CN105237369A - Isoborneol-dehydrogenated camphor refining method and equipment therefor - Google Patents
Isoborneol-dehydrogenated camphor refining method and equipment therefor Download PDFInfo
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- CN105237369A CN105237369A CN201510714006.XA CN201510714006A CN105237369A CN 105237369 A CN105237369 A CN 105237369A CN 201510714006 A CN201510714006 A CN 201510714006A CN 105237369 A CN105237369 A CN 105237369A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The invention relates to an isoborneol-dehydrogenated camphor refining method. The method sequentially comprises a dehydrogenation reaction and solvent recovery step, a camphor vaporization subliming step and a camphor sublimation collecting step, wherein the dehydrogenation reaction and solvent recovery step comprises the steps of feeding a mixed solution of the isoborneol and an isoborneol dissolving solvent and a dehydrogenation catalyst into a reactor, heating the reactor so as to realize dehydrogenation reaction, exhausting hydrogen gas produced from the dehydrogenation reaction by using a fractionating column, and recovering the isoborneol dissolving solvent. According to the method, the disadvantage in the existing isoborneol-dehydrogenated camphor refining process that the steps of dehydrogenation reaction, solvent recovery and vaporization subliming are required to be carried out sequentially in different devices is overcome, the integration of a dehydrogenation reactor, a solvent recovery device and a sublimation device can be realized, and thus the steps of dehydrogenation reaction, solvent recovery and vaporization subliming can be carried out in the same reactor; and the method has the advantages of reducing working procedures and greatly reducing manpower and equipment costs.
Description
Technical field
The present invention relates to a kind of method and equipment thereof of isocamphol dehydrogenation Gum Camphor, be applied in the production of camphor.
Background technology
Artificial camphor also known as camphanone, molecular formula C
10h
18o is a kind of white crystal, has refrigerant refreshing smell, is soluble in organic solvent, easily distil.Artificial camphor purposes is comparatively wide, mainly comprises: (1) is directly medicinal, can enter to fall beat, invigorate blood circulation external-applied ointment and medicinal oil (water) preparation, also can enter the oral Chinese patent medicine preparation etc. of relieving summer-heat restoring consciouness digestion promoting function; (2) pharmaceutical intermediate, for the production of medicine intermediate camphorsulfonic acid and the phenylglycine of central nervous excitation agent; (3) industrial raw material, can be used as zylonite, softening agent, smokeless powder, nitrocotton, sanitas etc.; (4) domestic camphor goods raw material, as the antitermite agent of clothing, woollen, books, file, archives etc.; (5) spices, is applied to the perfuming of daily chemical essence formula and household chemicals and industrial goods; (6) stacte, religion week are used.Camphor is again the main raw material producing campholenic nitrile, campholenates, bromo-camphor, camphor spirit and sodium camphorsulfonate.
Artificial camphor is generally be that raw material is produced under the effect of dehydrogenation catalyst with isocamphol, and its product comprises a small amount of unreacted isocamphol, and by product is borneol and fenchone, and needing carries out purifying just can obtain satisfactory camphor.Traditional dehydrogenation and method of purification add lime and the ventilation breather as dehydrogenation catalyst in reactor, if application number is the patent of invention of 90107669.4, take dimethylbenzene as solvent, at high temperature carry out dehydrogenation, after dehydrogenation completely, enter solvent recovery tower reclaim out dimethylbenzene, then enter distillation still and carry out sublimation purification, finally enter sublimation chamber and collect the camphor after purifying.Adopt dimethylbenzene as solvent in traditional technology, dimethylbenzene easily volatilizees and enters in air, and environmental pollution is larger; Ventilation breather can not reclaim use, and needs periodic exhaustion process as the ventilation breather decomposition generation cupric oxide of dehydrogenation catalyst, 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, cause loss of material serious, yield is low, unstable product quality, and the production cycle is long.After collecting in addition, product camphor manually need enter sublimation chamber shovel brain, and production efficiency is low.Therefore a kind of method and equipment thereof of novel isocamphol dehydrogenation Gum Camphor are provided, environmental protection, low cost can be realized, carry out the production of camphor expeditiously, and refining obtain the high product of good stability, content oneself become when business urgently.
Summary of the invention
The invention provides a kind of method and equipment thereof of isocamphol dehydrogenation Gum Camphor, which overcome dehydrogenation reaction in existing isocamphol dehydrogenation Gum Camphor technique, solvent recuperation and vaporization sublimation step to need sequentially to produce in different equipment, the integration of dehydrogenation reaction still, solvent recovery unit and sublimation apparatus can be realized, dehydrogenation reaction, solvent recuperation and vaporization sublimation step can be carried out in same reactor, there is saving operation, greatly reduce manpower and equipment cost advantage.
