inlet 1, and a reboiler 3 is connected in parallel to the bottom of the distillation column 2 to achieve reheating of the distillation column 2. The raw material rosin is fed into the distillation column 2 through the rosin inlet 1 for distillation, and two components, turpentine oil and heavy turpentine oil, are obtained. The turpentine oil passes through the condenser 7 from the top outlet of the distillation column 2. The reboiler 3 can provide energy to the distillation column 2, and other products can flow out from the reboiler outlet 17, so that the raw material inside the distillation column 2 can be continuously vaporized. The catalyst is placed in the fixed bed 6.

[0030] 200g of heavy turpentine oil (GC analysis showed it contained 46% caryophyllene) was stirred and preheated. 160g of macroporous adsorption strongly acidic cation exchange resin (after water soaking treatment) (20g of which was solid acid catalyst, the remainder being resin) was loaded into a fixed-bed reaction tower 2 equipped with a jacketed heating unit and a micro-interface enhancement unit. The reactants were pumped to the top of the fixed-bed reaction tower containing the catalyst using a constant flow pump. 20g of water entered the fixed-bed reaction tower 8 through the micro-interface enhancement unit 4. The preheating temperature of the materials and the jacket temperature were both controlled at 70℃. The reaction mixture is controlled to flow through the bed for approximately 20 minutes. Simultaneously, the reaction mixture flowing out of the fixed-bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 also provides energy to the vacuum distillation tower 9, enabling the internal components of the vacuum distillation tower 9 to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-distillate is fractionated, which can flow out from the reboiler outlet 16. Then, the 140℃-160℃ / 4mmHg-5mmHg fraction of caryophyllene alcohol is separated, yielding 86g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then the recrystallization tower 11. At the same time, petroleum ether enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. 96g of petroleum ether is dissolved at 50℃, hot filtered, and allowed to crystallize. After crystallization, the sample is filtered and then re-entered into recrystallization tower 11 via circulation pump 14 for recrystallization once more. After filtration and drying, 78g of needle-like white crystals are obtained. The mp value is 94.2℃-94.6℃, the purity is 99%, and the purification conversion rate is 90.7%.

[0031] Example 2: 700g of heavy turpentine oil (GC analysis showed it contained 25% caryophyllene) was stirred and preheated. 150g of macroporous adsorption strongly acidic cation exchange resin (after water soaking treatment) (70g of which was solid acid catalyst, the remainder being resin) was loaded into a fixed-bed reaction tower 2 equipped with a jacketed heating and micro-interface enhancement unit. The reactants were pumped to the top of the fixed-bed reaction tower containing the catalyst using a constant flow pump. 70g of water entered the fixed-bed reaction tower 8 through the micro-interface enhancement unit 4. The preheating temperature of the materials and the jacket temperature were both controlled at 50℃. The reaction mixture is controlled to flow through the bed for approximately 3 hours. Simultaneously, the reaction mixture flowing out of the fixed-bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 also provides energy to the vacuum distillation tower 9, enabling the internal components of the vacuum distillation tower 9 to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-distillate is fractionated, which can flow out from the reboiler outlet 16. Then, the 140℃-160℃ / 4mmHg-5mmHg fraction of caryophyllene alcohol is separated, yielding 138g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. It is dissolved in 200g of n-heptane at 50℃, hot filtered, and allowed to crystallize. After crystallization, the sample is filtered and then re-entered into recrystallization tower 11 via circulation pump 14 for recrystallization once more. After filtration and drying, 110g of needle-like white crystals are obtained. The mp value is 94.1℃-94.5℃, the purity is 99%, and the purification conversion rate is 79.7%.

