CN103254043B - Combined type asarin purification device and method - Google Patents
Combined type asarin purification device and method Download PDFInfo
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- CN103254043B CN103254043B CN201310193669.2A CN201310193669A CN103254043B CN 103254043 B CN103254043 B CN 103254043B CN 201310193669 A CN201310193669 A CN 201310193669A CN 103254043 B CN103254043 B CN 103254043B
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Abstract
The invention discloses a combined type asarin purification device and a method. The device comprises a buffer tank, a first film evaporator, a molecular stiller and a film filler distiller, wherein the buffer tank is connected with the first film evaporator; the first film evaporator is provided with a vacuum pumping port and a material outlet; the material outlet is connected with a feed port of the molecular stiller; the molecular stiller is provided with a vacuum pumping port, a beta-asarin distillation outlet and a distillate outlet; and the distillate outlet is connected with a feed port of the film filler distiller through a pump runner. The method comprises the following steps: preheating an artificially synthesized asarin crude product to 50-80 DEG C in the buffer tank, and performing first-stage distillation in the first film evaporator; performing second-stage molecular distillation on the raw material obtained by the first-stage film distillation to distill out beta-asarin; distilling out alpha-asarin through the third-stage film filler distiller; and dissolving with hot ethanol, recrystallizing with ethanol, and extracting. According to the method, the alpha-asarin product of which the purity is higher than 99% can be obtained.
Description
Technical field
The present invention relates to the purification of propenyl-2,4,5-trimethoxy beozene, particularly relate to a kind of apparatus and method of combined type purification propenyl-2,4,5-trimethoxy beozene, belong to pharmaceutical technology field.
Background technology
α ?propenyl-2,4,5-trimethoxy beozene be one of main active ingredient of Araeceae (Araceae) phytobezoar calamus (Acorus gramineus soland), have another name called α ?trans-Isoasarone, chemical name be 2,4,5 ?San Jia Yang Ji ?1 ?propenylbenzene, molecular formula C
12h
16o
3, relative molecular mass 208.25.Synthetic α ?propenyl-2,4,5-trimethoxy beozene process unavoidably produce by-product impurity particularly isomer propenyl-2,4,5-trimethoxy beozene ， α ?the cis-isomeride of propenyl-2,4,5-trimethoxy beozene be called β ?propenyl-2,4,5-trimethoxy beozene.From the sixties in last century, both at home and abroad Dui α ?propenyl-2,4,5-trimethoxy beozene conduct extensive research, confirmed that it has very strong pharmacologically active, tool cough-relieving, eliminate the phlegm, relieving asthma, calm, spasmolysis and anticonvulsant action.Pneumococcus, streptococcus aureus and colibacillary growth are also had to restraining effect in various degree.The monomer clinical application of extracting is achieved good results in pneumonia, asthma, epilepsy grand mal etc.
Prepare at present and in the reaction of propenyl-2,4,5-trimethoxy beozene, be always mixed with cis-isomeride and generate, and cis-isomeride has been proved and has had teratogenesis toxicity, therefore how to remove in product β ?propenyl-2,4,5-trimethoxy beozene, improve α ?the purity of propenyl-2,4,5-trimethoxy beozene become one of synthetic propenyl-2,4,5-trimethoxy beozene urgent problem of industry.
In synthetic propenyl-2,4,5-trimethoxy beozene, mainly comprise that trans-isomer(ide) α-propenyl-2,4,5-trimethoxy beozene is main, account for 89%, and contain a small amount of cis-isomeride β-propenyl-2,4,5-trimethoxy beozene, account for 10%, also contain moisture, solvent and other impurity.Current technique is by synthetic crude product, first underpressure distillation is removed after toluene, tetrahydrofuran (THF) equal solvent, resistates continues distillation and first collects 150 ℃ of following lower boiling fractions, regather vacuum tightness for-0.096～?0.098MPa, top temperature be the fine work fraction of 150～200 ℃, to color burn, top temperature, drop to 140 ℃ and stop distillation, the residual bottom sediment that heats up in a steamer discards, and fine work fraction obtains α-propenyl-2,4,5-trimethoxy beozene finished product through alcohol crystal again.Owing to taking conventional atmospheric vacuum distillation method in purification α-propenyl-2,4,5-trimethoxy beozene process, the temperature of the method low vacuum is up to 200 ℃ of heat-up times more than 4 hours, purification process temperature is high, heat-up time is long, at the raw material of still kettle because the long oxidation loss of being heated is large and color is dark.Current production technique perplexs the development of enterprise always, and it is low that enterprise wishes to seek a kind of efficient temperature, the method that yield height can industrialization.
