CN108250045B - Method for preparing borneol from borneol oxalate - Google Patents

Method for preparing borneol from borneol oxalate Download PDF

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CN108250045B
CN108250045B CN201810197790.5A CN201810197790A CN108250045B CN 108250045 B CN108250045 B CN 108250045B CN 201810197790 A CN201810197790 A CN 201810197790A CN 108250045 B CN108250045 B CN 108250045B
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borneol
crystallization
solvent
catalyst
kettle
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CN108250045A (en
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危景波
江承艳
杨斌
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Fujian Nanping Green Pine Chemical Co ltd
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FUJIAN GREEN PINE CO LTD
Fujian Nanping Green Pine Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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Abstract

The invention discloses a method for preparing borneol from borneol oxalate, which comprises the steps of feeding borneol oxalate, a catalyst and caustic soda liquid into a tubular reactor for saponification, recovering the catalyst, washing crude borneol with water, recovering a solvent, dissolving, crystallizing and drying to obtain high-purity borneol. By adopting the mode, the problems of long saponification reaction time, high energy consumption, low yield, non-compact production flow, high labor intensity and the like can be solved, and a new crystallization device is adopted, so that the crystallization period is shortened, and the production efficiency is improved; the novel environment-friendly solvent is used instead, so that the production is pollution-free and environment-friendly, the safety is good, the product yield is improved, the generation of impurities is reduced, the product quality is stable, and the borneol content reaches more than 65%.

Description

Method for preparing borneol from borneol oxalate
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to a method for preparing borneol from borneol oxalate.
Background
Borneol (1,7,72 trimethyl bicyclo [2,2,1] heptanol) is also called borneol, and the functions of the borneol include: inducing resuscitation, clearing away heat, and relieving pain, and can be used for treating fever, coma, spasm, apoplexy, phlegm syncope, convulsive epilepsy, phlegm coma, pharyngitis, toothache, aphtha, carbuncle, and conjunctival congestion. Borneol has many effects in Chinese patent medicine preparation, such as improving bioavailability of other active ingredients in the preparation, promoting transdermal effect, recovering myocardial infarction dead zone blood flow, slowing down heart rate, reducing myocardial oxygen consumption, and strongly regulating central nerve excitability by borneol, and has effects of tranquilizing and allaying excitement, resisting inflammation, relieving pain, and resisting bacteria. The synthetic borneol can also be used for cosmetics and daily necessities such as ink sticks, ink meters, oral cavity cleaning agents, disinfectants and the like; can also be used for preparing oriental flavor. Such as borneol propionate, norbornane, norbornene and its derivatives, and can be used for producing bornyl sugar, borneol cake, etc.
At present, the industrial production of borneol is mainly an intermittent production process, namely an intermittent esterification-saponification process of alpha-pinene. For example, chinese patent CN102101824A discloses a catalytic esterification-saponification process of α -pinene, in which α -pinene, a titanium catalyst, and anhydrous oxalic acid are put into a reaction tank with a stirring device, a heating device, and a thermometer, heated to react, then filtered, the filtered liquid oxalic acid borneol ester is added into a reaction kettle for saponification, and the product is obtained by washing, steaming light oil, saponifying and steaming brain, crystallizing, spin-drying, and air-drying. Chinese patents CN101318880, CN101830779A and CN1153764 and the like also adopt batch esterification-saponification processes, and the main difference is that the used catalyst systems are different.
The prior process for preparing borneol from borneol oxalate has the following problems:
1. the saponification reaction process of the borneol oxalate ester is complex; the borneol oxalate ester is insoluble with liquid alkali and is not a homogeneous system, so that the contact surface of two substances is increased by high-temperature and mechanical stirring under the external action, the reaction speed is accelerated, the saponification temperature in the prior art is high and needs 90-110 ℃, the reaction time is long and needs 12-15 hours, after the saponification is finished, the temperature is increased to ensure that the borneol is vaporized and sublimated into a gas state, the gas state enters a cooling tank to be cooled into a solid crystal, and the solid crystal is taken out, washed and centrifuged to obtain the crude borneol crystal. The step has high energy consumption and low yield;
2. the flow of each production step is not compact, and the production efficiency is low; because the intermittent production is adopted, after the borneol oxalate reacts with liquid caustic soda to generate crude borneol in the prior art, the crude borneol is steamed out and enters a cooling box, the cooled crude borneol is integrated on the box wall in a solid state, and then the crude borneol is manually shoveled out of the cooling box, washed and centrifuged to obtain the crude borneol; the crude borneol is finally dissolved, crystallized and dried to obtain a borneol finished product, and the steps are required to be produced on different equipment, so that the steps are complicated, the connection of the production steps is not very compact, the non-production time is increased, and the production efficiency is low;
3. the automatic control is inconvenient, the manual operation is mainly relied on, and the control precision is poor besides the high labor intensity; particularly, when the borneol is taken out of the cooling box, personnel need to enter the cooling box, and the working environment is severe.