Technical scheme of the present invention is as follows:
A method for isocamphol dehydrogenation Gum Camphor, comprises vaporize sublimation step and camphor of dehydrogenation reaction and solvent recovery step, camphor successively and distils and collect step;
Described dehydrogenation reaction and solvent recovery step send in reactor by the mixing solutions of isocamphol and isocamphol dissolution solvent, dehydrogenation catalyst, heating is carried out to reactor and realizes dehydrogenation reaction, the hydrogen utilizing fractional column dehydrogenation reaction to be generated is discharged, and isocamphol dissolution solvent is reclaimed, for recycling;
Described camphor vaporization sublimation step to be heated up further to remaining material after completing dehydrogenation reaction and solution recycling step in reactor by vaporizing column to heat, camphor is vaporized distil, the camphor of vaporization distillation carries out camphor distillation by vaporizing column feeding distillation collection still and collects step; Vaporizing column, with heating jacket, has thermal oil to heat in chuck, the material entering vaporizing column can not be cooled.
It is that vaporized by camphor to vaporize in the sublimation step camphor of distillation is sent into distillation and collected still and collect that step is collected in the distillation of described camphor.
In existing isocamphol dehydrogenation Gum Camphor technique, dehydrogenation reaction, solvent recuperation and vaporization sublimation step need separately to carry out, and in technique after improving in the application, dehydrogenation reaction, solvent recuperation and vaporization sublimation step are concentrated in a reactor and carry out, achieve by arranging fractional column the recycling can carrying out solvent while carrying out dehydrogenation reaction.Get back to storage tank by a transferpump part after isocamphol dissolution solvent is gathered by fractional column, another part is got back in reactor again and is utilized.After dehydrogenation reaction, by the vaporizing column on reactor, camphor is carried out vaporization distillation, make it enter in distillation collection still and collect.The method of the isocamphol dehydrogenation Gum Camphor of the application has saved operation widely, provide not only production efficiency, also greatly reduces production cost.
In described dehydrogenation reaction and solvent recovery step, dehydrogenation catalyst is palladium-carbon catalyst; The mass ratio that isocamphol and palladium-carbon catalyst use is 1:0.02-0.04.
Dehydrogenation catalyst in existing isocamphol dehydrogenation Gum Camphor technique uses ventilation breather, and it can not reclaim use, and ventilation breather decomposition generation cupric oxide needs periodic exhaustion process, and processing cost is higher.Used in this application is palladium-carbon catalyst, and this catalyzer can recycle, and reduce dehydrogenation reaction temperature, energy consumption is low, and decreases the generation of impurity, improves reaction yield and shortens the reaction times, therefore the more existing technique of this technique is advanced.The consumption of this dehydrogenation catalyst is best, not only can not waste, and also can ensure fully carrying out of reaction.
Described isocamphol dissolution solvent is Paracymene.
What the solvent in existing isocamphol dehydrogenation Gum Camphor technique adopted is dimethylbenzene, and it easily volatilizees and enters in air, and environmental pollution is larger.Now use Paracymene as solvent, substitute dimethylbenzene, more environmental protection.The Main Function of Paracymene solvent dissolves isocamphol to be convenient to prevent line clogging by pump delivery; Next makes isocamphol recrystallization to remove the impurity be included in crystal, improves the quality of the finished product.
In described dehydrogenation reaction and solution recycling step, temperature controls between 160-185 DEG C; In described camphor vaporization sublimation step, temperature controls between 190-220 DEG C.This isocamphol coordinates this dehydrogenation reaction temperature that the dehydrogenation reaction of isocamphol can be made more complete with the proportioning of palladium-carbon catalyst.This solvent recuperation temperature organic efficiency is higher.
Described camphor distillation is collected in step, collects in still and continues to pass into nitrogen, thus make the rapid sedimentation crystallization of camphor while passing into the camphor of vaporization distillation to distillation collection still to distillation; The temperature that step is collected in camphor distillation controls between 50-80 DEG C.
The method also comprises spray and collects step, after spray collection step is positioned at camphor distillation collection step, it is that spray column sent into by material camphor distillation being collected non-sedimentation in step that described spray collects step, and in spray column, continues to pass into spray water spray, to collect camphor further.After step is collected in camphor distillation, design spray collects step, can make do not have the camphor in the material of sedimentation to be recycled, improve the yield of camphor.
A kind of equipment utilizing the method for above-mentioned isocamphol dehydrogenation Gum Camphor, this equipment comprise interconnective for carry out dehydrogenation reaction and solvent recovery step and camphor vaporize sublimation step reactor and collect still for carrying out the camphor distillation of collecting step that distils, described reactor is connected with the heating unit that can be used for regulating temperature in the kettle, described reactor is provided with hydrogen for dehydrogenation reaction being generated and discharges and isocamphol dissolution solvent carried out the fractional column that reclaims, described reactor is also provided with for vaporizing flower Of camphor sent into the vaporizing column of reactor.