Summary of the invention
The drawback of bringing in order to solve conventional method of purification, the object of the present invention is to provide that a kind of product impurity is few, the apparatus and method of white color or micro-Huang, the combined type purification propenyl-2,4,5-trimethoxy beozene that of high grade and yield is high.
Object of the present invention is achieved through the following technical solutions:
A device for combined type purification propenyl-2,4,5-trimethoxy beozene, comprises surge tank, the first film vaporizer, molecular still and thin film filling distiller; Surge tank connects the first film vaporizer by pipeline and connects, and the first film vaporizer is provided with vacuum pumping opening and material outlet; Vacuum pumping opening is connected with vacuum pump, and material outlet is connected with the opening for feed of molecular still; Molecular still is provided with vacuum pumping opening, β ?propenyl-2,4,5-trimethoxy beozene distillation outlet and overhead product outlet, and overhead product outlet is connected with the opening for feed of thin film filling distiller through pump is defeated;
Described thin film filling vaporizer comprises the second thin-film evaporator, filler king-post, condenser and return channel; Described the second thin-film evaporator comprises evaporator tube, motor, mechanical seal, steams mouth, opening for feed, blade applicator, reflux inlet and collection mouth; Reflux inlet is arranged on evaporator tube, is positioned at the lower end that steams mouth; Evaporator tube upper end is provided with mechanical seal, motor lower end is provided with frame, frame is arranged on evaporator tube upper end, motor is connected with blade applicator with axle by speed reduction unit, evaporator tube upper end is provided with and steams mouth, bottom is provided with collects mouth, and opening for feed is arranged on evaporator tube, is positioned at the lower end that steams mouth; Evaporator tube periphery is provided with chuck, and chuck is connected with thermal source;
Described filler king-post comprises king-post, vapour outlet, upper end reflux inlet, lower end reflux inlet, filler, material steam entrance, bottom drain; In king-post, be provided with filler, the king-post of filler lower end is provided with material steam entrance, and the top of king-post and bottom are respectively equipped with vapour outlet and bottom drain; Upper end reflux inlet and lower end reflux inlet are arranged on king-post, lay respectively at upper end and the filler middle part of filler;
Described condenser comprises condenser bodies, condenser inlet, cooling water outlet, vacuum pumping opening, entrance of cooling water, material outlet; Condenser bodies upper end is provided with condenser inlet, and lower end is provided with vacuum pumping opening and material outlet, and cooling water outlet and entrance of cooling water are separately positioned on the two ends of condenser bodies;
Described return channel is provided with return channel opening for feed, return channel discharge port and bypass outlet;
The mouth that steams of described the second thin-film evaporator is communicated with the material steam entrance on filler king-post; Bottom drain on filler king-post is communicated with the reflux inlet of the second thin-film evaporator; Vapour outlet on filler king-post is communicated with the condenser inlet of condenser, and the vacuum pumping opening of condenser is connected with vacuum pump, and the material outlet of condenser is communicated with return channel opening for feed; The bypass outlet of return channel is communicated with upper end reflux inlet and the lower end reflux inlet of filler king-post respectively.
For further realizing the object of the invention, described filler is preferably wire packing, ceramic packing, plastic filler, conjugate ring or Pall ring.Described condenser is shell and tube, spiral plate type or tube in-tube condenser.Described return channel is that electromagnetic type is controlled formula, volume pump is controlled or valve control type return channel.
The method of the combined type purification propenyl-2,4,5-trimethoxy beozene of application said apparatus, comprises the steps:
(1) synthetic propenyl-2,4,5-trimethoxy beozene crude product is first preheated to 50～80 ℃ in surge tank, and the material after preheating enters the first film steaming device, at the first film steaming device, carries out first step distillation, degassed, dehydration, de-low-boiling-point substance; The processing condition of first step thin film evaporation are: 50～120 ℃ of temperature, vacuum tightness-0.06～?0.098Mpa;
(2) second stage molecular distillation the raw material of first step thin film evaporation steam β ?propenyl-2,4,5-trimethoxy beozene, the processing condition of second stage molecular distillation are: 80～180 ℃ of temperature, vacuum tightness 100～10Pa;
(3) by the overhead product after the molecular distillation of the second stage third stage thin film filling distiller steam α ?propenyl-2,4,5-trimethoxy beozene; Temperature at the second thin-film evaporator and filler king-post is 120～200 ℃, and the vacuum tightness in the second thin-film evaporator, filler king-post and condenser is at 20～0.1Pa, and the cooling temperature of condenser is at 60～80 ℃;
(4) hot ethanol dissolve from third stage thin film filling distill α ?propenyl-2,4,5-trimethoxy beozene, wash away impurity again with cold ethyl alcohol recrystallization then extracting complete.