4. In the crystallization process, gasoline is used as a solvent, so that the crystallization process is volatile, high in danger, easy to cause safety accidents, high in pollution, not environment-friendly enough and extremely high in requirements on site environment.
5. The borneol crystallization period is long, the natural cooling method is adopted for crystallization at present, the primary crystallization generally needs 8-10 days, the borneol content is about 50%, if the higher content is required to be obtained, the secondary crystallization is required to obtain about 55% of borneol, and the production efficiency is low;
6. because the saponification reaction is incomplete, the impurities are higher, the borneol content is lower than 50-55%, and the quality is unstable.
Disclosure of Invention
The invention provides a method for preparing borneol from borneol oxalate, aiming at overcoming the defects of long saponification reaction time, large energy consumption, low yield, non-compact production flow, high labor intensity and the like in the prior art, and the invention adopts a new crystallization device, thus shortening the crystallization period and improving the production efficiency; the novel environment-friendly solvent is used instead, so that the production is pollution-free and environment-friendly, the safety is good, the product yield is improved, the generation of impurities is reduced, the product quality is stable, and the borneol content reaches more than 65%.
In order to solve the technical problems, the invention adopts the following technical scheme:
provides a method for preparing borneol from borneol oxalate, which at least comprises the following steps:
s1: placing the borneol oxalate, a catalyst and liquid caustic soda in a tubular reactor for saponification, controlling the reaction temperature to be 50-60 ℃, and oscillating back and forth by using an oscillating pump to complete the saponification; adding a p-menthane solvent into the tubular reactor, mixing with the reacted materials, and feeding into a crude product intermediate storage tank;
s2: taking out the materials from the crude product intermediate tank, placing the materials into a catalyst recovery kettle, heating and controlling the kettle temperature to be 55-80 ℃, vaporizing the catalyst, cooling the catalyst into a liquid state from the top of the first fractionating column through a condenser, finally extracting part of the catalyst into the intermediate tank, and returning the rest of the liquid catalyst into the first fractionating column;
s3, feeding the solution obtained after catalyst recovery from the catalyst recovery kettle into a water scrubber, adding washing water for mixing, and controlling the temperature of the water scrubber to be 50-60 ℃ to obtain an oil phase and a water phase; the oil phase 22 enters the crystallization kettle from an oil phase outlet, and the water phase is discharged;
s4: heating the oil phase to 140-170 ℃ after the oil phase enters a crystallization kettle, vaporizing the solvent, cooling the oil phase from the top of a second distillation column through a cooler to form a liquid solvent, allowing part of the liquid solvent to enter a solvent recovery tank, returning part of the liquid solvent to the second distillation column, and separating out crude borneol in the crystallization kettle;
s5: adding a p-menthane solvent into a crystallization kettle, heating to 80-90 ℃, stirring for 3-5 h, cooling to 7-10 ℃, and keeping for 50-70 h for crystallization.
S6: after crystallization, discharging the p-menthane solvent from a solvent outlet of the crystallization kettle; and discharging the borneol crystal from the crystallization kettle to a vacuum drier for drying, controlling the drying temperature to be 50-55 ℃, and drying for 3h to obtain a finished product.
In the steps, the catalyst is a phase transfer catalyst, and an alcohol catalyst is adopted, so that the alcohol catalyst is easy to recover and can be repeatedly used; the catalyst, the liquid caustic soda and the borneol oxalate are mutually soluble, so that the catalyst, the liquid caustic soda and the borneol oxalate are in a homogeneous system, the contact surface of reaction liquid is increased, the reaction conditions are reduced, the reaction is carried out under mild conditions, the energy consumption is reduced, and continuous production is realized.
