CN105237369B - A kind of method of isoborneol dehydrogenation Gum Camphor and equipment thereof - Google Patents
A kind of method of isoborneol dehydrogenation Gum Camphor and equipment thereof Download PDFInfo
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- CN105237369B CN105237369B CN201510714006.XA CN201510714006A CN105237369B CN 105237369 B CN105237369 B CN 105237369B CN 201510714006 A CN201510714006 A CN 201510714006A CN 105237369 B CN105237369 B CN 105237369B
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- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
A kind of method that the present invention relates to isoborneol dehydrogenation Gum Camphor, includes dehydrogenation reaction successively and collects step with solvent recovery step, Camphora vaporization sublimation step and Camphora distillation；Described dehydrogenation reaction and solvent recovery step are to send in reactor by isoborneol with the mixed solution of isoborneol dissolution solvent, dehydrogenation, it is heated realizing dehydrogenation reaction to reactor, utilize the hydrogen that dehydrogenation reaction is generated by dephlegmator to discharge, and isoborneol dissolution solvent is reclaimed。This invention overcomes dehydrogenation reaction in existing isoborneol dehydrogenation Gum Camphor technique, solvent recovery and vaporization sublimation step to be needed sequentially to produce in different equipment, it is capable of the integration of dehydrogenation reaction still, solvent recovery unit and sublimation apparatus, dehydrogenation reaction, solvent recovery and vaporization sublimation step can be carried out in same reactor, there is saving operation, the advantage being substantially reduced manpower and equipment cost。
Description
Technical field
The present invention relates to a kind of method of isoborneol dehydrogenation Gum Camphor and equipment thereof, be applied in the production of Camphora。
Background technology
Artificial camphor is also known as camphanone, molecular formula C10H18O, is a kind of white crystal, has refrigerant refreshing abnormal smells from the patient, be soluble in organic solvent, easily distil。Artificial camphor purposes is relatively wide, specifically includes that (1) is directly medicinal, can enter traumatic injury, invigorate blood circulation external-applied ointment and medicinal oil (water) preparation, it is possible to enter the oral Chinese patent medicine preparation etc. of expelling summer-heat refreshment digestion promoting function；(2) pharmaceutical intermediate, for producing medicine intermediate camphorsulfonic acid and the phenylglycine of central nervous excitation agent；(3) raw material of industry, can be used as such as celluloid, plasticizer, cordite, nitrocellulose, preservative etc.；(4) domestic camphor goods raw material, as the antitermite agent of medicated clothing, woollen, books, file, archives etc.；(5) spice, is applied to the perfuming of daily chemical essence formula and household chemicals and industrial goods；(6) incense, religion week are used。Camphora is again the primary raw material producing campholenic nitrile, campholenates, bromo-camphor, camphor spirit and sodium camphorsulfonate。
Artificial camphor is usually and produces under the effect of dehydrogenation for raw material with isoborneol, and its product includes a small amount of unreacted isoborneol, and by-product is Borneolum Syntheticum and fenchone, it is necessary to carries out purifying and just can obtain satisfactory Camphora。Traditional dehydrogenation and method of purification are to add Calx and the basic copper carbonate as dehydrogenation in reactor, if application number is the patent of invention of 90107669.4, with dimethylbenzene for solvent, at high temperature carry out dehydrogenation, after dehydrogenation completely, enter solvent recovery tower reclaim out dimethylbenzene, carry out sublimation purification subsequently into distillation still, finally enter sublimation chamber and collect the Camphora after purifying。Adopting dimethylbenzene as solvent in traditional handicraft, in the readily volatilized entrance air of dimethylbenzene, environmental pollution is bigger；Basic copper carbonate can not reclaim use, and the basic copper carbonate decomposition generation copper oxide as dehydrogenation needs periodic exhaustion to process, and processing cost is higher；Need independent solvent recovery unit and sublimation apparatus input cost high；What distillation collection process adopted is natural cooling crystallization method。There is temperature shortcoming rambunctious in the method, causes that loss of material is serious, and yield is low, unstable product quality, and the production cycle is long。After additionally collecting, product Camphora need to be manually entered sublimation chamber shovel brain, and production efficiency is low。Therefore provide method and the equipment thereof of a kind of novel isoborneol dehydrogenation Gum Camphor, it is possible to realize environmental protection, low cost, carry out the production of Camphora expeditiously, and refining obtain the high product of good stability, content oneself become when business urgently。
Summary of the invention
The present invention provides method and the equipment thereof of a kind of isoborneol dehydrogenation Gum Camphor, which overcome dehydrogenation reaction in existing isoborneol dehydrogenation Gum Camphor technique, solvent recovery and vaporization sublimation step to need sequentially to produce in different equipment, it is capable of the integration of dehydrogenation reaction still, solvent recovery unit and sublimation apparatus, dehydrogenation reaction, solvent recovery and vaporization sublimation step can be carried out in same reactor, there is saving operation, be substantially reduced manpower and equipment cost advantage。
