Green and efficient caryophyllene hydration method and device

Abstract

The invention provides a green and efficient caryophyllene hydration method and device, and the process comprises the following steps: mixing a solid acid catalyst with a turpentine heavy fraction to obtain a mixed solution; adding water in a mass ratio of 100: (10-15) to the turpentine heavy fraction into the mixed solution, and after the reaction is finished, and / or filtering out the catalyst to obtain a filtrate; and carrying out reduced pressure rectification and recrystallization on the filtrate. The preparation method is simple, the raw material conversion rate can reach 90%-99%, reaction conditions are mild, product selectivity is high, side reactions are few, and production operation is easy; meanwhile, the reaction efficiency is high, the catalyst can be recycled after being filtered, and the concept of green chemistry is better met.

Description

Technical Field

[0001] The invention belongs to the field of chemical engineering and process technology, and in particular to a green and efficient caryophyllene hydration method and device. Background Art

[0002] Rosin distillation is an important process in the field of forestry. It refers to the process of separating the purified rosin liquid by steam or other methods to obtain rosin and turpentine. Rosin is mainly composed of rosin and turpentine, which have different boiling points and can be separated by distillation. In the distillation process, heating is used to liquefy the rosin, and then the turpentine (lower boiling point) is evaporated first, while the rosin (higher boiling point) is left as the residue. Among them, heavy turpentine can be used as a raw material for the production of caryophyllene alcohol.

[0003] Caryophyllene alcohol is naturally present in the high boiling point fraction of Asian mint oil or peppermint oil, has a unique aroma, can be used to prepare various spices, cosmetics, and can be used as a food additive. Caryophyllene alcohol also has antibacterial and anti-inflammatory biological activities, and can be used to synthesize a new antiasthmatic and antitussive drug with a lasting antiasthmatic effect and low toxicity. Therefore, the preparation process of caryophyllene alcohol has received extensive attention. The current preparation method is to use caryophyllene as a raw material and carry out a hydration reaction under acid catalysis, such as using sulfuric acid, chloroacetic acid, p-toluenesulfonic acid, macroporous adsorption strong acid cation exchange resin, molecular sieve, etc. as catalysts to react in different solvents, but no satisfactory results have been obtained (see: Cao Yurong et al., Journal of Chemistry of Colleges and Universities Vol. 20, No. 7, pp1086-1087, 1999). There is also the use of optically active D- and L-camphorsulfonic acid to act on caryophyllene to obtain optically active caryophyllene alcohol, or to separate caryophyllene alcohol with higher purity from the residue of isolongifolene. The above preparation methods all have defects that are difficult to solve: the catalysts and solvents used will cause a certain 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 carry out industrial production. Because as food additives and drug products, their hygiene indicators and specified purity must be guaranteed. Therefore, it is crucial to find a preparation process that can meet the requirements of food additives and drugs and is environmentally friendly and clean.

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

[0005] The first purpose of the present invention is to provide a green and efficient caryophyllene hydration method. The preparation method is simple, so that the raw material conversion rate can reach 90%-99%, the reaction conditions are mild, the product selectivity is high, the side reactions are few, and the production operation is easy; 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 purpose of the present invention is to provide a device used in the above-mentioned refined green and efficient caryophyllene hydration method, which utilizes a micro-interface strengthening device to effectively increase the mass transfer rate of the strengthened interface and greatly increase the reaction rate.

[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are specially adopted: The present invention provides a green and efficient caryophyllene hydration method, comprising the following steps: Mixing the solid acid catalyst with the turpentine heavy fraction to obtain a mixed liquid; Add water in a mass ratio of 100:(10-15) to the turpentine heavy fraction to the mixed solution, and after the reaction is completed, and / or filter out the catalyst to obtain a filtrate; The filtrate is subjected to vacuum distillation and recrystallization to obtain the product.

[0008] In the present invention, the content of turpentine heavy fraction and water is limited, and the content of water is slightly excessive at this mass ratio. The purpose of this setting is to ensure that turpentine can fully participate in the reaction, and at the same time, the loss of water generated during the reaction process is supplemented. And at this mass ratio, it is more possible to promote the positive occurrence of the reaction system and accelerate the progress of the reaction. When there is too little water, the water is consumed in advance, and the turpentine cannot be subjected to subsequent reactions, causing waste. At the same time, the reactants and the products are mixed to generate a mixture that is difficult to separate; in addition, the rate and efficiency of the reaction are reduced, and the purpose of the invention of the present invention cannot be achieved. When the content of water is too much, it will not only cause unnecessary waste, but also reduce the efficiency of the reaction.