Dehydrogenation reaction, solution recovery and camphor vaporization distillation concentrate in a reactor and carry out by this equipment, drastically increase production efficiency and have saved cost.
This heating unit is circulating heater, and it comprises both ends and is connected to falling-film reboiler and recycle pump that pipeline on reactor and this pipeline are arranged.
Dehydrogenation reaction is thermo-negative reaction, and circulating heater does not stop heat supply, to ensure the carrying out of dehydrogenation reaction can to reactor.Falling-film reboiler is compared with common reboiler, and material viscosity of its process can more greatly, and its thermo-sensitivity is strong, and thermo-efficiency comparatively greatly, is beneficial to the carrying out of dehydrogenation reaction.
This equipment also comprises spray column, and it is collected still with distillation and is connected, and collects step for carrying out spray.Collect the rear spray that increases in camphor distillation to collect, can make not fall camphor in heavy logistics partly and be recycled, improve camphor yield.
The fractional column of fractional column to be fractional column theoretical stage be 8-13 level, the inner side-wall of vaporizing column is connected with equi-spaced apart to interlock and be oppositely arranged two exhaust body striking plates, reactor is also provided with the surge tank be arranged on the hydrogen discharge passage of fractional column, the hydrogen that dehydrogenation reaction produces is by discharging reactor after surge tank; The whole central shaft of distillation collection still is provided with some squeegee devices of being extended to still wall direction by central shaft, 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 camphor 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 mainly camphor gas collects a connecting passage of still to distillation, arrange preventing gas punching, effectively can prevent the liquid camphor of also not vaporizing from directly pouring distillation and collect still, cause camphor product to turn yellow defective.
Compared with prior art, the present patent application has the following advantages:
1) the method adopts efficient, economy, the technique of environmental protection carries out sintetics, and refiningly obtains good stability, product that content is high;
2) in isocamphol dehydrogenation Gum Camphor technique, palladium-carbon catalyst is adopted to substitute the ventilation breather of current industrial use as dehydrogenation catalyst, not only can recycle, and dehydrogenation reaction temperature can be made to reduce, energy consumption is low, reduce the generation of impurity, improve reaction yield, shorten the reaction times;
3) use Paracymene instead as solvent, decrease environmental pollution, environmental protection;
4) camphor distillation is collected in step and is continued to pass into nitrogen mixing, is beneficial to the rapid sedimentation crystallization of camphor, shortens crystallization time;
5) what existing sublimation process adopted is natural cooling crystallization, there is temperature shortcoming rambunctious, and easily cause loss of material serious, yield is low, unstable product quality, and the production cycle is long.This application increases spray and collects after distillation is collected, and can fully collect the camphor do not fallen in heavy material, improve camphor yield;
6) dehydrogenation reaction, solvent recuperation, camphor vaporization distillation are all carried out in same reactor, and flow process is compact, shorten the production cycle;
7) circulating heater adopts falling-film reboiler, and use range is wider, is beneficial to reaction and carries out;
8) collection device that distils adopts reactor form to collect, and with squeegee devices, easy control of temperature, can operate continuously discharging, and stable and reliable product quality, reduces labour intensity;
9) use of surge tank and the vaporizing column with preventing gas punching on reactor, ensure that the safety of production is carried out, also ensure that the stabilised quality of product simultaneously.
The method of this isocamphol dehydrogenation Gum Camphor and the camphor obtained by equipment thereof, its purity >=97%.
Accompanying drawing explanation
Fig. 1 is the equipment schematic diagram of a kind of isocamphol dehydrogenation Gum Camphor of the present invention;
Fig. 2 is the structure sectional view of a kind of isocamphol dehydrogenation Gum Camphor fractional column of the present invention;
Fig. 3 is the structure sectional view of a kind of isocamphol dehydrogenation Gum Camphor vaporizing column of the present invention;
Fig. 4 is the vertical view of a kind of isocamphol dehydrogenation Gum Camphor vaporizing column of the present invention;
Fig. 5 is the structure sectional view of a kind of isocamphol dehydrogenation Gum Camphor surge tank of the present invention.
Label declaration:
The mixing solutions of 1-1 isocamphol and isocamphol dissolution solvent, 1-2 dehydrogenation catalyst, 1-3 hydrogen, 1-4 camphor, 1-5 nitrogen, the material of the non-sedimentation of 1-6, 1-7 spray water, 1-8 residue can not the material of sedimentation, 2 reactors, 21 fractional columns, 211 filler shaft collars, 212 ripple packings, 213 material receptors, 214 cooling water outlets, 215 entrance of cooling water, 216 material outlets, 217 material inlets, 218 material mouths, 219 hydrogen outlets, 22 vaporizing columns, 221 preventing gas punchings, 222 conduction oil interlayers, 223 thermal oil outlets, 224 heat conductive oil inlets, 23 surge tanks, 231 air outlets, 232 inlet mouths, 233 sewage draining exits, still is collected in 3 distillations, 31 squeegee devices, 32 nitrogen input channels, 33 camphor input channels, 34 material output channels, discharge opening is provided with bottom 35, 36 cooling water sandwich, 37 cooling water outlets, 38 entrance of cooling water, 4 spray columns, 5 heating units, 51 pipelines, 52 falling-film reboilers, 53 recycle pumps, 6 container for storing liquids.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in detail.