Further, described hot ethanol temperature is 60 ℃～80 ℃.
The present invention is by synthetic crude product, the raw material that first underpressure distillation is removed after toluene, tetrahydrofuran (THF) equal solvent adopts one-level thin film evaporation, one-level molecular distillation and the distillation of one-level thin film filling and re-crystallization step: the degassed processing of the first step, organic solvent is light molecular substance with respect to product, with thin-film evaporator, is easy to it thoroughly to remove reason; Second stage molecular still remove β ?propenyl-2,4,5-trimethoxy beozene, utilize α ?propenyl-2,4,5-trimethoxy beozene Yu β ?the molecular free path that causes of propenyl-2,4,5-trimethoxy beozene textural difference poor, steam β ?propenyl-2,4,5-trimethoxy beozene, the main α of overhead product ?propenyl-2,4,5-trimethoxy beozene; The thin film filling distiller of the third stage is refined and is steamed α ?propenyl-2,4,5-trimethoxy beozene, and then utilizing alcohol extraction and recrystallization is further to reduce impurity and pigment, obtains high purity white or micro-yellow pin lens product α ?propenyl-2,4,5-trimethoxy beozene.
With respect to prior art, tool of the present invention has the following advantages:
1, the course of processing of the present invention, in the temperature of the thin film filling distiller of the thin-film evaporator of the first step, the molecular still of the second stage and the third stage not higher than 200 ℃, the centrifugation time in each process is short, as at thin-film evaporator, material enters thin-film evaporator to flowing out, and material is only subject to action of gravity, from entering into the general heated time of outflow, be also no more than 30 seconds, and vacuum tightness is high, loss is few, and yield is high.
2, the method is alcohol extraction and recrystallization and three grades of techniques that compound purification combines; Hot ethanol dissolve from third stage thin film filling distill α ?propenyl-2,4,5-trimethoxy beozene wash away impurity again with cold ethyl alcohol recrystallization then extracting complete.60 ℃～80 ℃ of the ethanol of heat be easy to dissolve α ?propenyl-2,4,5-trimethoxy beozene, the process Rang α then lowering the temperature at leisure in cooling ?propenyl-2,4,5-trimethoxy beozene in ethanol, separate out obtain white or micro-yellow crystal body α ?propenyl-2,4,5-trimethoxy beozene.
3, due to the content of synthetic raw material α ?propenyl-2,4,5-trimethoxy beozene approach 90% left be mainly β ?propenyl-2,4,5-trimethoxy beozene and impurity seldom as long as β ?propenyl-2,4,5-trimethoxy beozene and impurity are separated and just obtained good product quality α ?propenyl-2,4,5-trimethoxy beozene, this technology can be brought up to the content of α ?propenyl-2,4,5-trimethoxy beozene more than 99%.
Accompanying drawing explanation:
Fig. 1 is the structural representation of the device of combined type purification propenyl-2,4,5-trimethoxy beozene of the present invention;
Fig. 2 is thin film filling distiller structural representation in Fig. 1;
Fig. 3 is thin-film evaporator structural representation in Fig. 2;
Fig. 4 is packing tower rod structure schematic diagram in Fig. 2;
Fig. 5 is condenser structure schematic diagram in Fig. 2.
Embodiment
For understanding better the present invention, below in conjunction with drawings and Examples, the present invention is further illustrated, but embodiment does not form the restriction to the claimed scope of the present invention.
As shown in Figure 1, a kind of device of combined type purification propenyl-2,4,5-trimethoxy beozene, comprises surge tank 11, the first film vaporizer 12, molecular still 13 and thin film filling distiller 14; Surge tank 11 connects the first film vaporizer 12 by pipeline and connects, and the first film vaporizer 12 is provided with vacuum pumping opening and material outlet; Vacuum pumping opening is connected with vacuum pump, and material outlet is connected with the opening for feed of molecular still 13 by punishment in advance pump; Molecular still 13 is provided with vacuum pumping opening, β ?propenyl-2,4,5-trimethoxy beozene distillation outlet and overhead product outlet, and overhead product outlet is connected with the opening for feed of thin film filling distiller 14 through pump is defeated.