[0009] Preferably, as a further specific implementation, the vacuum distillation step comprises the following steps: The filtrate is subjected to vacuum distillation at 90°C-110°C / 4mmHg-5mmHg to obtain a mixture; The mixture was fractionated twice at 140°C-160°C / 4mmHg-5mmHg.

[0010] In the present invention, based on the boiling point difference of liquid at different temperatures, the boiling point of impurities is reduced by decompression to 4mmHg-5mmHg, the low boiling point impurities are efficiently separated under the low temperature conditions of 90℃-110℃, and the crude product of caryophyllene alcohol is extracted by distillation at a higher temperature of 140℃-160℃, so the pressure cannot be easily changed in the present invention, and the change of pressure will lead to the change of the boiling point of impurities. When the pressure is too low, although the boiling point of impurities will be further reduced, a more energy-saving effect will be achieved, but at the same time, the separation efficiency of impurities will be greatly reduced; and when the pressure increases, a substantial increase in the boiling point will be caused, and a large amount of energy consumption will be required during separation. Therefore, in the present invention, it is necessary to limit the pressure during the decompression process to play a role in limiting the temperature, further ensuring a more efficient and energy-saving separation of impurities at a more reasonable temperature, while ensuring the efficiency of separation.

[0011] Preferably, as a further specific embodiment, in the step of adding water to the mixed solution, the reaction conditions are 10° C.-80° C. for 0.5 h-4 h.

[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 the temperature of a general hydration reaction. The reason is that, on the one hand, the method of the present invention is combined with the reaction device, which can significantly reduce the energy required in the reaction process; on the other hand, by screening and changing the reaction process, the reaction temperature can be significantly reduced while ensuring a high reaction efficiency.

[0013] Preferably, as a further specific implementation, 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 turpentine heavy fraction itself.

[0014] Solid acid participates in the reaction as a catalyst. In the present invention, the catalyst participating in the reaction can be recovered by filtering. There are acid centers on the solid acid catalyst, which can catalyze the reaction. Therefore, the quality of the solid acid catalyst will affect its quantity and ultimately affect the distribution intensity of the acid center. In addition, the structure of the solid acid catalyst itself also affects the reaction itself. It can be seen that in the reaction of the present invention, the intensity range of the effective catalyst needs to be controlled within -3 <H 0 <+1.5, so the mass ratio of solid acid catalyst to water needs to be limited to 1: (1-3), and the mass sum of solid acid catalyst and water is greater than or equal to 10% of the mass of turpentine heavy fraction itself to ensure the intensity of the reaction. When the content of solid acid catalyst is too little, the catalytic intensity is too low, which reduces the efficiency of the reaction; when the content of solid acid catalyst is too much, the catalyst is prone to aggregation and sedimentation, which reduces the total specific surface area of ​​the catalyst, reduces the effective contact area, and thus reduces the reaction rate.

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

[0016] This selection method can ensure that caryophyllene alcohol is first dissolved in the selected recrystallization reagent, while impurities are not dissolved, thereby obtaining caryophyllene alcohol with higher purity.

[0017] The present invention also provides a device used in a green and efficient caryophyllene hydration method, 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 part of a distillation tower, and a micro-interface strengthening unit is arranged at the bottom of the slurry bed reaction tower / solid bed reaction tower.

[0018] The method of the present invention is combined with the device, and the mass transfer rate of the interface can be enhanced by using the micro-interface strengthening unit, so that the mass transfer interface can reach several times or even dozens of times that of the traditional macro interface, and the reaction rate can be increased exponentially.

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

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

[0021] In the present invention, the catalyst in the fixed bed reactor is installed on the 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, and an additional filter is required to filter the catalyst.

[0022] Preferably, as a further specific implementation, the bottom outlet of the recrystallization tower is externally 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 provided on the circulation line, and a material outlet is provided on the condenser.