Technical scheme is as follows:
A kind of method of isoborneol dehydrogenation Gum Camphor, includes dehydrogenation reaction successively and collects step with solvent recovery step, Camphora vaporization sublimation step and Camphora distillation；
Described dehydrogenation reaction and solvent recovery step are to send in reactor by isoborneol with the mixed solution of isoborneol dissolution solvent, dehydrogenation, it is heated realizing dehydrogenation reaction to reactor, the hydrogen that dehydrogenation reaction is generated by dephlegmator is utilized to discharge, and isoborneol dissolution solvent is reclaimed, for recycling；
Described Camphora vaporization sublimation step is, by vaporizing column, remaining material after completing dehydrogenation reaction and solution recycling step in reactor is further heated up heating, making Camphora vaporization distillation, the Camphora that vaporization distils is collected still by vaporizing column feeding distillation and is carried out Camphora distillation collection step；Vaporizing column, with heating jacket, has conduction oil to be heated in chuck, make the material of entrance vaporizing column to cool down。
It is that vaporized by Camphora vaporize in the sublimation step Camphora of distillation is sent into distillation and collected still and be collected that step is collected in the distillation of described Camphora。
In existing isoborneol dehydrogenation Gum Camphor technique, dehydrogenation reaction, solvent recovery and vaporization sublimation step need separately performed, and dehydrogenation reaction, solvent recovery and vaporization sublimation step are concentrated on and carry out in a reactor by the technique after improving in the application, the recycling that solvent can be carried out while carrying out dehydrogenation reaction by arranging dephlegmator to achieve。Isoborneol dissolution solvent returns to storage tank by a delivery pump part after being gathered by dephlegmator, and another part is returned in reactor to utilize。After dehydrogenation reaction, by the vaporizing column on reactor, Camphora is vaporized distillation so that it is enter in distillation collection still and be collected。The method of the isoborneol dehydrogenation Gum Camphor of the application is saved greatly operation, provide not only production efficiency, has been greatly reduced production cost。
Described dehydrogenation reaction is with solvent recovery step, and dehydrogenation is palladium-carbon catalyst；The mass ratio that isoborneol uses with palladium-carbon catalyst is 1:0.02-0.04。
Dehydrogenation in existing isoborneol dehydrogenation Gum Camphor technique uses basic copper carbonate, and it can not reclaim use, and basic copper carbonate decomposes generation copper oxide and needs periodic exhaustion to process, and processing cost is higher。Used in this application is palladium-carbon catalyst, and this catalyst can recycle, and reduces dehydrogenation reaction temperature, and energy consumption is low, and decreases the generation of impurity, improves reaction yield and shortens the response time, therefore the more existing technique of this technique is advanced。The consumption of this dehydrogenation is best, not only will not waste, also can guarantee that the sufficiently conducted of reaction。
Described isoborneol dissolution solvent is paracymene。
What the solvent in existing isoborneol dehydrogenation Gum Camphor technique adopted is dimethylbenzene, and in its readily volatilized entrance air, environmental pollution is bigger。Now use paracymene as solvent, substitute dimethylbenzene, more environmental protection。The Main Function of paracymene solvent is to dissolve isoborneol to be easy to prevent line clogging with transport pump；Next to that make the impurity that isoborneol recrystallization is included in crystal with removing, improve the quality of final products。
Described dehydrogenation reaction is with solution recycling step, and temperature controls between 160-185 DEG C；In described Camphora vaporization sublimation step, temperature controls between 190-220 DEG C。This isoborneol coordinates the dehydrogenation reaction that this dehydrogenation reaction temperature can make isoborneol more complete with the proportioning of palladium-carbon catalyst。This solvent recovery temperature organic efficiency is higher。
The distillation of described Camphora is collected in step, collects in still to distillation and is continually fed into nitrogen, so that Camphora settles rapidly crystallization while pass into the Camphora of vaporization distillation to distillation collection still；Camphora distillation is collected the temperature of step and is controlled between 50-80 DEG C。
The method also includes spray and collects step, after spray collection step is positioned at Camphora distillation collection step, it is Camphora distillation collected in step the material not settled and send into spray column that described spray collects step, and is continually fed into shower water in spray column and sprays, to collect Camphora further。After step is collected in Camphora distillation, design spray collects step, the Camphora in the material not settled can be made to be recycled, improve the yield of Camphora。
A kind of equipment of the method utilizing above-mentioned isoborneol dehydrogenation Gum Camphor, this equipment includes the interconnective reactor for carrying out dehydrogenation reaction and solvent recovery step and Camphora vaporization sublimation step and collects the distillation collection still of step for carrying out Camphora distillation, described reactor is connected to the heater that can be used for regulating temperature in the kettle, described reactor is provided with hydrogen for dehydrogenation reaction being generated and discharges and isoborneol dissolution solvent carries out the dephlegmator reclaimed, and described reactor is additionally provided with for vaporizing flower Of camphor be sent to the vaporizing column of reactor。