As shown in Figure 2,3, 4, thin film filling vaporizer comprises the second thin-film evaporator 1, filler king-post 2, condenser 4 and return channel 3; The second thin-film evaporator 1 comprise evaporator tube, motor 1 ?1, mechanical seal 1 ?2, steam mouthful 1 ?3, opening for feed 1 ?4, blade applicator 1 ?5, reflux inlet 1 ?6 and collect mouthful 1 ?7; The second thin-film evaporator 1 be on general thin-film evaporator, set up reflux inlet 1 ?6, reflux inlet 1 ?6 be arranged on evaporator tube, be positioned at steam mouthful 1 ?3 lower end; Evaporator tube upper end be provided with mechanical seal 1 ?2, be used for sealing evaporator tube, motor 1 ?1 lower end be provided with frame, frame is arranged on evaporator tube upper end, motor 1 ?1 by speed reduction unit and axle and blade applicator 1 ?5 be connected, evaporator tube upper end be provided with steam mouthful 1 ?3, bottom be provided with collect mouthful 1 ?7, opening for feed 1 ?4 be arranged on evaporator tube, be positioned at steam mouthful 1 ?3 lower end; Evaporator tube periphery is provided with chuck, and chuck is connected with thermal source.
Filler king-post 2 comprises king-post, vapour outlet 2 ?1, upper end reflux inlet 2 ?2, lower end reflux inlet 2 ?3, filler 2 ?4, material steam entrance 2 ?5, bottom drain 2 ?6; In king-post, be provided with filler 2 ?4, filler 2 ?4 be wire packing, ceramic packing, plastic filler, conjugate ring, Pall ring etc.; Filler 2 ?the king-post of 4 lower ends be provided with material steam entrance 2 ?5, the top of king-post and bottom be respectively equipped with vapour outlet 2 ?1 and bottom drain 2 ?6; Upper end reflux inlet 2 ?2 and lower end reflux inlet 2 ?3 be arranged on king-post, lay respectively at filler 2 ?4 upper end and filler 2 ?4 middle parts; With respect to existing packing tower, this filler king-post 2 has saved the still kettle of king-post bottom;
Condenser 4 can be shell and tube, spiral plate type and tube in-tube condenser; Condenser 4 comprises condenser bodies, condenser inlet 4 ?1, cooling water outlet 4 ?2, vacuum pumping opening 4 ?3, entrance of cooling water 4 ?4, material outlet 4 ?5; Condenser bodies upper end be provided with condenser inlet 4 ?1, lower end be provided with vacuum pumping opening 4 ?3 and material outlet 4 ?5, cooling water outlet 4 ?2 and entrance of cooling water 4 ?4 two ends that are separately positioned on condenser bodies;
Return channel 3 can be controlled formula by electromagnetic type, volume pump is controlled or valve control type return channel, and return channel 3 is provided with return channel opening for feed, return channel discharge port and bypass outlet.
Mouthful 1 ?3 that steams of the second thin-film evaporator 1 is communicated with material steam entrance 2 ?5 on filler king-post 2; Bottom drain 2 ?6 on filler king-post 2 are communicated with reflux inlet 1 ?6 of the second thin-film evaporator 1; Vapour outlet 2 ?1 on filler king-post 2 are communicated with condenser inlet 4 ?1 of condenser 4, and vacuum pumping opening 4 ?3 of condenser 4 are connected with vacuum pump, and material outlet 4 ?5 of condenser 4 are communicated with return channel 3 opening for feeds; The bypass outlet of return channel 3 is communicated with upper end reflux inlet 2 ?2 and lower end reflux inlet 2 ?3 of filler king-post 2 respectively, regulates the ratio of backflow and discharging.
Motor 1 ?1 drive blade applicator 1 ?5 rotations, the opening for feed of material by the second thin-film evaporator 11 ?4 enter and in evaporator tube, form film, under Source, evaporate, form material steam, from steaming mouthful 1 ?3, enter filler king-post 2, material steam and the filler 2 of heat ?4 carry out mass transfer exchange, the heavy constituent after mass transfer exchanges (heavy constituent comprise impurity He α ?propenyl-2,4,5-trimethoxy beozene) by bottom drain 2 ?6 and reflux inlet 1 ?6 come back to thin-film evaporator 1 and again evaporate; Light constituent α after mass transfer exchange ?propenyl-2,4,5-trimethoxy beozene, by vapour outlet 2 ?1 enter condenser 4 condensation process, light constituent liquid α after condensation process ?propenyl-2,4,5-trimethoxy beozene product by discharge port and the bypass outlet of return channel 3, shunt, part light constituent liquid (mainly Shi α ?propenyl-2,4,5-trimethoxy beozene) is collected by return channel 3 discharge ports, product α ?propenyl-2,4,5-trimethoxy beozene product; Part light constituent liquid comprises that impurity and α ?propenyl-2,4,5-trimethoxy beozene enter filler king-post 2 again by bypass outlet.