[0023] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention optimizes the preparation method of caryophyllene alcohol, so that the conversion rate of raw materials can reach 90%-99%. No acidic by-products or acidic substances remain in the reaction product, and there is no need for neutralization, water washing and other operations. The process is simple and the reaction efficiency can be effectively improved. At the same time, there are fewer side reactions and the reaction purity is high.

[0024] (2) The reaction device was designed to increase the reaction rate exponentially while reducing the energy consumption of the reaction. It is environmentally friendly and more in line with the requirements of green chemistry. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0026] 1-rosin inlet, 2-distillation tower, 3-reboiler, 4-micro interface strengthening unit, 5-heavy turpentine inlet, 6-fixed bed, 7-condenser, 8-fixed bed reaction tower, 9-vacuum distillation tower, 10-recrystallization solvent inlet, 11-recrystallization tower, 12-condenser, 13-condenser, 14-circulation pump, 15- reboiler; 1'-rosin inlet, 2'-distillation tower, 3'-reboiler, 4'-micro-interface strengthening 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. DETAILED DESCRIPTION

[0027] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be appreciated by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work, all belong to the scope of protection of the present invention. If specific conditions are not indicated in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0028] Example 1 This embodiment uses a solid bed reaction device to carry out the reaction.

[0029] Specific connection method: Figure 1 As shown, the top of the distillation tower 2 is provided with an outlet connected in parallel with the condenser 7, and the condenser 7 is provided with an outlet, and the turpentine obtained by the reaction flows out from the condenser 7. The bottom of the distillation tower 2 is provided with a rosin inlet 1, and the bottom of the distillation tower 2 is connected in parallel with a reboiler 3 to achieve reheating of the distillation tower 2. The raw material rosin is passed into the distillation tower 2 from the rosin inlet 1 for distillation, and the distillation obtains two components of turpentine and heavy turpentine. The turpentine passes through the condenser 7 from the top outlet of the distillation tower 2. The reboiler 3 can supply energy to the distillation tower 2, so that the raw material inside the distillation tower 2 can be continuously vaporized, and the catalyst is placed in the fixed bed 6.

[0030] 200g of heavy turpentine (GC analysis shows that caryophyllene is 46%) was stirred and preheated, and 160g of macroporous adsorption strong acid cation exchange resin (after water immersion treatment) (of which the mass of solid acid catalyst is 20g and the remaining mass is resin) was taken and loaded into a fixed bed reaction tower 2 with jacket heating and micro-interface strengthening unit, and the reaction materials were transported to the top of the fixed bed reaction tower containing the catalyst by a constant flow pump, and 20g of water entered the fixed bed reaction tower 8 through the micro-interface strengthening unit 4. The material preheating temperature and the jacket temperature were both controlled at 70°C. The time for the reaction mixture to flow through the bed is controlled to be about 20 minutes. At the same time, the reaction mixture flowing out of the fixed bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum distillation. The reboiler 15 can also provide energy for the vacuum distillation tower 9, so that the internal components of the vacuum distillation tower 9 can be continuously vaporized; first, a 90°C-110°C / 4mmHg-5mmHg front fraction is fractionated, and then a product 140°C-160°C / 4mmHg-5mmHg fraction caryophyllene alcohol is separated to obtain 86g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then enters the recrystallization tower 11. At the same time, petroleum ether enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization, and 96g of petroleum ether is dissolved at 50°C, hot filtered, and allowed to crystallize. After the crystals are precipitated, they are filtered and re-entered into the recrystallization tower 11 through the circulation pump 14, and recrystallized once more, filtered, and dried to obtain 78 g of needle-shaped white crystals with a measured mp of 94.2°C-94.6°C, a purity of 99%, and a refined conversion rate of 90.7%.