Dehydrogenation reaction, solution recovery and Camphora vaporization distillation are concentrated in a reactor and carry out by this equipment, drastically increase production efficiency and have saved cost。
This heater is circulating heater, and it includes the falling-film reboiler and the circulating pump that arrange on pipeline that both ends are connected on reactor and this pipeline。
Dehydrogenation reaction is the endothermic reaction, and circulating heater does not stop heat supply can to reactor, to ensure the carrying out of dehydrogenation reaction。Falling-film reboiler is compared with common reboiler, and the material viscosity of its process can more greatly, and its thermal sensitivity is strong, and the thermal efficiency is relatively big, is beneficial to the carrying out of dehydrogenation reaction。
This equipment also includes spray column, and it is collected still with distillation and is connected, and is used for carrying out spray and collects step。After Camphora distillation collection, increase spray collect, it is possible to make not drop Camphora in heavy logistics partly and be recycled, improve Camphora yield。
Dephlegmator is dephlegmator theoretical stage is the dephlegmator of 8-13 level, the medial wall of vaporizing column is connected to the two aerofluxus body impingement baffles that equi-spaced apart is staggered and is oppositely arranged, being additionally provided with the surge tank on the hydrogen discharge passage being arranged at dephlegmator on reactor, the hydrogen that dehydrogenation reaction produces is by discharging reactor after surge tank；Distillation is collected and is provided with, on the whole central shaft of still, the some squeegee devices extended by central axial still wall direction, and this squeegee devices is the scraper of thickness 4-6mm, and the spacing distance of scraper and still wall is 0.5-1.5cm。
Distillation is collected in still can realize machine automatization spatula Camphora with squeegee devices, has saved manpower。This squeegee devices is the scraper of thickness 5mm, and the spacing distance of scraper and still wall is 1cm。Scraping effect under this state is best。The setting of surge tank effectively prevent liquid bumping in reactor and overflows。Vaporizing column is mainly Camphora gas and collects an interface channel of still to distillation, arranges preventing gas punching, it is possible to effectively prevents the liquid Camphora but without vaporization from collecting still directly into distillation, causes that Camphora product turns yellow defective。
Compared with prior art, the present patent application has the advantage that
1) the method adopt efficiently, economy, environmental protection technique carry out sintetics, and refining obtain good stability, product that content is high；
2) palladium-carbon catalyst is adopted to substitute the basic copper carbonate of current industrial use as dehydrogenation in isoborneol dehydrogenation Gum Camphor technique, it is possible not only to recycle, and can so that dehydrogenation reaction temperature reduces, energy consumption is low, reduce the generation of impurity, improve reaction yield, shorten the response time；
3) use paracymene instead as solvent, decrease environmental pollution, environmental protection；
4) Camphora distillation is collected and is continually fed into nitrogen mixing in step, is beneficial to Camphora and settles rapidly crystallization, shortens crystallization time；
5) what existing sublimation process adopted is natural cooling crystallization, there is temperature shortcoming rambunctious, it is easy to causing that loss of material is serious, yield is low, unstable product quality, and the production cycle is long。This application increases spray after distillation is collected and collects, and can fully collect the Camphora not dropped in heavy material, improve Camphora yield；
6) dehydrogenation reaction, solvent recovery, Camphora vaporization distillation all carry out in same reactor, and flow process is compact, shorten the production cycle；
7) circulating heater adopts falling-film reboiler, uses wider, is beneficial to reaction and carries out；
8) distillation collection device adopts reactor form to collect, and with squeegee devices, easy control of temperature, it is possible to continuous operation discharging, stable and reliable product quality, reduce labor intensity；
9) use of surge tank and the vaporizing column with preventing gas punching on reactor, it is ensured that the safety of production carries out, also ensure that the stabilised quality of product simultaneously。
Camphora obtained by the method for this isoborneol dehydrogenation Gum Camphor and equipment thereof, its purity >=97%。
Accompanying drawing explanation
Fig. 1 is the equipment schematic diagram of a kind of isoborneol dehydrogenation Gum Camphor of the present invention；
Fig. 2 is the structure sectional view of a kind of isoborneol dehydrogenation Gum Camphor dephlegmator of the present invention；
Fig. 3 is the structure sectional view of a kind of isoborneol dehydrogenation Gum Camphor vaporizing column of the present invention；
Fig. 4 is the top view of a kind of isoborneol dehydrogenation Gum Camphor vaporizing column of the present invention；
Fig. 5 is the structure sectional view of a kind of isoborneol dehydrogenation Gum Camphor surge tank of the present invention。
Label declaration:
The mixed solution of 1-1 isoborneol and isoborneol dissolution solvent, 1-2 dehydrogenation, 1-3 hydrogen, 1-4 Camphora, 1-5 nitrogen, the material that 1-6 does not settle, 1-7 shower water, 1-8 remains the material that can not settle, 2 reactors, 21 dephlegmators, 211 filler fixed disks, 212 ripple packings, 213 material receptors, 214 coolant outlets, 215 cooling water inlets, 216 material outlets, 217 material inlets, 218 material mouths, 219 hydrogen outlets, 22 vaporizing columns, 221 preventing gas punchings, 222 conduction oil interlayers, 223 conduction oil outlets, 224 heat conductive oil inlets, 23 surge tanks, 231 gas outlets, 232 air inlets, 233 sewage draining exits, still is collected in 3 distillations, 31 squeegee devices, 32 nitrogen input channels, 33 Camphora input channels, 34 material output channels, discharge port it is provided with bottom 35, 36 cooling water sandwich, 37 coolant outlets, 38 cooling water inlets, 4 spray columns, 5 heaters, 51 pipelines, 52 falling-film reboilers, 53 circulating pumps, 6 fluid reservoirs。
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is described in detail。
A kind of method of isoborneol dehydrogenation Gum Camphor, includes dehydrogenation reaction successively and collects step with solvent recovery step, Camphora vaporization sublimation step and Camphora distillation；
Described dehydrogenation reaction and solvent recovery step are to send in reactor 2 by isoborneol with the mixed solution 1-1 of paracymene, palladium-carbon catalyst 1-2, and the mass ratio that isoborneol uses with palladium-carbon catalyst is 1:0.02-0.04。It is heated realizing dehydrogenation reaction to reactor 2, temperature is controlled between 160-185 DEG C, utilize the hydrogen 1-3 that dehydrogenation reaction is generated by dephlegmator 21 to discharge, and isoborneol dissolution solvent is reclaimed；
Described Camphora vaporization sublimation step is remaining material after completing dehydrogenation reaction and solution recycling step in reactor 1 to further heat up heating between 190-220 DEG C by vaporizing column 22, making Camphora 1-4 vaporization distillation, the Camphora 1-4 of vaporization distillation collects, by vaporizing column 22 and distillation, the Camphora input channel arranged on still 3 and sends into distillation and collect still 3 and carry out Camphora distillation and collect step；
It is vaporize Camphora to be collected the nitrogen input channel being provided with on still 3 in sublimation step while collecting still 3 to distillation and pass into the Camphora of vaporization distillation by distilling and collect in still 3 to distillation and be continually fed into nitrogen 1-5 that step is collected in the distillation of described Camphora, making Camphora 1-4 settle rapidly crystallization, distillation is collected still temperature and is controlled between 50-80 DEG C。
The method also includes spray and collects step, after spray collection step is positioned at Camphora distillation collection step, it is that the material 1-6 not settled in Camphora distillation collection step is collected the material input channel feeding spray column 4 arranged on the material output channel and spray column 4 that arrange on still 3 through distillation that described spray collects step, and the shower water input channel passing through to arrange on spray column 4 is continually fed into shower water 1-7 in spray column and sprays, to collect Camphora 1-4 further。The material 1-8 that residue can not settle directly gets rid of spray column 4 by the material output channel arranged on spray column 4。
A kind of equipment of the method using above-mentioned isoborneol dehydrogenation Gum Camphor, it includes the interconnective reactor 2 for carrying out dehydrogenation reaction and solvent recovery step and Camphora vaporization sublimation step and collects the distillation collection still 3 of step for carrying out Camphora distillation, described reactor 2 is connected to the heater 5 that can be used for regulating temperature in the kettle, and described reactor 2 is provided with the hydrogen 1-3 for dehydrogenation reaction being generated and discharges and isoborneol dissolution solvent carries out the dephlegmator 21 reclaimed。This dephlegmator 21 is column structure, is filler fixed disk 211 bottom it, and under-filled within dephlegmator has ripple packing 212, and its internal top is provided with material receptor 213。Being provided with coolant outlet 214, cooling water inlet 215, material outlet 216, material inlet 217 on the lateral wall on dephlegmator top from top to bottom, dephlegmator top is provided with material mouth 218 and hydrogen outlet 219。The hydrogen carrying out dehydrogenation reaction generation in reactor 2 is discharged outside still by gas outlet 218。Material mouth 218 is for adding isoborneol dissolution solvent to reactor 2, when carrying out dehydrogenation reaction in reactor 2, isoborneol dissolution solvent by after the ripple packing 212 of dephlegmator, is recycled to fluid reservoir 6 through material outlet 216, and is re-entered by material inlet 217 and carry out reuse in reactor 2。Described reactor 2 is additionally provided with for vaporizing flower Of camphor be sent to the vaporizing column 22 of reactor 2。This vaporizing column 22 is cylindricality, and its sidewall is provided with the conduction oil interlayer 222 for depositing conduction oil。The top of this conduction oil interlayer 222 sidewall is provided with conduction oil outlet 223, and the bottom of its sidewall is provided with heat conductive oil inlet 224, is circulated heat supply by being continually fed into conduction oil, it is achieved the vaporization distillation of Camphora。