The solvent adopts p-menthane as the solvent, the p-menthane has stable property, low flash point, difficult volatilization, easy storage and transportation, safety and environmental protection, the effect of dissolving borneol under certain conditions is better than that of gasoline, and the influence on production environment and conditions is less.
Wherein, the tubular reactor is cylindrical, the length is 15000 mm-20000 mm, and the diameter is 300 mm-500 mm; the tubular reactor both ends are equipped with material import and material export respectively, and are equipped with buffer baffle in the tubular reactor, increase material dwell time, can guarantee that the material fully reacts, and the outside is equipped with the jacketed pipe, be equipped with hot water import and hot water export on the jacketed pipe respectively, use the thermal cycle water to carry out the reaction heating, guarantee that the reaction goes on under the constant temperature.
In step S1, preheating the borneol oxalate, the catalyst and the liquid caustic soda by a preheater, mixing in a static mixer, and placing in a tubular reactor for saponification; the preheater is a spiral plate preheater with a heat exchange area of 50m2. The static mixer has the advantages of simple structure, low energy consumption, simple and convenient installation and maintenance, good mixing performance and continuous operation.
Wherein, three crystallization plates are arranged in the crystallization kettle, each crystallization plate is cylindrical, and holes with the diameter of 10-12 mm are uniformly distributed on the crystallization plates, mainly for easily promoting the sheet formation of borneol crystals; and a scraping blade is arranged between the crystallization plates, the distance between the scraping blade and the crystallization plates is 20mm, and mainly after crystals are formed, the formed flaky borneol crystals begin to be scraped off to prevent the crystals from being stirred and crushed; the crystallization kettle is also internally provided with a nitrogen pipe, the nitrogen pipe extends out of the crystallization kettle through a nitrogen port, and the nitrogen pipe is mainly used for blowing the large-particle crystals attached to the kettle wall and the crystallization plate to a feed port during feeding; a jacket is arranged outside the crystallization kettle for heating and cooling; a fractionating column is arranged on the crystallization kettle, the theoretical stage number of the fractionating column is 10-15, and the fractionating column is externally connected with a condenser and a receiving tank to separate out the solvent; the bottom of crystallization kettle is equipped with drain hole and oil drain port, the external filter of drain hole prevents that the crystal from getting into in the solvent.
The catalyst recovery kettle is heated by an external half pipe, a fractionating column is arranged on the catalyst recovery kettle, the theoretical stage number of the fractionating column is 8-12, and a condenser and a receiving tank are externally connected with the fractionating column to separate out the solvent.
Wherein, the water scrubber is dumbbell-shaped and comprises an upper end container, a middle feeding end and a lower end container, wherein the volumes of the upper end container and the lower end container are both 6m3Connected by a mixing layer, the mixing layer is provided with an ultrasonic mixer; an oil phase outlet is arranged in the upper end container, a water phase outlet is arranged in the lower end container, and the height difference between the oil phase outlet and the water phase outlet is 300-600 mm; the lower end container is provided with a heating pipe; the middle feeding end is also provided with an ultrasonic oscillator, so that the materials are washed more fully.
Wherein, in the saponification reaction, the mass ratio of the borneol oxalate, the liquid alkali, the catalyst and the p-menthane solvent is 1 (0.15-0.3) to 0.04-0.1): (0.3-0.5).
In step S5, the mass ratio of the crude borneol to the p-menthane solvent is 1 (0.5-0.8).
In the catalyst recovery step, the temperature of a recovery kettle is controlled to be 55-80 ℃, and the reflux ratio is controlled to be 3-5.
In the solvent recovery step, the kettle temperature is controlled to be 140-170 ℃, and the reflux ratio is controlled to be 4-6.
In the crystallization step, the crystallization temperature is controlled to be 7-10 ℃, and the temperature is kept for 50-70 h.
Different from the prior art, the invention at least has the following beneficial effects:
1. the phase transfer catalyst and the p-menthane solvent are added in the saponification reaction, so that the borneol oxalate and the liquid alkali can react in a homogeneous phase, the reaction time is shortened, the reaction temperature is reduced, the efficiency is improved, and the energy consumption is reduced;
2. the saponification reaction is continuously carried out in the tubular reactor, so that the rapid and uniform reaction can be ensured to be complete;
3. p-menthane is used as an organic solvent to dissolve crude borneol, and the main effect is to dissolve the borneol and facilitate conveying by a pump to prevent pipeline blockage; secondly, the borneol is recrystallized to remove impurities contained in the crystals, the quality of a final product is improved, and the menthane is safe, environment-friendly and nontoxic, and the dissolving effect is better than that of gasoline;
4. a continuous water washing automatic layering device is adopted to ensure that the materials are fully washed and the oil phase and the water phase are completely separated;
5. adopt novel crystallization device, shorten crystallization time, reduce intensity of labour, crystallization effect is good, impurity is few, stable in quality.