Generally speaking, the feed separation efficiency of thin-film evaporator is high, but separation accuracy is poor; And packing tower feed separation treatment capacity is few, but separation accuracy is high, and as the obvious contrary technology of two relative merits, prior art is difficult to both to combine; The present invention, mainly by packing tower is improved, has saved the still kettle of packing tower, directly utilizes thin-film evaporator that the thermal source of material steam is provided, and material steam carries out efficient mass transfer exchange in packing tower; Thin film filling vaporizer of the present invention effectively combines the advantage of thin-film evaporator and packing tower, when making this thin film filling vaporizer have the high advantage of feed separation precision, also has advantages of that feed separation efficiency is high.Especially the separating-purifying to some heat-sensitive materials, because the separation efficiency of thin-film evaporator is high, the treatment time is short, and this thin film filling vaporizer provides effective means and means.Apparatus of the present invention be thin-film evaporator, filler king-post, condenser and return channel by the integral body of ingenious connection, can not split simply.
A method for combined type purification propenyl-2,4,5-trimethoxy beozene, comprises the steps:
(1) synthetic propenyl-2,4,5-trimethoxy beozene crude product is first preheated to 50～80 ℃ in surge tank 11, and the material after preheating enters the first film steaming device, at the first film steaming device, carries out first step distillation, degassed, dehydration, de-low-boiling-point substance; Object is removed the moisture in synthetic propenyl-2,4,5-trimethoxy beozene crude product and low-boiling-point substance, and low-boiling-point substance is mainly organic solvent, with respect to α ?propenyl-2,4,5-trimethoxy beozene product be light molecular substance; The processing condition of first step thin film evaporation are: 50～120 ℃ of temperature, vacuum tightness-0.06～?0.098Mpa; In synthetic propenyl-2,4,5-trimethoxy beozene, mainly comprise that trans-isomer(ide) α-propenyl-2,4,5-trimethoxy beozene is main, account for 89%, and contain a small amount of cis-isomeride β-propenyl-2,4,5-trimethoxy beozene, account for 10%, also contain moisture, solvent and other impurity.
(2) second stage molecular distillation steams β ?propenyl-2,4,5-trimethoxy beozene the raw material after degassed, and this one-level can all distill β ?propenyl-2,4,5-trimethoxy beozene as best one can, the purity of operation α ?propenyl-2,4,5-trimethoxy beozene after guaranteeing; The processing condition of second stage molecular distillation are: 80～180 ℃ of temperature, vacuum tightness 100～10Pa;
(3) third stage thin film filling distillation be by the overhead product after the molecular distillation of the second stage third stage thin film filling distiller steam α ?propenyl-2,4,5-trimethoxy beozene; Temperature at the second thin-film evaporator 1 and filler king-post 2 is 120～200 ℃, and the vacuum tightness in the second thin-film evaporator 1, filler king-post 2, condenser 4 is at 20～0.1Pa, and packing tower 2 will have good heat preservation effect, and the cooling temperature of condenser 4 is at 60～80 ℃.
(4) alcohol extraction and recrystallizing technology be hot ethanol dissolve from third stage thin film filling distill α ?propenyl-2,4,5-trimethoxy beozene wash away impurity again with cold ethyl alcohol recrystallization then extracting complete.Heat ethanol temperature be 60 ℃～80 ℃, be easy to dissolve α ?propenyl-2,4,5-trimethoxy beozene, then lower the temperature at leisure cooling process Rang α ?propenyl-2,4,5-trimethoxy beozene in ethanol, separate out obtain xln α ?propenyl-2,4,5-trimethoxy beozene.