[0032] Example 3: 1200g of heavy turpentine oil (GC analysis showed it contained 42% caryophyllene) was stirred and preheated, then stirred and heated to a constant temperature of 40°C. SO4 was then collected. 2 - Promotes the development of SO4 solid oxide supercatalysts 2200g of ZrO2 (treated with water immersion) was loaded into a fixed-bed reactor 2 equipped with a jacketed heating unit and a micro-interface enhancement unit. The reactants were pumped to the top of the fixed-bed reactor containing the catalyst using a constant flow pump. 200g of water was fed into the fixed-bed reactor 8 through the micro-interface enhancement unit 4. The preheating temperature of the materials and the jacket temperature were both controlled at 40℃. The reaction mixture is controlled to flow through the bed for approximately 3 hours. Simultaneously, the reaction mixture flowing out of the fixed-bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 also provides energy to the vacuum distillation tower 9, enabling the internal components of the vacuum distillation tower 9 to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-distillate is fractionated, which can flow out from the reboiler outlet 16. Then, the 140℃-160℃ / 4mmHg-5mmHg fraction of caryophyllene alcohol is separated, yielding 440g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. It is dissolved in 500g of n-heptane at 50℃, hot filtered, and allowed to crystallize. After crystallization, the sample is filtered and then re-entered into recrystallization tower 11 via circulation pump 14 for recrystallization once more. After filtration and drying, 398g of needle-like white crystals are obtained. The mp value is 94.0℃-94.6℃, the purity is 99%, and the purification conversion rate is 90.4%.

[0033] Example 4: 2000g of heavy turpentine oil (GC analysis showed it contained 70% caryophyllene) was stirred and preheated. 220g of dodecaphosphotungstic acid catalyst (treated with water soaking) was added to a fixed-bed reactor 2 equipped with a jacketed heating unit and a micro-interface enhancement unit. The reactants were pumped to the top of the fixed-bed reactor containing the catalyst using a constant flow pump. 220g of water entered the fixed-bed reactor 8 through the micro-interface enhancement unit 4. The preheating temperature of the materials and the jacket temperature were both controlled at 70℃ for the reaction. The reaction mixture is controlled to flow through the bed for approximately 3 hours. Simultaneously, the reaction mixture flowing out of the fixed-bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 also provides energy to the vacuum distillation tower 9, enabling the internal components of the vacuum distillation tower 9 to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-distillate is fractionated, and the fore-distillate can flow out from the reboiler outlet 16. Then, the 140℃-160℃ / 4mmHg-5mmHg fraction of caryophyllene alcohol is separated, yielding 1245g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12, and then enters the recrystallization tower 11. At the same time, solvent gasoline enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. It is dissolved in 1500g of solvent gasoline at 50℃, hot filtered, and allowed to crystallize. After crystallization, the sample is filtered and then re-entered into recrystallization tower 11 via circulation pump 14 for recrystallization once more. After filtration and drying, 1055g of needle-like white crystals are obtained. The mp value is 94.2℃-94.6℃, the purity is 99%, and the purification conversion rate is 84.7%.

[0034] Example 5: 200g of heavy turpentine oil (GC analysis showed it contained 46% caryophyllene) was stirred and preheated. 160g of macroporous adsorption strongly acidic cation exchange resin (after water soaking treatment) (20g of which was solid acid catalyst, the remainder being resin) was loaded into a fixed-bed reaction tower 2 equipped with a jacketed heating and micro-interface enhancement unit. The reactants were pumped to the top of the fixed-bed reaction tower containing the catalyst using a constant flow pump. 20g of water entered the fixed-bed reaction tower 8 through the micro-interface enhancement unit 4. The preheating temperature of the materials and the jacket temperature were both controlled at 40℃. The reaction mixture is controlled to flow through the bed for approximately 30 minutes. Simultaneously, the reaction mixture flowing out of the fixed-bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 also provides energy to the vacuum distillation tower 9, enabling the internal components of the vacuum distillation tower 9 to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-distillate is fractionated, which can flow out from the reboiler outlet 16. Then, the 140℃-160℃ / 4mmHg-5mmHg fraction of caryophyllene alcohol is separated, yielding 65g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. It is dissolved in 96g of petroleum ether at 50℃, hot filtered, and allowed to crystallize. After crystallization, the sample is filtered and then re-entered into recrystallization tower 11 via circulating pump 14 for recrystallization once more. After filtration and drying, 56g of needle-like white crystals are obtained. The mp value is 94.2℃-94.6℃, the purity is 99%, and the purification conversion rate is 86.1%.