A method for isocamphol dehydrogenation Gum Camphor, comprises vaporize sublimation step and camphor of dehydrogenation reaction and solvent recovery step, camphor successively and distils and collect step;
Described dehydrogenation reaction and solvent recovery step send in reactor 2 by mixing solutions 1-1, the palladium-carbon catalyst 1-2 of isocamphol and Paracymene, and the mass ratio that isocamphol and palladium-carbon catalyst use is 1:0.02-0.04.Carry out heating to reactor 2 and realize dehydrogenation reaction, temperature controlled between 160-185 DEG C, the hydrogen 1-3 utilizing fractional column 21 dehydrogenation reaction to be generated discharges, and is reclaimed by isocamphol dissolution solvent;
Described camphor vaporization sublimation step is undertaken heating up further being heated between 190-220 DEG C by remaining material after completing dehydrogenation reaction and solution recycling step in vaporizing column 22 pairs of reactors 1, camphor 1-4 is vaporized distil, the camphor 1-4 of distillation of vaporizing carries out camphor distillation collection step by vaporizing column 22 and the camphor input channel feeding distillation collection still 3 collecting setting on still 3 that distils;
It is vaporized by camphor in sublimation step to collect in still 3 to distillation and continue to pass into nitrogen 1-5 collecting the nitrogen input channel collecting by distilling while still 3 passes into the camphor of vaporization distillation and still 3 is provided with to distillation that step is collected in the distillation of described camphor, make the rapid sedimentation crystallization of camphor 1-4, distillation is collected still temperature and is controlled between 50-80 DEG C.
The method also comprises spray and collects step, after spray collection step is positioned at camphor distillation collection step, the described collection step that sprays is the material input channel feeding spray column 4 that will the material output channel of material 1-6 setting on distillation collection still 3 of non-sedimentation in camphor distillation collection step and spray column 4 be arranged, and in spray column, continue to pass into spray water 1-7 spray by the spray water input channel that spray column 4 is arranged, to collect camphor 1-4 further.Residue can not sedimentation material 1-8 by spray column 4 arrange material output channel directly get rid of spray column 4.
A kind of equipment using the method for above-mentioned isocamphol dehydrogenation Gum Camphor, it comprise interconnective for carry out dehydrogenation reaction and solvent recovery step and camphor vaporize sublimation step reactor 2 and collect still 3 for carrying out the camphor distillation of collecting step that distils, described reactor 2 is connected with the heating unit 5 that can be used for regulating temperature in the kettle, and described reactor 2 is provided with hydrogen 1-3 for dehydrogenation reaction being generated and discharges and isocamphol dissolution solvent carried out the fractional column 21 that reclaims.This fractional column 21 is columnar structure, is filler shaft collar 211 bottom it, and the under-filled of fractional column inside has ripple packing 212, and the top of its inside is provided with material receptor 213.The outer side wall on fractional column top is provided with from top to bottom cooling water outlet 214, entrance of cooling water 215, material outlet 216, material inlet 217, fractional column 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 air outlet 218.Material mouth 218 adds isocamphol dissolution solvent for giving reactor 2, when carrying out dehydrogenation reaction in reactor 2, isocamphol dissolution solvent, by after the ripple packing 212 of fractional column, is recycled to container for storing liquid 6 through material outlet 216, and is re-entered in reactor 2 by material inlet 217 and carry out reuse.Described reactor 2 is also provided with for vaporizing flower Of camphor sent into 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 thermal oil.The top of this conduction oil interlayer 222 sidewall is provided with thermal oil outlet 223, and the bottom of its sidewall is provided with heat conductive oil inlet 224, carries out circulation heating by continuing to pass into thermal oil, realizes the vaporization distillation of camphor.