[0031] Example 2 700g of heavy turpentine (GC analysis shows that caryophyllene contains 25%) is stirred and preheated, and 150g of macroporous adsorption strong acidic cation exchange resin (after water immersion treatment) (of which the mass of solid acid catalyst is 70g and the remaining mass is resin) is taken and loaded into a fixed bed reaction tower 2 with jacket heating and micro-interface strengthening unit, and the reaction material is transported to the top of the fixed bed reaction tower containing the catalyst by a constant flow pump, and 70g of water enters the fixed bed reaction tower 8 through the micro-interface strengthening unit 4. The material preheating temperature and the jacket temperature are both controlled at 50°C. The time for the reaction mixture to flow through the bed is controlled to be about 3 hours. At the same time, the reaction mixture flowing out of the fixed bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum distillation. The reboiler 15 can also provide energy for the vacuum distillation tower 9, so that the internal components of the vacuum distillation tower 9 can be continuously vaporized; first, a 90°C-110°C / 4mmHg-5mmHg front fraction is fractionated, and then a product 140°C-160°C / 4mmHg-5mmHg fraction caryophyllene alcohol is separated to obtain 138g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then enters the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. 200g of n-heptane is used to dissolve at 50°C, hot filtration is performed, and crystallization is allowed to proceed. After the crystals are precipitated, they are filtered and re-entered into the recrystallization tower 11 through the circulation pump 14, and recrystallized once more, filtered, and dried to obtain 110 g of needle-shaped white crystals with a measured mp of 94.1°C-94.5°C, a purity of 99%, and a refining conversion rate of 79.7%.

[0032] Example 3 Preheat 1200 g of heavy turpentine (GC analysis showed caryophyllene content 42%) by stirring, and heat to 40 °C by stirring. 4 2- Promoted oxide solid super catalyst SO 4 2- / ZrO 2200g (after water soaking treatment) is loaded into a fixed bed reaction tower 2 with a jacket heating and micro-interface strengthening unit, and the reaction materials are transported to the top of the fixed bed reaction tower containing the catalyst by a constant flow pump, and 200g of water enters the fixed bed reaction tower 8 through the micro-interface strengthening unit 4. The material preheating temperature and the jacket temperature are both controlled at 40°C. The time for the reaction mixture to flow through the bed is controlled to be about 3 hours. At the same time, the reaction mixture flowing out of the fixed bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum fractionation. The reboiler 15 can also provide energy for the vacuum distillation tower 9, so that the internal components of the vacuum distillation tower 9 can be continuously vaporized; first, a 90°C-110°C / 4mmHg-5mmHg front fraction is fractionated, and then a product 140°C-160°C / 4mmHg-5mmHg fraction caryophyllene alcohol is separated to obtain 440g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then enters the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. 500g of n-heptane is used to dissolve at 50°C, hot filtration is performed, and crystallization is allowed to proceed. After the crystals are precipitated, they are filtered and re-entered into the recrystallization tower 11 through the circulation pump 14, and recrystallized once more, filtered, and dried to obtain 398 g of needle-shaped white crystals with a measured mp of 94.0°C-94.6°C, a purity of 99%, and a refined conversion rate of 90.4%.

[0033] Example 4 2000g of heavy turpentine (GC analysis shows that caryophyllene is 70%) was stirred and preheated, and 220g of heteropolyacid catalyst dodecaphosphotungstic acid (after water soaking treatment) was taken and loaded into a fixed bed reaction tower 2 with a jacket heating and micro-interface strengthening unit. The reaction materials were transported to the top of the fixed bed reaction tower containing the catalyst by a constant flow pump, and 220g of water entered the fixed bed reaction tower 8 through the micro-interface strengthening unit 4. The material preheating temperature and the jacket temperature were controlled at 70°C for reaction. The time for the reaction mixture to flow through the bed is controlled to be about 3 hours. At the same time, the reaction mixture flowing out of the fixed bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum distillation. The reboiler 15 can also provide energy for the vacuum distillation tower 9, so that the internal components of the vacuum distillation tower 9 can be continuously vaporized; first, the 90℃-110℃ / 4mmHg-5mmHg front fraction is distilled out, and then the product 140℃-160℃ / 4mmHg-5mmHg fraction caryophyllene alcohol is separated to obtain 1245g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then enters the recrystallization tower 11. At the same time, the solvent gasoline enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. 1500g of solvent gasoline is dissolved at 50℃, hot filtered, and allowed to crystallize. After the crystals are precipitated, they are filtered and re-entered into the recrystallization tower 11 through the circulation pump 14, and recrystallized once more, filtered, and dried to obtain 1055 g of needle-shaped white crystals with a measured mp of 94.2°C-94.6°C, a purity of 99%, and a refined conversion rate of 84.7%.