Described heater 5 is circulating heater, and it includes the falling-film reboiler 52 and the circulating pump 53 that arrange on pipeline 51 that both ends are connected on reactor 2 and this pipeline 51。Distillation is collected still 3 top and is provided with Camphora input channel 33, nitrogen input channel 32 and material output channel 34, and bottom is provided with discharge port 35。Distillation is collected still 3 sidewall and is provided with cooling water sandwich 36, and the side wall upper part of cooling water sandwich is provided with coolant outlet 37, and its lower sidewall is provided with cooling water inlet 38。This equipment also includes spray column 4, and it is collected still 3 with distillation and is connected, and is used for carrying out spray and collects step。Spray column 4 is provided with material input channel, shower water input channel and material output channel。Dephlegmator 21 is the dephlegmator that dephlegmator theoretical stage is 8-13 level, and the medial wall of vaporizing column 22 is connected to the two aerofluxus body impingement baffles 221 that equi-spaced apart is staggered and is oppositely arranged。Reactor 2 is additionally provided with the surge tank 23 on the hydrogen 1-3 discharge-channel being arranged at dephlegmator 21。The top of surge tank 23 is provided with gas outlet 231 and air inlet 232, and bottom is provided with sewage draining exit 233。Distillation is collected and is provided with, on the whole central shaft of still 3, the some squeegee devices 31 extended by central axial still wall direction。This squeegee devices is the scraper of thickness 4-6mm, and the spacing distance of scraper and still wall is 0.5-1.5cm。
Embodiment 1
A kind of method of isoborneol dehydrogenation Gum Camphor, includes dehydrogenation reaction successively and collects step with solvent recovery step, Camphora vaporization sublimation step and Camphora distillation；
Described dehydrogenation reaction and solvent recovery step are to send in reactor 2 by isoborneol with the mixed solution 1-1 of paracymene, palladium-carbon catalyst 1-2, and the mass ratio that isoborneol uses with palladium-carbon catalyst is 1:0.02。It is heated realizing dehydrogenation reaction to reactor 2, temperature is controlled between 185 DEG C, utilize the hydrogen 1-3 that dehydrogenation reaction is generated by dephlegmator 21 to discharge, and isoborneol dissolution solvent is reclaimed；
Described Camphora vaporization sublimation step is remaining material after completing dehydrogenation reaction and solution recycling step in reactor 1 to further heat up heating between 190 DEG C by vaporizing column 22, making Camphora 1-4 vaporization distillation, the Camphora 1-4 of vaporization distillation collects, by vaporizing column 22 and distillation, the Camphora input channel arranged on still 3 and sends into distillation and collect still 3 and carry out Camphora distillation and collect step；
It is vaporize in sublimation step by Camphora that step is collected in the distillation of described Camphora, while pass into the Camphora of vaporization distillation to distillation collection still 3, collected the nitrogen input channel being provided with on still 3 by distilling be continually fed into nitrogen 1-5 in distillation collection still 3, making Camphora 1-4 settle rapidly crystallization, distillation is collected still temperature and is controlled between 80 DEG C。
The method also includes spray and collects step, after spray collection step is positioned at Camphora distillation collection step, it is that the material 1-6 not settled in Camphora distillation collection step is collected the material input channel feeding spray column 4 arranged on the material output channel and spray column 4 that arrange on still 3 through distillation that described spray collects step, and the shower water input channel passing through to arrange on spray column 4 is continually fed into shower water 1-7 in spray column and sprays, to collect Camphora 1-4 further。The material 1-8 that residue can not settle directly gets rid of spray column 4 by the material output channel arranged on spray column 4。
A kind of equipment of the method using above-mentioned isoborneol dehydrogenation Gum Camphor, it includes the interconnective reactor 2 for carrying out dehydrogenation reaction and solvent recovery step and Camphora vaporization sublimation step and collects the distillation collection still 3 of step for carrying out Camphora distillation, described reactor 2 is connected to the heater 5 that can be used for regulating temperature in the kettle, described reactor 2 is provided with the hydrogen 1-3 for dehydrogenation reaction being generated and discharges and isoborneol dissolution solvent carries out the dephlegmator 21 reclaimed, described reactor 2 is additionally provided with for vaporizing flower Of camphor be sent to the vaporizing column 22 of reactor 2。This heater 5 is circulating heater, and it includes the falling-film reboiler 52 and the circulating pump 53 that arrange on pipeline 51 that both ends are connected on reactor 2 and this pipeline 51。Distillation is collected and is provided with Camphora input channel, nitrogen input channel and material output channel on still 3。This equipment also includes spray column 4, and it is collected still 3 with distillation and is connected, and is used for carrying out spray and collects step。Spray column 4 is provided with material input channel, shower water input channel and material output channel。Dephlegmator 21 is dephlegmator that dephlegmator theoretical stage is 8 grades, the medial wall of vaporizing column 22 is connected to the two aerofluxus body impingement baffles 221 that equi-spaced apart is staggered and is oppositely arranged, reactor 2 is additionally provided with the surge tank 23 on the hydrogen 1-3 discharge-channel being arranged at dephlegmator 21；Distillation is collected and is provided with, on the whole central shaft of still 3, the some squeegee devices 31 extended by central axial still wall direction, and this squeegee devices is the scraper of thickness 6mm, and the spacing distance of scraper and still wall is 0.5cm。