Embodiment 1
As figure 1 ?as shown in 5, a kind of device of combined type purification propenyl-2,4,5-trimethoxy beozene, comprises surge tank 11, the first film vaporizer 12, molecular still 13 and thin film filling distiller 14; Surge tank 11 connects the first film vaporizer 12 by pipeline and connects, and the first film vaporizer 12 is provided with vacuum pumping opening and material outlet; Vacuum pumping opening is connected with vacuum pump, and material outlet is connected with the opening for feed of molecular still 13 by punishment in advance pump; Molecular still 13 is provided with vacuum pumping opening, β ?propenyl-2,4,5-trimethoxy beozene distillation outlet and overhead product outlet, and overhead product outlet is connected with the opening for feed of thin film filling distiller 14 through pump is defeated.Crowd artificial complete synthesis propenyl-2,4,5-trimethoxy beozene crude product 50Kg of Guangxi Yi Kang pharmaceutcal corporation, Ltd weighs.It is 60 ℃ that raw material is preheating to temperature through volume pump from surge tank 11, is input into the first film vaporizer 12 and carries out degassed, dehydration, de-low-boiling-point substance, and processing condition are: temperature 60 C, very empty degree ?0.095MPa, degassed, dehydration, de-low-boiling-point substance.Cut after degassed, water, desolventizing carries out molecular distillation through the molecular still 13 of the pump input second stage, steam β ?propenyl-2,4,5-trimethoxy beozene, processing condition are: 100 ℃ of temperature, vacuum tightness 10Pa, the about 41.3Kg of overhead product product weight obtaining, steam β ?propenyl-2,4,5-trimethoxy beozene and part α ?propenyl-2,4,5-trimethoxy beozene, amount to 8.7Kg, with guarantee substantially not have in the raw material of next step processing β ?propenyl-2,4,5-trimethoxy beozene.Overhead product after the molecular distillation of the second stage again through the thin film filling distiller 14 of the pump input third stage steam α ?propenyl-2,4,5-trimethoxy beozene, temperature at the second thin-film evaporator 1 and filler king-post 2 is 180 ℃, the vacuum tightness in the second thin-film evaporator 1, filler king-post 2, condenser 4 is at 1Pa, and the cooling temperature of condenser 4 is at 60 ℃.α ?propenyl-2,4,5-trimethoxy beozene from return channel discharge port out.Then the third stage be steamed out α ?propenyl-2,4,5-trimethoxy beozene alcohol extraction recrystallization, approximately 65 ℃ of the ethanol of heat be easy to dissolve α ?propenyl-2,4,5-trimethoxy beozene, the process Rang α then lowering the temperature at leisure in cooling ?propenyl-2,4,5-trimethoxy beozene in ethanol, separate out obtain xln α ?propenyl-2,4,5-trimethoxy beozene.Obtain white crystals needles.After testing, acquisition α ?propenyl-2,4,5-trimethoxy beozene purity more than 99%.
The temperature of the thin film filling distiller 14 of the process the first film vaporizer 12 of the first step or the molecular still 13 of the second stage and the third stage is all lower than 200 ℃, short action time at every flash trapping stage, no longer than 30 seconds, and less energy consumption.
Embodiment 2
As figure 1 ?as shown in 5, a kind of device of combined type purification propenyl-2,4,5-trimethoxy beozene, comprises surge tank 11, the first film vaporizer 12, molecular still 13 and thin film filling distiller 14; Surge tank 11 connects the first film vaporizer 12 by pipeline and connects, and the first film vaporizer 12 is provided with vacuum pumping opening and material outlet; Vacuum pumping opening is connected with vacuum pump, and material outlet is connected with the opening for feed of molecular still 13 by punishment in advance pump; Molecular still 13 is provided with vacuum pumping opening, β ?propenyl-2,4,5-trimethoxy beozene distillation outlet and overhead product outlet, and overhead product outlet is connected with the opening for feed of thin film filling distiller 14 through pump is defeated.50 ℃ of Guangxi hundred million health of weighing, are input into the first film vaporizer 12 and carry out degassed, dehydration, de-low-boiling-point substance, and processing condition are: 120 ℃ of temperature, Zhen Kong Du ?0.065MPa, degassed, dehydration, de-low-boiling-point substance.Cut after the solvent of degassed, water, de-low-boiling-point substance carries out molecular distillation through the molecular still 13 of the pump input second stage, steam β ?propenyl-2,4,5-trimethoxy beozene, processing condition are: 80 ℃ of temperature, vacuum tightness 100Pa, the about 31.6Kg of overhead product product weight obtaining, steam β ?propenyl-2,4,5-trimethoxy beozene and part α ?propenyl-2,4,5-trimethoxy beozene, amount to 8Kg, with guarantee substantially not have in the raw material of next step processing β ?propenyl-2,4,5-trimethoxy beozene.Overhead product after the molecular distillation of the second stage again through the thin film filling distiller 14 of the pump input third stage steam α ?propenyl-2,4,5-trimethoxy beozene, processing condition are: the temperature at the second thin-film evaporator 1 and filler king-post 2 is 200 ℃, vacuum tightness in the second thin-film evaporator 1, filler king-post 2, condenser 4 is at 20Pa, and the cooling temperature of condenser 4 is at 80 ℃.α ?propenyl-2,4,5-trimethoxy beozene from return channel discharge port out.Then the third stage be steamed out α ?propenyl-2,4,5-trimethoxy beozene alcohol extraction recrystallization, approximately 60 ℃ of the ethanol of heat be easy to dissolve α ?propenyl-2,4,5-trimethoxy beozene, the process Rang α then lowering the temperature at leisure in cooling ?propenyl-2,4,5-trimethoxy beozene in ethanol, separate out obtain xln α ?propenyl-2,4,5-trimethoxy beozene.Obtain white crystals needles.Owing to taking above technological process, after testing, acquisition α ?propenyl-2,4,5-trimethoxy beozene purity more than 99%.