[0034] Example 5 200g of heavy turpentine (GC analysis shows 46% caryophyllene) was stirred and preheated, and 160g of macroporous adsorption strong acid cation exchange resin (after water immersion treatment) (of which the mass of solid acid catalyst is 20g and the remaining mass is resin) was taken and loaded into a fixed bed reaction tower 2 with jacket heating and micro-interface strengthening unit, and the reaction materials were transported to the top of the fixed bed reaction tower with catalyst by a constant flow pump, and 20g of water entered the fixed bed reaction tower 8 through the micro-interface strengthening unit 4. The material preheating temperature and the jacket temperature were controlled at 40°C. The time for the reaction mixture to flow through the bed is controlled to be about 30 minutes. At the same time, the reaction mixture flowing out of the fixed bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum distillation. The reboiler 15 can also provide energy for the vacuum distillation tower 9, so that the internal components of the vacuum distillation tower 9 can be continuously vaporized; first, a 90°C-110°C / 4mmHg-5mmHg front fraction is fractionated, and then a product 140°C-160°C / 4mmHg-5mmHg fraction caryophyllene alcohol is separated to obtain 65g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then enters the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization, and 96g of petroleum ether is used to dissolve at 50°C, hot filtered, and allowed to crystallize. After the crystals are precipitated, they are filtered and re-entered into the recrystallization tower 11 through the circulation pump 14, and recrystallized once more, filtered, and dried to obtain 56 g of needle-shaped white crystals with a measured mp of 94.2°C-94.6°C, a purity of 99%, and a refined conversion rate of 86.1%.

[0035] Example 6 700g of heavy turpentine (GC analysis shows that caryophyllene contains 25%) was stirred and preheated, and 160g of macroporous adsorption strong acid cation exchange resin (after water immersion treatment) (of which the mass of solid acid catalyst is 70g and the remaining mass is resin) was taken and loaded into a fixed bed reaction tower 2 with jacket heating and micro-interface strengthening unit, and the reaction materials were transported to the top of the fixed bed reaction tower containing the catalyst by a constant flow pump, and 70g of water entered the fixed bed reaction tower 8 through the micro-interface strengthening unit 4. The material preheating temperature and the jacket temperature were both controlled at 60°C. The time for the reaction mixture to flow through the bed is controlled to be about 3 hours. At the same time, the reaction mixture flowing out of the fixed bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum distillation. The reboiler 15 can also provide energy for the vacuum distillation tower 9, so that the internal components of the vacuum distillation tower 9 can be continuously vaporized; first, a 90°C-110°C / 4mmHg-5mmHg front fraction is fractionated, and then a product 140°C-160°C / 4mmHg-5mmHg fraction caryophyllene alcohol is separated to obtain 143g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then enters the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. 200g of n-heptane is used to dissolve at 40°C, hot filtration is performed, and crystallization is allowed to proceed. After the crystals are precipitated, they are filtered and re-entered into the recrystallization tower 11 through the circulation pump 14, recrystallized once more, filtered, and dried to obtain 125 g of needle-shaped white crystals with a measured mp of 94.1°C-94.5°C, a purity of 99%, and a refined conversion rate of 87.4%.

[0036] Example 7 1200 g of heavy turpentine (GC analysis showed 42% caryophyllene) was stirred and preheated, and SO42- was taken to promote the solid super catalyst SO 4 2- / ZrO 2200g (after water soaking treatment) is loaded into a fixed bed reaction tower 2 with a jacket heating and micro-interface strengthening unit, and the reaction materials are transported to the top of the fixed bed reaction tower containing the catalyst by a constant flow pump, and 200g of water enters the fixed bed reaction tower 8 through the micro-interface strengthening unit 4. The material preheating temperature and the jacket temperature are both controlled at 60°C. The time for the reaction mixture to flow through the bed is controlled to be about 3 hours. At the same time, the reaction mixture flowing out of the fixed bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum distillation. The reboiler 15 can also provide energy for the vacuum distillation tower 9, so that the internal components of the vacuum distillation tower 9 can be continuously vaporized; first, a 90°C-110°C / 4mmHg-5mmHg front fraction is fractionated, and then a product 140°C-160°C / 4mmHg-5mmHg fraction caryophyllene alcohol is separated to obtain 468g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then enters the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization. 500g of n-heptane is used to dissolve at 60°C, hot filtration is performed, and crystallization is allowed to proceed. After the crystals are precipitated, they are filtered and re-entered into the recrystallization tower 11 through the circulation pump 14, and recrystallized once more, filtered, and dried to obtain 416 g of needle-shaped white crystals with a measured mp of 94.0°C-94.6°C, a purity of 99%, and a refined conversion rate of 88.9%.