[0035] Example 6: 700g of heavy turpentine oil (GC analysis showed it contained 25% caryophyllene) was stirred and preheated. 160g of macroporous adsorption strong acid cation exchange resin (after water soaking treatment) (70g of which was solid acid catalyst, the remainder being resin) was loaded into a fixed-bed reaction tower 2 equipped with a jacketed heating and micro-interface enhancement unit. The reactants were pumped to the top of the fixed-bed reaction tower containing the catalyst using a constant flow pump. 70g of water entered the fixed-bed reaction tower 8 through the micro-interface enhancement unit 4. The preheating temperature of the materials and the jacket temperature were both controlled at 60℃. The reaction mixture is controlled to flow through the bed for approximately 3 hours. Simultaneously, the reaction mixture flowing out of the fixed-bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 also provides energy to the vacuum distillation tower 9, enabling the internal components of the vacuum distillation tower 9 to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-distillate is fractionated, which can flow out from the reboiler outlet 16. Then, the 140℃-160℃ / 4mmHg-5mmHg fraction of caryophyllene alcohol is separated, yielding 143g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. It is dissolved in 200g of n-heptane at 40℃, hot filtered, and allowed to crystallize. After crystallization, the sample is filtered and then re-entered into recrystallization tower 11 via circulation pump 14 for recrystallization once more. After filtration and drying, 125g of needle-like white crystals are obtained. The mp value is 94.1℃-94.5℃, the purity is 99%, and the purification conversion rate is 87.4%.

[0036] Example 7: 1200g of heavy turpentine oil (GC analysis showed it contained 42% caryophyllene) was stirred and preheated. SO42- was then used to promote the production of solid supercatalysts for oxides, SO42-. 2200g of ZrO2 (treated with water immersion) was loaded into a fixed-bed reactor 2 equipped with a jacketed heating unit and a micro-interface enhancement unit. The reactants were pumped to the top of the fixed-bed reactor containing the catalyst using a constant flow pump. 200g of water entered the fixed-bed reactor 8 through the micro-interface enhancement unit 4. The preheating temperature of the materials and the jacket temperature were both controlled at 60℃. The reaction mixture is controlled to flow through the bed for approximately 3 hours. Simultaneously, the reaction mixture flowing out of the fixed-bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 also provides energy to the vacuum distillation tower 9, enabling the internal components of the vacuum distillation tower 9 to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-distillate is fractionated, which can flow out from the reboiler outlet 16. Then, the 140℃-160℃ / 4mmHg-5mmHg fraction of caryophyllene alcohol is separated, yielding 468g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. It is dissolved in 500g of n-heptane at 60℃, hot filtered, and allowed to crystallize. After crystallization, the sample is filtered and then re-entered into recrystallization tower 11 via circulation pump 14 for recrystallization once more. After filtration and drying, 416g of needle-like white crystals are obtained. The mp value is 94.0℃-94.6℃, the purity is 99%, and the purification conversion rate is 88.9%.

[0037] Example 8: 2000g of heavy turpentine oil (GC analysis showed it contained 70% caryophyllene) was stirred and preheated. 220g of dodecaphosphotungstic acid catalyst (treated with water soaking) was added to a fixed-bed reactor 2 equipped with a jacketed heating unit and a micro-interface enhancement unit. The reactants were pumped to the top of the fixed-bed reactor containing the catalyst using a constant flow pump. 220g of water entered the fixed-bed reactor 8 through the micro-interface enhancement unit 4. The preheating temperature of the materials and the jacket temperature were both controlled at 50°C for the reaction. The reaction mixture is controlled to flow through the bed for approximately 3 hours. Simultaneously, the reaction mixture flowing out of the fixed-bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 also provides energy to the vacuum distillation tower 9, enabling the internal components of the vacuum distillation tower 9 to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-distillate is fractionated, which can flow out from the reboiler outlet 16. Then, the 140℃-160℃ / 4mmHg-5mmHg caryophyllene alcohol fraction is separated, yielding 1178g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then the recrystallization tower 11. Simultaneously, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. It is dissolved in 1500g of solvent gasoline at 50℃, hot filtered, and allowed to crystallize. After crystallization, the sample is filtered and then re-entered into recrystallization tower 11 via circulation pump 14 for recrystallization once more. After filtration and drying, 996g of needle-like white crystals are obtained. The mp value is 94.2℃-94.6℃, the purity is 99%, and the purification conversion rate is 84.5%.