Drawings
FIG. 1 is a schematic flow chart of the apparatus for preparing borneol from borneol oxalate according to the present invention;
FIG. 2 is a schematic view of the structure of the tubular reactor of FIG. 1;
FIG. 3 is a schematic structural view of the crystallization kettle in FIG. 1;
FIG. 4 is a schematic structural view of the water scrubber of FIG. 1.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
As shown in fig. 1 to fig. 4, this embodiment is a method for preparing borneol from borneol oxalate, which at least includes the following steps:
1. saponification reaction: the preparation method comprises the steps of enabling the borneol oxalate, the catalyst and the liquid caustic soda to pass through a preheater 4 and a static mixer 5 respectively through conveying pumps 1, 2 and 3, enabling a mixed solution 6 to enter a tubular reactor 8 for reaction, controlling the reaction temperature to be 50-60 ℃, enabling a vibration pump 7 to vibrate materials back and forth, after saponification is completed, enabling a solvent to be pumped into the reactor from the rear end of the reactor through a conveying pump 9 to be mixed with the reacted materials, and enabling qualified materials 10 to enter a crude product intermediate storage tank 11.
2. Catalyst recovery: feeding the material 12 in the crude product intermediate tank into a catalyst recovery kettle 13, controlling the kettle temperature at 55-80 ℃, cooling the gaseous catalyst from the top of the fractionating column into a liquid state by a condenser 14, extracting a part of the liquid catalyst 15 into a catalyst intermediate tank 16, and returning a part of the liquid catalyst to the fractionating column; the remaining solution in the kettle after the catalyst is separated is ready for water washing.
3. Washing with water: the solution 17 after the catalyst recovery passes through a delivery pump 18, the solvent enters a homogenizing mixing pump 20 together from a delivery pump 19, the mixture is mixed and enters a water scrubber 21, and the temperature of the water scrubber is kept at 50-60 ℃. And (3) feeding the water-washed oil phase 22 into a solvent recovery kettle from an oil phase outlet, and discharging the water-washed water phase 23.
4. And (3) solvent recovery: and (3) feeding the oil phase 22 after water washing into a solvent recovery kettle 25, heating to 140-170 ℃, cooling the gaseous solvent from the top of the fractionating column into liquid by a cooler 27, feeding a part of the liquid solvent 28 into a solvent recovery tank 29, and returning a part of the solvent to the fractionating column.
5. Dissolving and crystallizing: adding a fresh p-menthane solvent 24 into a crystallization kettle, heating to 80-90 ℃, stirring for 3-5 h, cooling to 7-10 ℃, and keeping for 50-70 h.
6. And (3) drying the crystal: after crystallization, discharging the solvent 26 from the solvent outlet for the next batch; and discharging the borneol crystal 30 from the crystallization kettle to a vacuum drier 31 for drying at the drying temperature of 50-55 ℃ for 3h to obtain a finished product, wherein the content of the finished product is 65-75%.
In the steps, the catalyst is a phase transfer catalyst, and an alcohol catalyst is adopted, so that the alcohol catalyst is easy to recover and can be repeatedly used; the catalyst, the liquid caustic soda and the borneol oxalate are mutually soluble, so that the catalyst, the liquid caustic soda and the borneol oxalate are in a homogeneous system, the contact surface of reaction liquid is increased, the reaction conditions are reduced, the reaction is carried out under mild conditions, the energy consumption is reduced, and continuous production is realized.
The solvent adopts p-menthane as the solvent, the p-menthane has stable property, low flash point, difficult volatilization, easy storage and transportation, safety and environmental protection, the effect of dissolving borneol under certain conditions is better than that of gasoline, and the influence on production environment and conditions is less.