[0037] Example 8 2000g of heavy turpentine (GC analysis shows that caryophyllene is 70%) was stirred and preheated, and 220g of heteropolyacid catalyst dodecaphosphotungstic acid (after water soaking treatment) was taken and loaded into a fixed bed reaction tower 2 with a jacket heating and micro-interface strengthening unit. The reaction material was transported to the top of the fixed bed reaction tower containing the catalyst by a constant flow pump, and 220g of water entered the fixed bed reaction tower 8 through the micro-interface strengthening unit 4. The material preheating temperature and the jacket temperature were both controlled at 50°C for reaction. The time for the reaction mixture to flow through the bed is controlled to be about 3 hours. At the same time, the reaction mixture flowing out of the fixed bed reaction tower 8 enters the vacuum distillation tower 9 for vacuum distillation. The reboiler 15 can also provide energy for the vacuum distillation tower 9, so that the internal components of the vacuum distillation tower 9 can be continuously vaporized; first, a 90°C-110°C / 4mmHg-5mmHg front fraction is distilled out, and then a product 140°C-160°C / 4mmHg-5mmHg fraction caryophyllene alcohol is separated to obtain 1178g of crude caryophyllene alcohol. The crude caryophyllene alcohol enters the condenser 12 and then enters the recrystallization tower 11. At the same time, n-heptane enters the recrystallization tower 11 through the recrystallization solvent inlet 10 for recrystallization, and 1500g of solvent gasoline is dissolved at 50°C, hot filtered, and allowed to crystallize. After the crystals are precipitated, they are filtered and re-entered into the recrystallization tower 11 through the circulation pump 14, and recrystallized once more, filtered, and dried to obtain 996 g of needle-shaped white crystals with a measured mp of 94.2°C-94.6°C, a purity of 99%, and a refining conversion rate of 84.5%.

[0038] Example 9 The specific implementation method is consistent with Example 5, and the reaction conditions are changed. The reaction results are shown in Table 1.

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

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

[0041] Specific connection method: Figure 2 As shown, the top of the distillation tower 2' is provided with an outlet connected in parallel with the condenser 7', and the condenser 7' is provided with an outlet, and the turpentine obtained by the reaction flows out from the condenser 7'. The bottom of the distillation tower 2' is provided with a rosin inlet 1', and the bottom of the distillation tower 2' is connected in parallel with a reboiler 3' to achieve reheating of the distillation tower 2'. The raw material rosin is passed into the distillation tower 2' from the rosin inlet 1' for distillation, and the distillation obtains two components of turpentine and heavy turpentine. The turpentine passes through the condenser 7' from the top outlet of the distillation tower 2', and the reboiler 3' can supply energy to the distillation tower 2', so that the raw material inside the distillation tower 2' can be continuously vaporized.

[0042] 200g of heavy turpentine (GC analysis shows 46% caryophyllene) was stirred and preheated, and 160g of macroporous adsorption strong acidic cation exchange resin (after water soaking treatment) (of which the mass of solid acid catalyst is 20g and the remaining mass is resin) was taken and loaded into a slurry bed reaction tower 2' with jacket heating and micro-interface strengthening unit, and the reaction materials were transported to the top of the slurry bed reaction tower with catalyst by a constant flow pump, and 20g of water entered the slurry bed reaction tower 8' through the micro-interface strengthening unit 4'. The material preheating temperature and the jacket temperature were both controlled at 40°C. The reaction mixture is controlled to flow through the bed for about 30 minutes, and then enters the reaction mixture filter 9' which flows out from the slurry bed reaction tower 8 to filter, and the catalyst is recovered. The recovered mixture enters the vacuum distillation tower 10' for vacuum fractionation. The reboiler 15' can also provide energy for the vacuum distillation tower 10', so that the internal components of the vacuum distillation tower 10' can be continuously vaporized. First, a 90°C-110°C / 4mmHg-5mmHg front fraction is fractionated, and then a product 140°C-160°C / 4mmHg-5mmHg fraction 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'. At the same time, n-heptane enters the recrystallization tower 12' through the recrystallization solvent inlet 11' for recrystallization, and 96g of petroleum ether is used to dissolve at 50°C, hot filtration is performed, and crystallization is allowed to proceed. After the crystals are precipitated, they are filtered and enter the recrystallization tower 12' again through the circulation pump 14', recrystallized once more, filtered, and dried to obtain 56 g of needle-shaped white crystals with a measured mp of 94.2°C-94.6°C, a purity of 99%, and a refined conversion rate of 86.1%.