[0038] Example 9 The specific implementation method is the same as that of Example 5, but the reaction conditions are changed. The reaction results are shown in Table 1.

[0039] Table 1: Effects of different reaction conditions on the conversion rate and purity of raw materials

[0040] Example 10: The reaction was carried out using a slurry bed reactor.

[0041] The specific connection method is shown in Figure 2. The top of the distillation column 2' is provided with an outlet connected in parallel with the condenser 7'. The condenser 7' has an outlet, from which the turpentine oil obtained from the reaction flows out. The bottom of the distillation column 2' is provided with a rosin inlet 1', and a reboiler 3' is connected in parallel at the bottom of the distillation column 2' to achieve reheating of the distillation column 2'. The raw material rosin is fed into the distillation column 2' through the rosin inlet 1' for distillation, and two components, turpentine oil and heavy turpentine oil, are obtained. The turpentine oil passes through the condenser 7' from the top outlet of the distillation column 2'. The reboiler 3' can provide energy to the distillation column 2', and other products can flow out from the reboiler outlet 18', so that the raw material inside the distillation column 2' can be continuously vaporized.

[0042] 200g of heavy turpentine oil (GC analysis showed it contained 46% caryophyllene) was stirred and preheated. 160g of macroporous adsorption strongly acidic cation exchange resin (after water soaking treatment) (20g of which was solid acid catalyst, the remainder being resin) was loaded into a slurry bed reactor 2' equipped with a jacketed heating and micro-interface enhancement unit. The reactants were pumped to the top of the slurry bed reactor containing the catalyst using a constant flow pump. 20g of water entered the slurry bed reactor 8' through the micro-interface enhancement unit 4'. The preheating temperature of the materials and the jacket temperature were both controlled at 40℃. The reaction mixture is controlled to flow through the bed for approximately 30 minutes, and then filtered through a filter 9' that simultaneously flows out of the slurry bed reaction tower 8 to recover the catalyst. The recovered mixture then enters a vacuum distillation tower 10' for vacuum fractionation. The reboiler 15' also provides energy to the vacuum distillation tower 10', allowing the internal components of the vacuum distillation tower 10' to continuously vaporize. First, the 90℃-110℃ / 4mmHg-5mmHg fore-fraction is fractionated, which can flow out from the reboiler outlet 17'. Then, the 140℃-160℃ / 4mmHg-5mmHg fraction of caryophyllene alcohol is separated to obtain 65g of crude caryophyllene alcohol. The crude caryophyllene alcohol then enters the condenser 16' for condensation, and then enters the recrystallization tower 12'. Simultaneously, n-heptane enters the recrystallization tower 12' through the recrystallization solvent inlet 11' for recrystallization, dissolved in 96g of petroleum ether at 50℃, hot filtered, and allowed to crystallize. After crystallization, the sample was filtered and then re-entered into recrystallization tower 12' via circulating pump 14' for recrystallization once more. After filtration and drying, 56g of needle-like white crystals were obtained. The mp value was 94.2℃-94.6℃, the purity was 99%, and the purification conversion rate was 86.1%.

[0043] Comparative Example 1: The specific implementation method is consistent with Example 5, except that the ratio of heavy turpentine oil to water is changed, as shown in Table 2.

[0044] Table 2: Effect of changing the mass ratio of water to heavy turpentine on the reaction

[0045] Based on the above data, the following conclusions can be drawn: In this invention, mp is the melting point. The melting point of caryophyllene alcohol is around 94℃-95℃. Therefore, the closer the melting point of the prepared product is to this range, the purer the product is. However, in this invention, not only the purity of the final product should be considered, but also the purification conversion rate and reaction efficiency. Therefore, considering all factors, Example 5 is selected as the optimal example of this invention.

[0046] The experimental results from Examples 1-8 show that changing the reaction conditions within the range set by this invention does not affect the purification conversion rate and purity, while also taking into account the reaction efficiency. The experimental results from Example 10 show that the slurry bed reaction tower and the solid bed reaction tower do not affect the reaction results; they only change the reaction process. Therefore, in practical applications, the appropriate reaction device can be selected according to needs.