Wherein, the tubular reactor 100 is cylindrical, the length is 15000 mm-20000 mm, and the diameter is 300 mm-500 mm; the tubular reactor 100 is provided with a material inlet 110 and a material outlet 120 at two ends respectively, a solvent inlet 130 is arranged on the wall of the intermediate container, a buffer baffle 140 is arranged in the tubular reactor 100 to increase the retention time of the material and ensure the sufficient reaction of the material, a jacketed pipe 150 is arranged outside the tubular reactor, a hot water inlet 160 and a hot water outlet 170 are arranged on the jacketed pipe 150 respectively, and the tubular reactor is heated by using hot circulating water to perform reaction, so that the reaction is ensured to be performed at constant temperature.
In step S1, preheating the borneol oxalate, the catalyst and the liquid caustic soda by a preheater, mixing in a static mixer, and placing in a tubular reactor for saponification; the preheater is a spiral plate preheater with a heat exchange area of 50m2. The static mixer has the advantages of simple structure, low energy consumption, simple and convenient installation and maintenance, good mixing performance and continuous operation.
Wherein, three crystallization plates 210 are arranged in the crystallization kettle 200, each crystallization plate 210 is cylindrical, and holes with the diameter of 10-12 mm are uniformly distributed on the crystallization plates 210, mainly for easily promoting the sheet formation of borneol crystals; a scraping blade 220 is arranged between the crystallization plates 210, the distance between the scraping blade 220 and the crystallization plates 210 is 20mm, and mainly after crystals are formed, the formed flaky borneol crystals are scraped off to prevent the crystals from being stirred and smashed; a nitrogen pipe is also arranged in the crystallization kettle 200, the nitrogen pipe extends out of the crystallization kettle 200 through a nitrogen port 230, and the nitrogen pipe is mainly used for blowing the large-particle crystals attached to the kettle wall and the crystallization plate to a feed opening during discharging; a jacket 240 is arranged outside the crystallization kettle 200 for heating and cooling; the crystallization kettle 200 is provided with a fractionating column 250, the theoretical stage number of the fractionating column 250 is 10-15, and the fractionating column 250 is externally connected with a condenser and a receiving tank to separate out the solvent; the bottom of crystallization kettle 200 is equipped with drain 260 and oil drain 270, the external filter of drain 260 prevents in the crystal entering solvent.
The catalyst recovery kettle is heated by an external half pipe, a fractionating column is arranged on the catalyst recovery kettle, the theoretical stage number of the fractionating column is 8-12, and a condenser and a receiving tank are externally connected with the fractionating column to separate out the solvent.
Wherein, the water scrubber 300 is dumbbell-shaped and comprises an upper end container 310, a middle feeding end 320 and a lower end container 330, wherein the volumes of the upper end container 310 and the lower end container 330 are both 6m3Connected by a mixing layer, the mixing layer is provided with an ultrasonic mixer; an oil phase outlet 311 is arranged in the upper end container 310, a water phase outlet 331 is arranged in the lower end container 330, and the height difference between the oil phase outlet 311 and the water phase outlet 331 is 300-600 mm; the lower container 330 is provided with a heating pipe 332; the middle feed end 320 is also provided with an ultrasonic oscillator 321, so that the materials are washed more fully.
Wherein, in the saponification reaction, the mass ratio of the borneol oxalate, the liquid alkali, the catalyst and the p-menthane solvent is 1 (0.15-0.3) to 0.04-0.1): (0.3-0.5).
In step S5, the mass ratio of the crude borneol to the p-menthane solvent is 1 (0.5-0.8).
In the catalyst recovery step, the temperature of a recovery kettle is controlled to be 55-80 ℃, and the reflux ratio is controlled to be 3-5.
In the solvent recovery step, the kettle temperature is controlled to be 140-170 ℃, and the reflux ratio is controlled to be 4-6.
In the crystallization step, the crystallization temperature is controlled to be 7-10 ℃, and the temperature is kept for 50-70 h.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.