The temperature of the thin film filling distiller 14 of the process the first film vaporizer 12 of the first step or the molecular still 13 of the second stage and the third stage is not higher than 200 ℃, short in the centrifugation time of every one-level, no longer than 30 seconds, and less energy consumption.
Embodiment 3
As figure 1 ?as shown in 5, a kind of device of combined type purification propenyl-2,4,5-trimethoxy beozene, comprises surge tank 11, the first film vaporizer 12, molecular still 13 and thin film filling distiller 14; Surge tank 11 connects the first film vaporizer 12 by pipeline and connects, and the first film vaporizer 12 is provided with vacuum pumping opening and material outlet; Vacuum pumping opening is connected with vacuum pump, and material outlet is connected with the opening for feed of molecular still 13 by punishment in advance pump; Molecular still 13 is provided with vacuum pumping opening, β ?propenyl-2,4,5-trimethoxy beozene distillation outlet and overhead product outlet, and overhead product outlet is connected with the opening for feed of thin film filling distiller 14 through pump is defeated.Crowd artificial complete synthesis propenyl-2,4,5-trimethoxy beozene crude product 40Kg of Guangxi Yi Kang pharmaceutcal corporation, Ltd weighs.Raw material is preheating to temperature through volume pump from surge tank 11 and is 80 ℃ and is input into the first film vaporizer 12 and carries out degassed, dehydration, de-low-boiling-point substance, and condition is: 100 ℃ of temperature, very empty degree ?0.083MPa, degassed, dehydration, de-low-boiling-point substance.Cut after degassed, water, desolventizing carries out molecular distillation through the molecular still 13 of the pump input second stage, steam β ?propenyl-2,4,5-trimethoxy beozene, condition is: 180 ℃ of temperature, vacuum tightness 10Pa, the about 30.8Kg of overhead product product weight obtaining, steam β ?propenyl-2,4,5-trimethoxy beozene and part α ?propenyl-2,4,5-trimethoxy beozene, amount to 9Kg, with guarantee substantially not have in the raw material of next step processing β ?propenyl-2,4,5-trimethoxy beozene.Overhead product after the molecular distillation of the second stage again through the thin film filling distiller 14 of the pump input third stage steam α ?propenyl-2,4,5-trimethoxy beozene, processing condition are: the temperature at the second thin-film evaporator 1 and filler king-post 2 is 120 ℃, vacuum tightness in the second thin-film evaporator 1, filler king-post 2, condenser 4 is at 0.1Pa, and the cooling temperature of condenser 4 is at 70 ℃.α ?propenyl-2,4,5-trimethoxy beozene from return channel discharge port out.Then the third stage be steamed out α ?propenyl-2,4,5-trimethoxy beozene alcohol extraction recrystallization, approximately 80 ℃ of the ethanol of heat be easy to dissolve α ?propenyl-2,4,5-trimethoxy beozene, the process Rang α then lowering the temperature at leisure in cooling ?propenyl-2,4,5-trimethoxy beozene in ethanol, separate out obtain xln α ?propenyl-2,4,5-trimethoxy beozene.Obtain white crystals needles.Owing to taking above technological process, after testing, acquisition α ?propenyl-2,4,5-trimethoxy beozene purity more than 99%.
The treatment temp of the thin film filling distiller 14 of the raw material process the first film vaporizer 12 of the first step or the molecular still 13 of the second stage and the third stage is not higher than 200 ℃, the centrifugation time in every one-level is short, no longer than 30 seconds, less energy consumption, obtain highly purified α ?propenyl-2,4,5-trimethoxy beozene more than 99%.
