CN100391919C - Method and apparatus for continuous preparation of alpha, beta-unsaturated primary alcohol - Google Patents
Method and apparatus for continuous preparation of alpha, beta-unsaturated primary alcohol Download PDFInfo
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- CN100391919C CN100391919C CNB2005100940268A CN200510094026A CN100391919C CN 100391919 C CN100391919 C CN 100391919C CN B2005100940268 A CNB2005100940268 A CN B2005100940268A CN 200510094026 A CN200510094026 A CN 200510094026A CN 100391919 C CN100391919 C CN 100391919C
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Abstract
The present invention discloses a method for continuously preparing alpha, beta-unsaturated primary alcohol. Alpha, beta-unsaturated tertiary alcohol and a catalyst are added in a reactor for reacting by stir, and following raw materials are introduced into the bottom of the reactor continuously for reacting together; reaction products are collected and filtered, and the alpha, beta-unsaturated primary alcohol and the alpha, beta-unsaturated tertiary alcohol can be obtained respectively by the distillation or the rectification of filter liquor. The present invention also discloses a device for implementing the method, which is composed of the reactor, a raw material storage tank, a receiving tank and a stirring device, wherein a constant flow pump is arranged between the reactor and the raw material storage tank, and the outlet of the constant flow pump is communicate with the bottom of the reactor of which the upper part is communicated with the receiving tank; a stirring paddle of the stirring device is positioned in the reactor which is provided with a temperature sensor and is sheathed with a heater. The present invention has the advantages of simple operation, no waste, no need of a solvent and a large quantity of reaction reagent, low price of the catalyst, convenient source of the catalyst, low production cost, easy industrialization, etc.
Description
Technical field
The present invention relates to a kind of preparation α, the method for alpha, beta-unsaturated primary alcohol and device, particularly by α, β-unsaturated tertiary alcohols serialization prepares α, the method for alpha, beta-unsaturated primary alcohol and device thereof.
Background technology
α, alpha, beta-unsaturated primary alcohol mainly is meant a class at α, β-position has the primary alconol compounds of unsaturated double-bond.α, alpha, beta-unsaturated primary alcohol can be by its α, and the β position has the tertiary carbon alcohol compound (being α, β-unsaturated tertiary alcohols) of terminal ethylenyl groups and other corresponding chemical structure through catalytic isomerization, the allylic rearrangement reaction takes place obtain.α, alpha, beta-unsaturated primary alcohol, as: Geraniol, vernol, farnesol, trans-Geranylgeraniol, pohytol etc., itself just can be used as spices usually and use, also be the intermediate of synthetic perfume or some drugs simultaneously, purposes is comparatively extensive, and added value is higher.
By α, β-unsaturated tertiary alcohols prepares α existing, in the method for alpha, beta-unsaturated primary alcohol, mainly is divided into direct catalytic isomerization and esterified isomerizedization method.
Directly catalytic isomerization generally all adopts the intermittently mode of catalytic isomerization reaction, under catalyst action, finish reaction, through filtration, decomposition catalyst, washing, purification with operating process such as separate and obtain crude product, obtain target product through rectifying separation at last then.The catalyzer that uses comprises: the organic ester of liquid acid, transition metal, transition metal oxide, the acid of transition metal high price etc.Because there is transformation efficiency low (mostly being lower than 45%) in this law, yield is also low, and main drawback such as during operational cost does not industrially generally use.For example, Pierre Chabardes has introduced the preparation method of some main isomerization catalysts in JP 4823407, adopt ortho-vanadic acid tetrahydrochysene virtue camphor tree ester as catalyzer, makes the nerolidol isomerization obtain farnesol, reaction conversion ratio 23%, selectivity 89.9%; Ninagawa (USP 4006193) has reported the preparation method of multiple vanadium, molybdenum, tungsten ester class isomerization catalyst, such as being catalyzer with former alum tert-butyl acrylate, and isomerization reaction transformation efficiency 14.3%, selectivity 85%.Wood positive down first-class (JP 57045121, and JP 56034645) has been reported vanadium silicon ester and germanium vanadium esters of gallic acid Preparation of catalysts and isomerization application, with vanadium silicon ester (Ph
3SiO)
3When VO was catalyzer, nerolidol isomerization reaction transformation efficiency was 41.3%, and selectivity is 85%; With vanadium germanic acid ester (Ph
3GeO)
3When VO was catalyzer, the isomerization reaction selectivity was 90%.Fujita etc. (Ger Offen 2557837) are when adopting VB, group vib transition metal derivative to make the nerolidol isomerization synthesize farnesol, also investigated the suitable antistructure of nerolidol and farnesol, the catalyzer of use mainly is the original carboxylic acid ester's class such as the VO (OBu) of transition metal
3, (AcAc)
2VO,
, VO (OBu)
3, MoO (OBu)
4, VO (OPr)
3, VO (OSiMe
3)
3, VO (OSiEt
3)
3, WO (OSiEt
3)
4NEt
3Deng.