Embodiment 2
A kind of method of isoborneol dehydrogenation Gum Camphor, includes dehydrogenation reaction successively and collects step with solvent recovery step, Camphora vaporization sublimation step and Camphora distillation；
Described dehydrogenation reaction and solvent recovery step are to send in reactor 2 by isoborneol with the mixed solution 1-1 of paracymene, palladium-carbon catalyst 1-2, and the mass ratio that isoborneol uses with palladium-carbon catalyst is 1:0.03。It is heated realizing dehydrogenation reaction to reactor 2, temperature is controlled between 172 DEG C, utilize the hydrogen 1-3 that dehydrogenation reaction is generated by dephlegmator 21 to discharge, and isoborneol dissolution solvent is reclaimed；
Described Camphora vaporization sublimation step is remaining material after completing dehydrogenation reaction and solution recycling step in reactor 1 to further heat up heating between 200 DEG C by vaporizing column 22, making Camphora 1-4 vaporization distillation, the Camphora 1-4 of vaporization distillation collects, by vaporizing column 22 and distillation, the Camphora input channel arranged on still 3 and sends into distillation and collect still 3 and carry out Camphora distillation and collect step；
The distillation of described Camphora collect step be Camphora is vaporized sublimation step collects, to distillation, the Camphora that still 3 passes into vaporization distillation while collected the nitrogen input channel that still 3 is provided with by distilling and collect in still 3 to distillation and be continually fed into nitrogen 1-5, making Camphora 1-4 settle rapidly crystallization, distillation is collected still temperature and is controlled between 65 DEG C。
The method also includes spray and collects step, after spray collection step is positioned at Camphora distillation collection step, it is that the material 1-6 not settled in Camphora distillation collection step is collected the material input channel feeding spray column 4 arranged on the material output channel and spray column 4 that arrange on still 3 through distillation that described spray collects step, and the shower water input channel passing through to arrange on spray column 4 is continually fed into shower water 1-7 in spray column and sprays, to collect Camphora 1-4 further。The material 1-8 that residue can not settle directly gets rid of spray column 4 by the material output channel arranged on spray column 4。
A kind of equipment of the method using above-mentioned isoborneol dehydrogenation Gum Camphor, it includes the interconnective reactor 2 for carrying out dehydrogenation reaction and solvent recovery step and Camphora vaporization sublimation step and collects the distillation collection still 3 of step for carrying out Camphora distillation, described reactor 2 is connected to the heater 5 that can be used for regulating temperature in the kettle, described reactor 2 is provided with the hydrogen 1-3 for dehydrogenation reaction being generated and discharges and isoborneol dissolution solvent carries out the dephlegmator 21 reclaimed, described reactor 2 is additionally provided with for vaporizing flower Of camphor be sent to the vaporizing column 22 of reactor 2。This heater 5 is circulating heater, and it includes the falling-film reboiler 52 and the circulating pump 53 that arrange on pipeline 51 that both ends are connected on reactor 2 and this pipeline 51。Distillation is collected and is provided with Camphora input channel, nitrogen input channel and material output channel on still 3。This equipment also includes spray column 4, and it is collected still 3 with distillation and is connected, and is used for carrying out spray and collects step。Spray column 4 is provided with material input channel, shower water input channel and material output channel。Dephlegmator 21 is dephlegmator that dephlegmator theoretical stage is 11 grades, the medial wall of vaporizing column 22 is connected to the two aerofluxus body impingement baffles 221 that equi-spaced apart is staggered and is oppositely arranged, reactor 2 is additionally provided with the surge tank 23 on the hydrogen 1-3 discharge-channel being arranged at dephlegmator 21；Distillation is collected and is provided with, on the whole central shaft of still 3, the some squeegee devices 31 extended by central axial still wall direction, and this squeegee devices is the scraper of thickness 5mm, and the spacing distance of scraper and still wall is 1.2cm。
Embodiment 3
A kind of method of isoborneol dehydrogenation Gum Camphor, includes dehydrogenation reaction successively and collects step with solvent recovery step, Camphora vaporization sublimation step and Camphora distillation；
Described dehydrogenation reaction and solvent recovery step are to send in reactor 2 by isoborneol with the mixed solution 1-1 of paracymene, palladium-carbon catalyst 1-2, and the mass ratio that isoborneol uses with palladium-carbon catalyst is 1:0.04。It is heated realizing dehydrogenation reaction to reactor 2, temperature is controlled between 160 DEG C, utilize the hydrogen 1-3 that dehydrogenation reaction is generated by dephlegmator 21 to discharge, and isoborneol dissolution solvent is reclaimed；