[0047] Comparing Example 5 with Example 9, it can be found that when the reaction temperature is too high, the purity of the reaction product decreases. This is because high temperatures promote various side reactions, thereby reducing the purity of the product. Conversely, low temperatures lead to incomplete reaction of the raw materials, which also reduces the refining conversion rate and the purity of the product, preventing the achievement of the technical effect of this invention. Adjusting the mass ratio of water to catalyst has a relatively small impact on the conversion and purity of the raw materials when the catalyst content is low; it mainly affects the reaction efficiency, reducing the efficiency of the reaction and preventing the formation of a highly efficient reaction. When the water content is low, and the water + catalyst content cannot exceed 10% of the weight of the turpentine heavy fraction, it not only reduces the reaction efficiency but also results in a lower content of crude product and a lower content of refined product, further affecting the purity and refining conversion rate of the final product, preventing the reaction from achieving the technical effect of this invention.

[0048] Comparing Example 5 with Comparative Example 1 reveals that when water is in excess, the hydration reaction proceeds smoothly, with minimal impact on the refining conversion rate and product purity. Its main effect is on the reaction rate, reducing reaction efficiency. However, when the water content is too low, water is consumed prematurely during the reaction, leading not only to a significant waste of turpentine heavy fractions but also to incomplete reaction, ultimately resulting in reduced refining conversion rate, crude product yield, and product purity.

[0049] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A green and efficient method for hydrating caryophyllene, characterized in that, Includes the following steps: A solid acid catalyst was mixed with a heavy fraction of turpentine oil to obtain a mixture. Add water at a mass ratio of 100:(10-15) to the heavy fraction of turpentine to the mixture. After the reaction is complete, and / or filter out the catalyst to obtain the filtrate. The filtrate is obtained by vacuum distillation and recrystallization.

2. The green and efficient caryophyllene hydration method according to claim 1, characterized in that, The vacuum distillation process includes the following steps: The filtrate was subjected to vacuum distillation at 90℃-110℃ / 4mmHg-5mmHg to obtain a mixture. The mixture was subjected to secondary distillation at 140℃-160℃ / 4mmHg-5mmHg.

3. The green and efficient caryophyllene hydration method according to claim 1, characterized in that, In the water addition reaction step of the mixture, the reaction conditions are 10℃-80℃ for 0.5h-4h.

4. The green and efficient caryophyllene hydration method according to claim 1, characterized in that, The mass ratio of the solid acid catalyst to water is 1:(1-3), and the total mass of the solid acid catalyst and water is greater than or equal to 10% of the mass of the turpentine heavy fraction itself.

5. The green and efficient caryophyllene hydration method according to claim 1, characterized in that, The reagent used for recrystallization is any one or more of alkane reagents, ethanol, or petroleum ether. Preferably, the alkane reagent is n-heptane.

6. An apparatus used in the green and efficient caryophyllene hydration method as described in any one of claims 1-5, characterized in that, include: A slurry bed reaction tower or a fixed bed reaction tower is provided, wherein the slurry bed reaction tower or the fixed bed reaction tower is directly connected to the middle of the distillation tower, and a micro-interface enhancement unit is provided at the bottom of the slurry bed reaction tower / solid bed reaction tower.

7. The apparatus used in the green and efficient caryophyllene hydration method according to claim 6, characterized in that, The inlet of the slurry bed reaction tower is directly connected to a filter, and the bottom outlet of the filter is directly connected to a vacuum distillation tower. A condenser is installed at the top of the vacuum distillation tower, and a reboiler is installed at the bottom of the vacuum distillation tower. The condenser is directly connected to a recrystallization tower.

8. The apparatus used in the green and efficient caryophyllene hydration method according to claim 6, characterized in that, The solid reaction column is directly connected to the middle inlet of the vacuum distillation column. A condenser is installed at the top of the vacuum distillation column, and a reboiler is installed at the bottom of the vacuum distillation column. The condenser is directly connected to the recrystallization column.

9. The apparatus used in the green and efficient caryophyllene hydration method according to any one of claims 7-8, characterized in that, The bottom outlet of the recrystallization tower is connected to a circulation pipeline, and the inlet of the circulation pipeline is connected to the top of the recrystallization tower; a delivery pump and a condenser are installed on the circulation pipeline, and a material outlet is provided on the condenser.

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