Esterified isomerizedization method is present the most frequently used industrial method, be a kind of the improving one's methods that Kane (USP 4254291) proposes, promptly adopt ortho-vanadic acid ester class catalyzer, and add assisted reaction reagent boric acid ester and be with aqua, through steps such as transesterify, dehydration, isomerization and hydrolysis, the yield of farnesol is brought up to about 80%.Esterified isomerizedization method that Here it is.Principal feature be with boric acid ester as esterification reagent, the molar weight that adds boric acid ester is suitable with the feed molar amount.Response feature is with raw material α, and β-unsaturated tertiary alcohols class is finished isomerization reaction under the effect of catalyzer, and isomerization product of Xing Chenging and boric acid ester carry out transesterification reaction simultaneously, impels isomerization reaction to transform to the product direction, thereby improves the isomerization productive rate.After finishing isomerization transesterify reaction,, obtain crude product through operating process such as washing, defecate and purify, separation, dryings then with the ester that the obtains saponification reaction that is hydrolyzed.Separation and purification obtains target product through high vacuum rectification at last.The main drawback of present method is to need a large amount of boric acid esters as reaction reagent, and operating process is more numerous and diverse, and economy is poor, the production cost height, and the industrialized developing difficulty is bigger.For the very high product of unit value, can not consider, but for the lower product of unit value, its economy then can't satisfy the actual production requirement.
The disclosed method by the synthetic transformation of geraniol/nerol of phantol of Jiang Huanfeng etc. (ZL 03113784.9) also belongs to esterified isomerizedization method.This method employing adds transition metal in phantol or its oxide compound is made catalyzer, using molecular weight is that 5000～10000 boric acid macrogol ester or acid polyol ester are as reaction reagent, though the defective phantol product that has used low levels is as reaction raw materials, raw materials cost can suitably reduce, but other technology shortcoming is not resolved equally, exists economy can't satisfy the problem of actual production requirement equally.
By α, β-unsaturated tertiary alcohols serialization prepares α, and the method for alpha, beta-unsaturated primary alcohol does not have disclosed bibliographical information so far.
Summary of the invention
The invention provides a kind of waste simple to operate, no, do not need solvent and a large amount of reaction reagent, catalyzer cheapness and convenient sources, production cost is low, very easily realize that industrialized serialization prepares α, the method for alpha, beta-unsaturated primary alcohol and device thereof.
The present invention adopts following technical scheme:
Preparation method of the present invention, that is: a kind of serialization prepares α, the method for alpha, beta-unsaturated primary alcohol:
The first step: in reactor, add the α that is equivalent to reactor useful volume 1/10～1/2, β-unsaturated tertiary alcohols, add and be equivalent to this α, the catalyzer of β-unsaturated tertiary alcohols quality 0.1%～1.0%, the controlling reactor temperature is 100 ℃～250 ℃, stirring reaction 1h～10h, to raw material α, β-unsaturated tertiary alcohols content drops to 60%～75% and product α, and the content of alpha, beta-unsaturated primary alcohol rises to 20%～35%, above-mentioned catalyzer is the salt of VB or the acid of group vib transition metal high price
Second step: the speed of pressing air speed 0.003cm/s～0.06cm/s is with follow-up raw material α, the reaction that β-unsaturated tertiary alcohols feeds the bottom of reactor continuously and participates in having generated mixes liquid and reacts together, liquid level improves gradually in the reactor, overflow by reactor head and with its collection until reaction mixture, again the liquid of collecting is filtered, the catalyzer of the filter residue that obtains for reclaiming, filtrate can obtain α respectively through distillation or rectifying, alpha, beta-unsaturated primary alcohol and α, β-unsaturated tertiary alcohols.