Claims (6)
1. a device for combined type purification propenyl-2,4,5-trimethoxy beozene, is characterized in that comprising surge tank, the first film vaporizer, molecular still and thin film filling distiller; Surge tank connects the first film vaporizer by pipeline and connects, and the first film vaporizer is provided with vacuum pumping opening and material outlet; Vacuum pumping opening is connected with vacuum pump, and material outlet is connected with the opening for feed of molecular still; Molecular still is provided with vacuum pumping opening, β ?propenyl-2,4,5-trimethoxy beozene distillation outlet and overhead product outlet, and overhead product outlet is connected with the opening for feed of thin film filling distiller through pump is defeated;
Described thin film filling vaporizer comprises the second thin-film evaporator, filler king-post, condenser and return channel; Described the second thin-film evaporator comprises evaporator tube, motor, mechanical seal, steams mouth, opening for feed, blade applicator, reflux inlet and collection mouth; Reflux inlet is arranged on evaporator tube, is positioned at the lower end that steams mouth; Evaporator tube upper end is provided with mechanical seal, motor lower end is provided with frame, frame is arranged on evaporator tube upper end, motor is connected with blade applicator with axle by speed reduction unit, evaporator tube upper end is provided with and steams mouth, bottom is provided with collects mouth, and opening for feed is arranged on evaporator tube, is positioned at the lower end that steams mouth; Evaporator tube periphery is provided with chuck, and chuck is connected with thermal source;
Described filler king-post comprises king-post, vapour outlet, upper end reflux inlet, lower end reflux inlet, filler, material steam entrance, bottom drain; In king-post, be provided with filler, the king-post of filler lower end is provided with material steam entrance, and the top of king-post and bottom are respectively equipped with vapour outlet and bottom drain; Upper end reflux inlet and lower end reflux inlet are arranged on king-post, lay respectively at upper end and the filler middle part of filler;
Described condenser comprises condenser bodies, condenser inlet, cooling water outlet, vacuum pumping opening, entrance of cooling water, material outlet; Condenser bodies upper end is provided with condenser inlet, and lower end is provided with vacuum pumping opening and material outlet, and cooling water outlet and entrance of cooling water are separately positioned on the two ends of condenser bodies;
Described return channel is provided with return channel opening for feed, return channel discharge port and bypass outlet;
The mouth that steams of described the second thin-film evaporator is communicated with the material steam entrance on filler king-post; Bottom drain on filler king-post is communicated with the reflux inlet of the second thin-film evaporator; Vapour outlet on filler king-post is communicated with the condenser inlet of condenser, and the vacuum pumping opening of condenser is connected with vacuum pump, and the material outlet of condenser is communicated with return channel opening for feed; The bypass outlet of return channel is communicated with upper end reflux inlet and the lower end reflux inlet of filler king-post respectively.
2. the device of combined type purification propenyl-2,4,5-trimethoxy beozene according to claim 1, is characterized in that: described filler is wire packing, conjugate ring or Pall ring.
3. the device of combined type purification propenyl-2,4,5-trimethoxy beozene according to claim 1, is characterized in that: described condenser is shell and tube, spiral plate type or tube in-tube condenser.
4. the device of combined type purification propenyl-2,4,5-trimethoxy beozene according to claim 1, is characterized in that: described return channel is that electromagnetic type is controlled formula, volume pump is controlled or valve control type return channel.
Application rights require 1 ?the method of the combined type purification propenyl-2,4,5-trimethoxy beozene that installs described in 4 any one, it is characterized in that comprising the steps:
(1) synthetic propenyl-2,4,5-trimethoxy beozene crude product is first preheated to 50～80 ℃ in surge tank, and the material after preheating enters the first film steaming device, at the first film steaming device, carries out first step distillation, degassed, dehydration, de-low-boiling-point substance; The processing condition of first step thin film evaporation are: 50～120 ℃ of temperature, vacuum tightness (?0.06～?0.098) Mpa;
(2) second stage molecular distillation the raw material of first step thin film evaporation steam β ?propenyl-2,4,5-trimethoxy beozene, the processing condition of second stage molecular distillation are: 80～180 ℃ of temperature, vacuum tightness 100～10Pa; Second stage molecular distillation carries out in molecular still;
(3) by the overhead product after the molecular distillation of the second stage thin film filling distiller steam α ?propenyl-2,4,5-trimethoxy beozene; Temperature at the second thin-film evaporator and filler king-post is 120～200 ℃, and the vacuum tightness in the second thin-film evaporator, filler king-post and condenser is at 20～0.1Pa, and the cooling temperature of condenser is at 60～80 ℃;
(4) hot ethanol dissolve from thin film filling distiller distill α ?propenyl-2,4,5-trimethoxy beozene, wash away impurity again with cold ethyl alcohol recrystallization then extracting complete.
6. the method for combined type purification propenyl-2,4,5-trimethoxy beozene according to claim 5, is characterized in that: described hot ethanol temperature is 60 ℃～80 ℃.
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Address after: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Co-patentee after: Guangxi Yikang Pharmaceutical Co., Ltd. Patentee after: South China University of Technology Co-patentee after: Guangzhou Haoli Technology Co., Ltd. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Co-patentee before: Guangxi Yikang Pharmaceutical Industry Co., Ltd. Patentee before: South China University of Technology Co-patentee before: Guangzhou Haoli Technology Co., Ltd. |