Claims (7)

1. The method for preparing borneol from borneol oxalate is characterized by at least comprising the following steps:
s1: placing the borneol oxalate, a catalyst and liquid caustic soda in a tubular reactor for saponification, controlling the reaction temperature to be 50-60 ℃, and oscillating back and forth by using an oscillating pump to complete the saponification; adding a p-menthane solvent into the tubular reactor, mixing with the reacted materials, and feeding into a crude product intermediate storage tank;
s2: taking out the materials from the crude product intermediate tank, placing the materials into a catalyst recovery kettle, heating and controlling the kettle temperature to be 55-80 ℃, vaporizing the catalyst, cooling the catalyst into a liquid state from the top of the first fractionating column through a condenser, finally extracting part of the catalyst into the intermediate tank, and returning the rest of the catalyst into the first fractionating column;
s3: the solution after catalyst recovery enters a water scrubber from a catalyst recovery kettle, washing water is added for mixing, and the temperature of the water scrubber is controlled to be 50-60 ℃ to obtain an oil phase and a water phase; the oil phase 22 enters the crystallization kettle from an oil phase outlet, and the water phase is discharged;
s4: heating the oil phase to 140-170 ℃ after the oil phase enters a crystallization kettle, vaporizing the solvent, cooling the oil phase from the top of a second distillation column through a cooler to form a liquid solvent, allowing part of the liquid solvent to enter a solvent recovery tank, returning part of the liquid solvent to the second distillation column, and separating out crude borneol in the crystallization kettle;
s5: adding a p-menthane solvent into a crystallization kettle, heating to 80-90 ℃, stirring for 3-5 h, cooling to 7-10 ℃, and keeping for 50-70 h for crystallization;
three crystallization plates are arranged in the crystallization kettle, each crystallization plate is cylindrical, and holes with the diameter of 10-12 mm are uniformly distributed on each crystallization plate; a scraping blade is arranged between the crystallization plates, and the distance between the scraping blade and the crystallization plates is 20 mm; the crystallization kettle is also internally provided with a nitrogen pipe, and the nitrogen pipe extends out of the crystallization kettle through a nitrogen port; a jacket is arranged outside the crystallization kettle; a fractionating column is arranged on the crystallization kettle, and the theoretical stage number of the fractionating column is 10-15; the bottom of the crystallization kettle is provided with a discharge hole and an oil discharge hole, and the discharge hole is externally connected with a filter;
s6: after crystallization, discharging the p-menthane solvent from a solvent outlet of the crystallization kettle; and discharging the borneol crystal from the crystallization kettle to a vacuum drier for drying, controlling the drying temperature to be 50-55 ℃, and drying for 3h to obtain a finished product.
2. The method for preparing borneol from borneol oxalate as claimed in claim 1, wherein the tubular reactor is cylindrical, has a length of 15000mm to 20000mm and a diameter of 300mm to 500 mm; the tubular reactor both ends are equipped with material import and material export respectively, and are equipped with buffer baffle in the tubular reactor, and the outside is equipped with double-layered sleeve pipe, be equipped with hot water import and hot water export on the double-layered sleeve pipe respectively.
3. The method for preparing borneol from borneol oxalate as claimed in claim 1, wherein in step S1, after preheating the borneol oxalate, the catalyst and the liquid caustic soda by a preheater, the mixture enters a static mixer for mixing, and then is placed in a tubular reactor for saponification; the preheater is a spiral plate preheater with a heat exchange area of 50m2。
4. The method for preparing borneol from borneol oxalate as claimed in claim 1, wherein the catalyst recovery kettle is heated by an external half-pipe, the catalyst recovery kettle is provided with a fractionating column, the theoretical stage number of the fractionating column is 8-12, and the fractionating column is externally connected with a condenser and a receiving tank.
5. The method for preparing borneol from borneol oxalate according to claim 1, wherein the water washer is in a dumbbell shape and comprises an upper container, a middle feeding end and a lower container, wherein the volumes of the upper container and the lower container are all 6m in year and are connected by a mixing layer, and the mixing layer is provided with an ultrasonic mixer; an oil phase outlet is arranged in the upper end container, a water phase outlet is arranged in the lower end container, and the height difference between the oil phase outlet and the water phase outlet is 300-600 mm; the lower end container is provided with a heating pipe; the middle feed end is also provided with an ultrasonic oscillator.
6. The method for preparing borneol from borneol oxalate as claimed in claim 1, wherein the mass ratio of the borneol oxalate to the liquid alkali to the catalyst to the p-menthane solvent is 1 (0.15-0.3) to (0.04-0.1): (0.3-0.5).
7. The method for preparing borneol from borneol oxalate as claimed in claim 1, wherein in step S5, the mass ratio of crude borneol to p-menthane solvent is 1 (0.5-0.8).
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