The device that is used to implement aforesaid method of the present invention, that is: a kind of be used to implement above-mentioned by α, β-unsaturated tertiary alcohols serialization prepares α, the device of the method for alpha, beta-unsaturated primary alcohol, by reactor, material storaging tank, receiving tank and agitator are formed, the import that is provided with constant flow pump and constant flow pump between reactor and material storaging tank is communicated with material storaging tank, the constant current pump outlet is communicated with the bottom of reactor, the top of reactor is communicated with receiving tank, the stirring rake of above-mentioned agitator is positioned at reactor, on reactor, be provided with temperature sensor, on reactor, be arranged with well heater.
Principle of the present invention: basic chemical reaction process of the present invention is seen reaction formula 1.α, β-position has the tertiary carbon alcohol compound (being α, β-unsaturated tertiary alcohols) of terminal ethylenyl groups can be by VB or group vib transition metal derivative catalytic isomerization, allylic rearrangement takes place, form α, β-position has the primary alconol compounds (being α, alpha, beta-unsaturated primary alcohol) of unsaturated double-bond.Indication α of the present invention, alpha, beta-unsaturated primary alcohol comprises: Geraniol, vernol, farnesol, trans-Geranylgeraniol, geranyl vernol, pohytol etc., α, β-unsaturated tertiary alcohols comprises: phantol, nerolidol, geranyl linalool, different vegetable alcohol etc.Catalyzer is molybdate, tungstate, phosphomolybdate, Lin Wusuanyan, vanadate, metavanadate etc.
Reaction formula 1 α, β-unsaturated tertiary alcohols isoversion reaction
The continuous reacting device (seeing accompanying drawing 1) of the present invention's design mainly comprises: reactor, material storaging tank, constant flow pump and receiving tank etc.Reactor is column (mainly being in order to increase raw material and catalyzer contact reacts time), there is the heating jacket of temperature controllable the outside, there is mechanical stirring (or induction stirring is equipped with in the bottom) inside, the opening for feed of reactor is positioned at the bottom side of bottom (or near) of reactor, and the overflow discharge port of reactor is positioned at the top side of top (or near) of reactor.
The continuous reaction process of the present invention's design, mainly comprise: be stored in the raw material α in the material storaging tank, β-unsaturated tertiary alcohols, continuously enter in reactor by certain flow velocity by reactor bottom through constant flow pump, under the suitable reaction temperature condition with reactor in the catalyzer contact reacts, produce isomerization product α, alpha, beta-unsaturated primary alcohol; Along with the increase of inlet amount, liquid level improves gradually in the reactor, until reaching reactor head, and is entered in the product receiving tank by the overflow outlet, obtains the α of certain content ratio continuously, alpha, beta-unsaturated primary alcohol and α, β-unsaturated tertiary alcohols.
Identical gas chromatography analysis method is all adopted in the analysis of reaction raw materials involved in the present invention, reaction mixture and final product.Gas chromatograph is last minute 1102GC type, and chromatographic column is SE-54 (0.25mm * 30m * 0.25 a μ m) quartz capillary chromatographic column, and column temperature control condition is: 120 ℃ keep 5min, rise to 160 ℃ and keep 30min with the heat-up rate of 4 ℃/min.Carrier gas is a nitrogen, splitting ratio 47: 1; Detector is FID, 220 ℃ of detector temperatures; 280 ℃ of sampler temperature.