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

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

[0045] Based on the above data, we can draw the following conclusions: In the present invention, mp is the melting point, and the melting point of caryophyllene alcohol is about 94°C-95°C. Therefore, the closer the melting point of the prepared finished product is to this range, the purer the product is. However, in the present invention, not only the purity of the final product but also the refining conversion rate and reaction efficiency must be considered. Therefore, Example 5 is selected as the optimal embodiment of the present invention after comprehensive consideration.

[0046] It can be seen from the experimental results of Examples 1 to 8 that changing the reaction conditions within the range set by the present invention does not affect the refining conversion rate and purity, while taking into account the efficiency of the reaction. It can be seen from the experimental results of Example 10 that the slurry bed reaction tower and the solid bed reaction tower do not affect the reaction results, but only change the reaction process, so in practical applications, the corresponding reaction device can be selected as needed.

[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 will be reduced. The reason is that high temperature will promote the occurrence of various side reactions, thereby reducing the purity of the product; while low temperature will lead to insufficient reaction of the raw materials, which will also reduce the refining conversion rate and the purity of the product, making it impossible to achieve the technical effect of the present invention. The adjustment of the mass ratio of water to catalyst has little effect on the conversion and purity of the raw materials when the catalyst is less. It mainly affects the reaction efficiency of the reaction, reduces the efficiency of the reaction, and cannot form an efficient reaction. When the water content is less, the content of water + catalyst cannot exceed 10% of the weight of the turpentine heavy fraction itself, which will not only reduce the efficiency of the reaction, but also make the content of the generated crude product less, and the content of the refined product obtained by conversion less, further affecting the purity and refining conversion rate of the final product, so that the reaction cannot achieve the technical effect of the present invention.

[0048] Comparing Example 5 with Comparative Example 1, it can be seen that when water is excessive, the hydration reaction can occur smoothly, and its influence on the refining conversion rate and product purity is small, and its main influence is reflected in the influence on the reaction rate, which reduces the reaction efficiency. When the water content is too low, water is consumed in advance during the reaction, which not only leads to a large amount of waste of turpentine heavy fractions, but also makes the reaction incomplete, and ultimately leads to a reduction in the refining conversion rate, the yield of the crude product and the product purity.

[0049] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements 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 caryophyllene hydration method, characterized in that: The steps include: Mixing the solid acid catalyst with the turpentine heavy fraction to obtain a mixed liquid; Add water in a mass ratio of 100:(10-15) to the turpentine heavy fraction to the mixed solution, and after the reaction is completed, and / or filter out the catalyst to obtain a filtrate; The filtrate is subjected to vacuum distillation and recrystallization to obtain the product.

2. The green and efficient caryophyllene hydration method according to claim 1, characterized in that: The step of vacuum distillation comprises the following steps: The filtrate is subjected to vacuum distillation at 90°C-110°C / 4mmHg-5mmHg to obtain a mixture; The mixture was fractionated twice at 140°C-160°C / 4mmHg-5mmHg.

3. The green and efficient caryophyllene hydration method according to claim 1, characterized in that: In the step of adding water to the mixed solution, the reaction conditions are 10° C.-80° C. for 0.5 h-4 h.

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 sum of the 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 the recrystallization is any one or more of an alkane reagent, ethanol or petroleum ether; Preferably, the alkane reagent is n-heptane.

6. A device used in the green and efficient caryophyllene hydration method according to any one of claims 1 to 5, characterized in that: include: 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 the distillation tower, and a micro-interface strengthening unit is arranged at the bottom of the slurry bed reaction tower / solid bed reaction tower.

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

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

9. The device 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 externally 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 arranged on the circulation line, and a material outlet is arranged on the condenser.

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