Described heating unit 5 is circulating heater, and it comprises both ends and is connected to falling-film reboiler 52 and recycle pump 53 that pipeline 51 on reactor 2 and this pipeline 51 are arranged.Distillation is collected still 3 top and is provided with camphor input channel 33, nitrogen input channel 32 and material output channel 34, and bottom is provided with discharge opening 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 cooling water outlet 37, and its lower sidewall is provided with entrance of cooling water 38.This equipment also comprises spray column 4, and it is collected still 3 with distillation and is connected, and collects step for carrying out spray.Spray column 4 is provided with material input channel, spray water input channel and material output channel.Fractional column 21 is the fractional column of 8-13 level for fractional column theoretical stage, the inner side-wall of vaporizing column 22 is connected with equi-spaced apart and interlocks and be oppositely arranged two exhaust body striking plates 221.Reactor 2 is also provided with the surge tank 23 be arranged on the hydrogen 1-3 discharge-channel of fractional column 21.The top of surge tank 23 is provided with air outlet 231 and inlet mouth 232, and bottom is provided with sewage draining exit 233.The whole central shaft of distillation collection still 3 is provided with some squeegee devices 31 of being extended to still wall direction by central shaft.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 method for isocamphol dehydrogenation Gum Camphor, comprises vaporize sublimation step and camphor of dehydrogenation reaction and solvent recovery step, camphor successively and distils and collect step;
Described dehydrogenation reaction and solvent recovery step send in reactor 2 by mixing solutions 1-1, the palladium-carbon catalyst 1-2 of isocamphol and Paracymene, and the mass ratio that isocamphol and palladium-carbon catalyst use is 1:0.02.Carry out heating to reactor 2 and realize dehydrogenation reaction, temperature controlled between 185 DEG C, the hydrogen 1-3 utilizing fractional column 21 dehydrogenation reaction to be generated discharges, and is reclaimed by isocamphol dissolution solvent;
Described camphor vaporization sublimation step is undertaken heating up further being heated between 190 DEG C by remaining material after completing dehydrogenation reaction and solution recycling step in vaporizing column 22 pairs of reactors 1, camphor 1-4 is vaporized distil, the camphor 1-4 of distillation of vaporizing carries out camphor distillation collection step by vaporizing column 22 and the camphor input channel feeding distillation collection still 3 collecting setting on still 3 that distils;
It is vaporize in sublimation step by camphor that step is collected in described camphor distillation, while passing into the camphor of vaporization distillation to distillation collection still 3, collect the nitrogen input channel that still 3 is provided with continue to pass into nitrogen 1-5 in distillation collection still 3 by distilling, make the rapid sedimentation crystallization of camphor 1-4, distillation is collected still temperature and is controlled between 80 DEG C.
The method also comprises spray and collects step, after spray collection step is positioned at camphor distillation collection step, the described collection step that sprays is the material input channel feeding spray column 4 that will the material output channel of material 1-6 setting on distillation collection still 3 of non-sedimentation in camphor distillation collection step and spray column 4 be arranged, and in spray column, continue to pass into spray water 1-7 spray by the spray water input channel that spray column 4 is arranged, to collect camphor 1-4 further.Residue can not sedimentation material 1-8 by spray column 4 arrange material output channel directly get rid of spray column 4.
A kind of equipment using the method for above-mentioned isocamphol dehydrogenation Gum Camphor, it comprise interconnective for carry out dehydrogenation reaction and solvent recovery step and camphor vaporize sublimation step reactor 2 and collect still 3 for carrying out the camphor distillation of collecting step that distils, described reactor 2 is connected with the heating unit 5 that can be used for regulating temperature in the kettle, described reactor 2 is provided with hydrogen 1-3 for dehydrogenation reaction being generated and discharges and isocamphol dissolution solvent carried out the fractional column 21 that reclaims, described reactor 2 is also provided with for vaporizing flower Of camphor sent into the vaporizing column 22 of reactor 2.This heating unit 5 is circulating heater, and it comprises both ends and is connected to falling-film reboiler 52 and recycle pump 53 that pipeline 51 on reactor 2 and this pipeline 51 are arranged.Distillation is collected on still 3 and is provided with camphor input channel, nitrogen input channel and material output channel.This equipment also comprises spray column 4, and it is collected still 3 with distillation and is connected, and collects step for carrying out spray.Spray column 4 is provided with material input channel, spray water input channel and material output channel.Fractional column 21 for fractional column theoretical stage be the fractional column of 8 grades, the inner side-wall of vaporizing column 22 is connected with equi-spaced apart to interlock and be oppositely arranged two exhaust body striking plates 221, reactor 2 is also provided with the surge tank 23 be arranged on the hydrogen 1-3 discharge-channel of fractional column 21; The whole central shaft of distillation collection still 3 is provided with some squeegee devices 31 of being extended to still wall direction by central shaft, 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 method for isocamphol dehydrogenation Gum Camphor, comprises vaporize sublimation step and camphor of dehydrogenation reaction and solvent recovery step, camphor successively and distils and collect step;
Described dehydrogenation reaction and solvent recovery step send in reactor 2 by mixing solutions 1-1, the palladium-carbon catalyst 1-2 of isocamphol and Paracymene, and the mass ratio that isocamphol and palladium-carbon catalyst use is 1:0.03.Carry out heating to reactor 2 and realize dehydrogenation reaction, temperature controlled between 172 DEG C, the hydrogen 1-3 utilizing fractional column 21 dehydrogenation reaction to be generated discharges, and is reclaimed by isocamphol dissolution solvent;
Described camphor vaporization sublimation step is undertaken heating up further being heated between 200 DEG C by remaining material after completing dehydrogenation reaction and solution recycling step in vaporizing column 22 pairs of reactors 1, camphor 1-4 is vaporized distil, the camphor 1-4 of distillation of vaporizing carries out camphor distillation collection step by vaporizing column 22 and the camphor input channel feeding distillation collection still 3 collecting setting on still 3 that distils;
It is vaporized by camphor to collect to distillation in sublimation step to collect nitrogen input channel that still 3 is provided with while still 3 passes into the camphor of vaporization distillation by distilling and to collect in still 3 to distillation and continue to pass into nitrogen 1-5 that step is collected in the distillation of described camphor, make the rapid sedimentation crystallization of camphor 1-4, distillation is collected still temperature and is controlled between 65 DEG C.