Described Camphora vaporization sublimation step is remaining material after completing dehydrogenation reaction and solution recycling step in reactor 1 to further heat up heating between 220 DEG C by vaporizing column 22, making Camphora 1-4 vaporization distillation, the Camphora 1-4 of vaporization distillation collects, by vaporizing column 22 and distillation, the Camphora input channel arranged on still 3 and sends into distillation and collect still 3 and carry out Camphora distillation and collect step；
The distillation of described Camphora collect step be Camphora is vaporized sublimation step collects, to distillation, the Camphora that still 3 passes into vaporization distillation while collected the nitrogen input channel that still 3 is provided with by distilling and collect in still 3 to distillation and be continually fed into nitrogen 1-5, making Camphora 1-4 settle rapidly crystallization, distillation is collected still temperature and is controlled between 50 DEG C。
The method also includes spray and collects step, after spray collection step is positioned at Camphora distillation collection step, it is that the material 1-6 not settled in Camphora distillation collection step is collected the material input channel feeding spray column 4 arranged on the material output channel and spray column 4 that arrange on still 3 through distillation that described spray collects step, and the shower water input channel passing through to arrange on spray column 4 is continually fed into shower water 1-7 in spray column and sprays, to collect Camphora 1-4 further。The material 1-8 that residue can not settle directly gets rid of spray column 4 by the material output channel arranged on spray column 4。
A kind of equipment of the method using above-mentioned isoborneol dehydrogenation Gum Camphor, it includes the interconnective reactor 2 for carrying out dehydrogenation reaction and solvent recovery step and Camphora vaporization sublimation step and collects the distillation collection still 3 of step for carrying out Camphora distillation, described reactor 2 is connected to the heater 5 that can be used for regulating temperature in the kettle, described reactor 2 is provided with the hydrogen 1-3 for dehydrogenation reaction being generated and discharges and isoborneol dissolution solvent carries out the dephlegmator 21 reclaimed, described reactor 2 is additionally provided with for vaporizing flower Of camphor be sent to the vaporizing column 22 of reactor 2。This heater 5 is circulating heater, and it includes the falling-film reboiler 52 and the circulating pump 53 that arrange on pipeline 51 that both ends are connected on reactor 2 and this pipeline 51。Distillation is collected and is provided with Camphora input channel, nitrogen input channel and material output channel on still 3。This equipment also includes spray column 4, and it is collected still 3 with distillation and is connected, and is used for carrying out spray and collects step。Spray column 4 is provided with material input channel, shower water input channel and material output channel。Dephlegmator 21 is dephlegmator that dephlegmator theoretical stage is 13 grades, the medial wall of vaporizing column 22 is connected to the two aerofluxus body impingement baffles 221 that equi-spaced apart is staggered and is oppositely arranged, reactor 2 is additionally provided with the surge tank 23 on the hydrogen 1-3 discharge-channel being arranged at dephlegmator 21；Distillation is collected and is provided with, on the whole central shaft of still 3, the some squeegee devices 31 extended by central axial still wall direction, and this squeegee devices is the scraper of thickness 4mm, and the spacing distance of scraper and still wall is 1.5cm。
Camphora purity obtained by above example 1-3 is as follows:
| Purity |
| Embodiment 1 | 97% |
| Embodiment 2 | 99% |
| Embodiment 3 | 98.2% |
The method of a kind of isoborneol dehydrogenation Gum Camphor of the present invention and equipment thereof are not only limited only to above-described embodiment, every any improvement according to the principle of the invention or replacement, all should within protection scope of the present invention。
Claims (10)
1. the method for an isoborneol dehydrogenation Gum Camphor, it is characterised in that: include dehydrogenation reaction successively and collect step with solvent recovery step, Camphora vaporization sublimation step and Camphora distillation；
Described dehydrogenation reaction and solvent recovery step are to send in reactor (2) by isoborneol and the mixed solution (1-1) of isoborneol dissolution solvent, dehydrogenation (1-2), it is heated realizing dehydrogenation reaction to reactor (2), the hydrogen (1-3) that dehydrogenation reaction is generated by the dephlegmator (21) that utilization is arranged on reactor (2) is discharged, and utilizes this dephlegmator (21) to be reclaimed by isoborneol dissolution solvent simultaneously；
Described Camphora vaporization sublimation step is, by the vaporizing column (22) being arranged on reactor (2), remaining material after completing dehydrogenation reaction and solution recycling step in reactor (2) is further heated up heating, making Camphora (1-4) vaporization distillation, the Camphora (1-4) that vaporization distils is collected still (3) by vaporizing column (22) feeding distillation and is carried out Camphora distillation collection step；
It is that vaporized by Camphora vaporize in the sublimation step Camphora (1-4) of distillation is sent into distillation and collected still (3) and be collected that step is collected in the distillation of described Camphora。
2. the method for isoborneol dehydrogenation Gum Camphor according to claim 1, it is characterised in that: described dehydrogenation reaction is with solvent recovery step, and dehydrogenation (1-2) is palladium-carbon catalyst；The mass ratio that isoborneol uses with palladium-carbon catalyst is 1:0.02-0.04。