The method also comprises spray and collects step, after spray collection step is positioned at camphor distillation collection step, the described collection step that sprays is the material input channel feeding spray column 4 that will the material output channel of material 1-6 setting on distillation collection still 3 of non-sedimentation in camphor distillation collection step and spray column 4 be arranged, and in spray column, continue to pass into spray water 1-7 spray by the spray water input channel that spray column 4 is arranged, to collect camphor 1-4 further.Residue can not sedimentation material 1-8 by spray column 4 arrange material output channel directly get rid of spray column 4.
A kind of equipment using the method for above-mentioned isocamphol dehydrogenation Gum Camphor, it comprise interconnective for carry out dehydrogenation reaction and solvent recovery step and camphor vaporize sublimation step reactor 2 and collect still 3 for carrying out the camphor distillation of collecting step that distils, described reactor 2 is connected with the heating unit 5 that can be used for regulating temperature in the kettle, described reactor 2 is provided with hydrogen 1-3 for dehydrogenation reaction being generated and discharges and isocamphol dissolution solvent carried out the fractional column 21 that reclaims, described reactor 2 is also provided with for vaporizing flower Of camphor sent into the vaporizing column 22 of reactor 2.This heating unit 5 is circulating heater, and it comprises both ends and is connected to falling-film reboiler 52 and recycle pump 53 that pipeline 51 on reactor 2 and this pipeline 51 are arranged.Distillation is collected on still 3 and is provided with camphor input channel, nitrogen input channel and material output channel.This equipment also comprises spray column 4, and it is collected still 3 with distillation and is connected, and collects step for carrying out spray.Spray column 4 is provided with material input channel, spray water input channel and material output channel.Fractional column 21 for fractional column theoretical stage be the fractional column of 11 grades, the inner side-wall of vaporizing column 22 is connected with equi-spaced apart to interlock and be oppositely arranged two exhaust body striking plates 221, reactor 2 is also provided with the surge tank 23 be arranged on the hydrogen 1-3 discharge-channel of fractional column 21; The whole central shaft of distillation collection still 3 is provided with some squeegee devices 31 of being extended to still wall direction by central shaft, 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 method for isocamphol dehydrogenation Gum Camphor, comprises vaporize sublimation step and camphor of dehydrogenation reaction and solvent recovery step, camphor successively and distils and collect step;
Described dehydrogenation reaction and solvent recovery step send in reactor 2 by mixing solutions 1-1, the palladium-carbon catalyst 1-2 of isocamphol and Paracymene, and the mass ratio that isocamphol and palladium-carbon catalyst use is 1:0.04.Carry out heating to reactor 2 and realize dehydrogenation reaction, temperature controlled between 160 DEG C, the hydrogen 1-3 utilizing fractional column 21 dehydrogenation reaction to be generated discharges, and is reclaimed by isocamphol dissolution solvent;
Described camphor vaporization sublimation step is undertaken heating up further being heated between 220 DEG C by remaining material after completing dehydrogenation reaction and solution recycling step in vaporizing column 22 pairs of reactors 1, camphor 1-4 is vaporized distil, the camphor 1-4 of distillation of vaporizing carries out camphor distillation collection step by vaporizing column 22 and the camphor input channel feeding distillation collection still 3 collecting setting on still 3 that distils;
It is vaporized by camphor to collect to distillation in sublimation step to collect nitrogen input channel that still 3 is provided with while still 3 passes into the camphor of vaporization distillation by distilling and to collect in still 3 to distillation and continue to pass into nitrogen 1-5 that step is collected in the distillation of described camphor, make the rapid sedimentation crystallization of camphor 1-4, distillation is collected still temperature and is controlled between 50 DEG C.