3. the method for isoborneol dehydrogenation Gum Camphor according to claim 1, it is characterised in that: described isoborneol dissolution solvent is paracymene。
4. the method for isoborneol dehydrogenation Gum Camphor according to claim 1, it is characterised in that: described dehydrogenation reaction is with solution recycling step, and temperature controls between 160-185 DEG C；In described Camphora vaporization sublimation step, temperature controls between 190-220 DEG C。
5. the method for isoborneol dehydrogenation Gum Camphor according to claim 1, it is characterized in that: the distillation of described Camphora is collected in step, it is continually fed into nitrogen (1-5), so that Camphora (1-4) settles rapidly crystallization collecting to distillation to collect in still (3) to distillation while still (3) passes into the Camphora (1-4) that vaporization distils；Camphora distillation is collected the temperature of step and is controlled between 50-80 DEG C。
6. the method for isoborneol dehydrogenation Gum Camphor according to claim 1, it is characterized in that: the method also includes spray and collects step, after spray collection step is positioned at Camphora distillation collection step, it is Camphora distillation is collected the material (1-6) not settled in step send into spray column (4) that described spray collects step, and in spray column, be continually fed into shower water (1-7) spray, to collect Camphora (1-4) further。
7. the equipment for the method for the isoborneol dehydrogenation Gum Camphor described in any one of claim 1-6, it is characterized in that: this equipment includes interconnective for carrying out the reactor (2) of dehydrogenation reaction and solvent recovery step and Camphora vaporization sublimation step and collecting distillation collection still (3) of step for carrying out Camphora distillation, described reactor (2) is connected to the heater (5) that can be used for regulating temperature in the kettle, described reactor (2) is provided with the hydrogen (1-3) for dehydrogenation reaction being generated and discharges and isoborneol dissolution solvent carries out the dephlegmator (21) reclaimed, described reactor (2) is additionally provided with for vaporize flower Of camphor and be sent to distillation collect still (3) vaporizing column (22)。
8. the equipment of isoborneol dehydrogenation Gum Camphor according to claim 7, it is characterized in that: this heater (5) is circulating heater, it includes pipeline (51) that both ends are connected on reactor (2) and the upper falling-film reboiler (52) arranged of this pipeline (51) and circulating pump (53)。
9. the equipment of isoborneol dehydrogenation Gum Camphor according to claim 7, it is characterised in that: this equipment also includes spray column (4), and it is collected still (3) with distillation and is connected, and is used for carrying out spray and collects step。
10. the equipment of isoborneol dehydrogenation Gum Camphor according to claim 7, it is characterized in that: dephlegmator (21) is dephlegmator that dephlegmator theoretical stage is 8-13 level, the medial wall of vaporizing column (22) is connected to two aerofluxuss body impingement baffle (221) that equi-spaced apart is staggered and is oppositely arranged, reactor (2) is additionally provided with the surge tank (23) on hydrogen (1-3) discharge-channel being arranged at dephlegmator (21)；Distillation is collected and is provided with, on the whole central shaft of still (3), the some squeegee devices (31) extended by central axial still wall direction, and this squeegee devices is the scraper of thickness 4-6mm, and the spacing distance of scraper and still wall is 0.5-1.5cm。
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| CN105669411B (en) * | 2016-03-07 | 2018-06-26 | 华北电力大学 | A kind of method that yellow cinnamon leaf catalysis pyrolysis prepares camphor |
| CN105753667B (en) * | 2016-05-04 | 2019-01-18 | 福州大学 | A kind of method that isoborneol continuous dehydrogenation prepares camphor |
| CN107459445B (en) * | 2017-07-27 | 2021-01-15 | 福建南平青松化工有限公司 | Method for recycling camphor foot oil |
| CN108314611B (en) * | 2017-12-27 | 2021-04-27 | 福建南平青松化工有限公司 | Equipment and production process for preparing camphor by continuous gas phase dehydrogenation of isoborneol |
| CN108250057A (en) * | 2018-03-14 | 2018-07-06 | 梧州黄埔化工药业有限公司 | A kind of camphor production method and its isoborneol dissolution equipment |
| CN110668931B (en) * | 2019-10-21 | 2024-05-14 | 福建南平青松化工有限公司 | Apparatus and method for continuously preparing camphor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190907315A (en) * | 1909-03-26 | 1910-03-17 | August Zimmermann | Improved Catalysts for the Hydrogenation or Dehydrogenation of Organic Compounds. |
| SU870393A1 (en) * | 1978-04-05 | 1981-10-07 | Институт Нефтехимического Синтеза Им. А.В.Топчиева Ан Ссср | Method of simultaneous production of cyclopentene and colophony |
| CN1287993A (en) * | 1999-09-10 | 2001-03-21 | 中国科学院福建物质结构研究所 | Process for recovery and comprehensive utilization of by-product oil from hydration method synthesis of camphor |
-
2015
- 2015-10-28 CN CN201510714006.XA patent/CN105237369B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190907315A (en) * | 1909-03-26 | 1910-03-17 | August Zimmermann | Improved Catalysts for the Hydrogenation or Dehydrogenation of Organic Compounds. |
| SU870393A1 (en) * | 1978-04-05 | 1981-10-07 | Институт Нефтехимического Синтеза Им. А.В.Топчиева Ан Ссср | Method of simultaneous production of cyclopentene and colophony |
| CN1287993A (en) * | 1999-09-10 | 2001-03-21 | 中国科学院福建物质结构研究所 | Process for recovery and comprehensive utilization of by-product oil from hydration method synthesis of camphor |
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