The method also comprises spray and collects step, after spray collection step is positioned at camphor distillation collection step, the described collection step that sprays is the material input channel feeding spray column 4 that will the material output channel of material 1-6 setting on distillation collection still 3 of non-sedimentation in camphor distillation collection step and spray column 4 be arranged, and in spray column, continue to pass into spray water 1-7 spray by the spray water input channel that spray column 4 is arranged, to collect camphor 1-4 further.Residue can not sedimentation material 1-8 by spray column 4 arrange material output channel directly get rid of spray column 4.
A kind of equipment using the method for above-mentioned isocamphol dehydrogenation Gum Camphor, it comprise interconnective for carry out dehydrogenation reaction and solvent recovery step and camphor vaporize sublimation step reactor 2 and collect still 3 for carrying out the camphor distillation of collecting step that distils, described reactor 2 is connected with the heating unit 5 that can be used for regulating temperature in the kettle, described reactor 2 is provided with hydrogen 1-3 for dehydrogenation reaction being generated and discharges and isocamphol dissolution solvent carried out the fractional column 21 that reclaims, described reactor 2 is also provided with for vaporizing flower Of camphor sent into the vaporizing column 22 of reactor 2.This heating unit 5 is circulating heater, and it comprises both ends and is connected to falling-film reboiler 52 and recycle pump 53 that pipeline 51 on reactor 2 and this pipeline 51 are arranged.Distillation is collected on still 3 and is provided with camphor input channel, nitrogen input channel and material output channel.This equipment also comprises spray column 4, and it is collected still 3 with distillation and is connected, and collects step for carrying out spray.Spray column 4 is provided with material input channel, spray water input channel and material output channel.Fractional column 21 for fractional column theoretical stage be the fractional column of 13 grades, the inner side-wall of vaporizing column 22 is connected with equi-spaced apart to interlock and be oppositely arranged two exhaust body striking plates 221, reactor 2 is also provided with the surge tank 23 be arranged on the hydrogen 1-3 discharge-channel of fractional column 21; The whole central shaft of distillation collection still 3 is provided with some squeegee devices 31 of being extended to still wall direction by central shaft, and this squeegee devices is the scraper of thickness 4mm, and the spacing distance of scraper and still wall is 1.5cm.
Camphor purity obtained by above embodiment 1-3 is as follows:
| Purity |
| Embodiment 1 | 97％ |
| Embodiment 2 | 99％ |
| Embodiment 3 | 98.2％ |
The method of a kind of isocamphol dehydrogenation Gum Camphor of the present invention and equipment thereof have more than and are only confined to above-described embodiment, and every any improvement according to the principle of the invention or replacement, all should within protection scope of the present invention.
Claims (10)
1. a method for isocamphol dehydrogenation Gum Camphor, is characterized in that: comprise vaporize sublimation step and camphor of dehydrogenation reaction and solvent recovery step, camphor successively and distil and collect step;
Described dehydrogenation reaction and solvent recovery step send in reactor (2) by the mixing solutions (1-1) of isocamphol and isocamphol dissolution solvent, dehydrogenation catalyst (1-2), heating is carried out to reactor (2) and realizes dehydrogenation reaction, the hydrogen (1-3) utilizing fractional column (21) dehydrogenation reaction to be generated is discharged, and is reclaimed by isocamphol dissolution solvent;
Described camphor vaporization sublimation step to be heated up further to remaining material after completing dehydrogenation reaction and solution recycling step in reactor (1) by vaporizing column (22) to heat, camphor (1-4) is vaporized distil, the camphor (1-4) of vaporization distillation carries out camphor distillation by vaporizing column (22) feeding distillation collection still (3) and collects step;
It is that vaporized by camphor to vaporize in the sublimation step camphor (1-4) of distillation is sent into distillation and collected still (3) and collect that step is collected in the distillation of described camphor.
2. the method for isocamphol dehydrogenation Gum Camphor according to claim 1, is characterized in that: in described dehydrogenation reaction and solvent recovery step, dehydrogenation catalyst (1-2) is palladium-carbon catalyst; The mass ratio that isocamphol and palladium-carbon catalyst use is 1:0.02-0.04.
3. the method for isocamphol dehydrogenation Gum Camphor according to claim 1, is characterized in that: described isocamphol dissolution solvent is Paracymene.
4. the method for isocamphol dehydrogenation Gum Camphor according to claim 1, is characterized in that: in described dehydrogenation reaction and solution recycling step, temperature controls between 160-185 DEG C; In described camphor vaporization sublimation step, temperature controls between 190-220 DEG C.
5. the method for isocamphol dehydrogenation Gum Camphor according to claim 1, it is characterized in that: described camphor distillation is collected in step, collect in still (3) to distillation while the camphor (1-4) passing into vaporization distillation to distillation collection still (3) and continue to pass into nitrogen (1-5), thus make the rapid sedimentation crystallization of camphor (1-4); The temperature that step is collected in camphor distillation controls between 50-80 DEG C.
6. the method for isocamphol dehydrogenation Gum Camphor according to claim 1, it is characterized in that: the method also comprises spray and collects step, after spray collection step is positioned at camphor distillation collection step, it is that spray column (4) sent into by the material (1-6) camphor distillation being collected non-sedimentation in step that described spray collects step, and in spray column, continue to pass into spray water (1-7) spray, to collect camphor (1-4) further.
7. the equipment for the method for the isocamphol dehydrogenation Gum Camphor described in any one of claim 1-7, it is characterized in that: this equipment comprise interconnective for carry out dehydrogenation reaction and solvent recovery step and camphor vaporize sublimation step reactor (2) and collect still (3) for carrying out the camphor distillation of collecting step that distils, described reactor (2) is connected with the heating unit (5) that can be used for regulating temperature in the kettle, described reactor (2) is provided with hydrogen (1-3) for dehydrogenation reaction being generated and discharges and isocamphol dissolution solvent carried out the fractional column (21) that reclaims, described reactor (2) is also provided with for vaporizing flower Of camphor sent into the vaporizing column (22) of reactor (2).
8. the equipment of isocamphol dehydrogenation Gum Camphor according to claim 7, it is characterized in that: this heating unit (5) is circulating heater, it comprises both ends and is connected to pipeline (51) on reactor (2) and the upper falling-film reboiler (52) that arranges of this pipeline (51) and recycle pump (53).
9. the equipment of isocamphol dehydrogenation Gum Camphor according to claim 7, is characterized in that: this equipment also comprises spray column (4), and it is collected still (3) with distillation and is connected, and collects step for carrying out spray.
10. the equipment of isocamphol dehydrogenation Gum Camphor according to claim 7, it is characterized in that: fractional column (21) for fractional column theoretical stage be the fractional column of 8-13 level, the inner side-wall of vaporizing column (22) is connected with equi-spaced apart interlock and be oppositely arranged two exhaust body striking plate (221), reactor (2) is also provided be arranged at fractional column (21) hydrogen (1-3) discharge-channel on surge tank (23); The whole central shaft of distillation collection still (3) is provided with some squeegee devices (31) of being extended to still wall direction by central shaft, 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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| CN105669411A (en) * | 2016-03-07 | 2016-06-15 | 华北电力大学 | A kind of method for preparing camphor by catalytic pyrolysis of camphor leaves |
| CN105753667A (en) * | 2016-05-04 | 2016-07-13 | 福州大学 | Method for preparing camphor through continuous dehydrogenation of isoborneol |
| CN107459445A (en) * | 2017-07-27 | 2017-12-12 | 福建青松股份有限公司 | The method that camphor pin oil recycles |
| 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 |
| CN108314611A (en) * | 2017-12-27 | 2018-07-24 | 福建青松股份有限公司 | The equipment and production technology of the continuous gas-phase dehydrogenation camphor of isoborneol |
| CN110668931A (en) * | 2019-10-21 | 2020-01-10 | 福建南平青松化工有限公司 | Apparatus and method for continuously preparing camphor |
| CN112403207A (en) * | 2020-11-25 | 2021-02-26 | 梧州黄埔化工药业有限公司 | Camphor sublimation tail gas recovery unit |
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| CN105669411A (en) * | 2016-03-07 | 2016-06-15 | 华北电力大学 | A kind of method for preparing camphor by catalytic pyrolysis of camphor leaves |
| CN105669411B (en) * | 2016-03-07 | 2018-06-26 | 华北电力大学 | Method for preparing camphor by catalytic pyrolysis of camphor leaves |
| CN105753667A (en) * | 2016-05-04 | 2016-07-13 | 福州大学 | Method for preparing camphor through continuous dehydrogenation of isoborneol |
| CN105753667B (en) * | 2016-05-04 | 2019-01-18 | 福州大学 | A kind of method that isoborneol continuous dehydrogenation prepares camphor |
| CN107459445A (en) * | 2017-07-27 | 2017-12-12 | 福建青松股份有限公司 | The method that camphor pin oil recycles |
| 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 |
| CN108314611A (en) * | 2017-12-27 | 2018-07-24 | 福建青松股份有限公司 | The equipment and production technology of the continuous gas-phase dehydrogenation camphor of isoborneol |
| 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 |
| CN110668931A (en) * | 2019-10-21 | 2020-01-10 | 福建南平青松化工有限公司 | Apparatus and method for continuously preparing camphor |
| 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 |
| CN112403207A (en) * | 2020-11-25 | 2021-02-26 | 梧州黄埔化工药业有限公司 | Camphor sublimation tail gas recovery unit |
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