Compared with prior art, the present invention has following technique effect:
(1) simple to operate, can realize serialization and control automatically, the plant factor height.Reaction unit involved in the present invention does not need specific installation, generally can make the form of reaction tower, take up an area of less, and it is easy to operate, material can be back to back, and can realize automatic control easily, because material residence time in present device is shorter than batch production equipment, and do not need to change up hill and dale continually reaction system in producing, so plant factor height;
(2) do not have waste substantially, do not need solvent, do not need a large amount of reaction reagents, highly beneficial to operating environment and surrounding enviroment.The present invention removes reaction raw materials α, outside β-unsaturated tertiary alcohols and the catalyzer, does not have other any organic solvent and assisted reaction reagent, and adding can recycling into the raw material of reaction and catalyzer, is the preparation technology of environmental protection therefore;
(3) catalyzer cheapness and convenient sources, catalyst activity is stable, the reaction favorable reproducibility, production control is convenient.Catalyzer involved in the present invention is molybdate, tungstate, phosphomolybdate, Lin Wusuanyan, vanadate, metavanadate etc., all be can make a big purchase in large quantities, convenient sources, the stable shaping industry product of product, fixedly specification is arranged, therefore the favorable reproducibility of using can guarantee smooth implementation of the present invention;
(4), overcome production cost height in the prior art, the irrational problem of economy by the mode of continuous reaction and recycle raw material and catalyzer.In existing production technology, remove reaction raw materials α, outside β-unsaturated tertiary alcohols and the catalyzer, also need a large amount of borate ester assisted reaction reagent, a large amount of organic solvents are as the band aqua, more operation stepss such as reactions steps needs through transesterify, dehydration, isomerization and hydrolysis, washing, sedimentation, separates, drying, and assisted reaction reagent and catalyzer are disposable consumption, can not recycling, Financial cost is apparently higher than the present invention.
Description of drawings
Fig. 1 is the preparation facilities structural representation.
Fig. 2 is the typical gas chromatogram of phantol continuous catalysis isomerization mix products, among the figure, peak A is raw material phantol (chromatographic retention is 7.04min), and peak B is product vernol (chromatographic retention is 10.88min), and peak C is product Geraniol (chromatographic retention is 11.82min).
Embodiment
Embodiment 1
A kind of by α, β-unsaturated tertiary alcohols serialization prepares α, the method of alpha, beta-unsaturated primary alcohol, be with α, β-unsaturated tertiary alcohols is a raw material, with the salt of VB or the acid of group vib transition metal high price, the ammonium salt, sodium salt etc. that are preferably high price molybdenum, tungsten, vanadium carboxylic acid are catalyzer, the isoversion reaction takes place in continuous reacting device, prepares α continuously, the method for alpha, beta-unsaturated primary alcohol.Specifically comprise the steps:
The first step: in reactor, add the α that is equivalent to reactor useful volume 1/10～1/2, β-unsaturated tertiary alcohols, add and be equivalent to this α, the catalyzer of β-unsaturated tertiary alcohols quality 0.1%～1.0%, the controlling reactor temperature is 100 ℃～250 ℃, stirring reaction 1h～10h, to raw material α, β-unsaturated tertiary alcohols content drops to 60%～75% and product α, the content of alpha, beta-unsaturated primary alcohol rises to 20%～35% (as: 20%, 35%, 23%, 28%, 30% or 34%), above-mentioned catalyzer is the salt of VB or the acid of group vib transition metal high price, above-mentioned α, the add-on of β-unsaturated tertiary alcohols can be to be equivalent to 1/10 of reactor useful volume, 1/2,1/8,1/7,1/5, or 1/3, the catalyzer add-on can be to be equivalent to α, β-unsaturated tertiary alcohols adds 0.1% of quality, 1.0%, 0.3%, 0.5%, 0.7% or 0.9%, the controlling reactor temperature can be 100 ℃, 250 ℃, 130 ℃, 180 ℃, 200 ℃ or 240 ℃, stirring reaction can be selected 1h, 10h, 3h, 5h, 6h, 8h
Second step: the speed of pressing air speed 0.003cm/s～0.06cm/s is with follow-up raw material α, the reaction that β-unsaturated tertiary alcohols feeds the bottom of reactor continuously and participates in having generated mixes liquid and reacts together, liquid level improves gradually in the reactor, overflow by reactor head and with its collection until reaction mixture, again the liquid of collecting is filtered, the catalyzer of the filter residue that obtains for reclaiming, filtrate can obtain α respectively through distillation or rectifying, alpha, beta-unsaturated primary alcohol and α, β-unsaturated tertiary alcohols, resulting α, alpha, beta-unsaturated primary alcohol comprises: Geraniol and vernol, farnesol, trans-Geranylgeraniol, the geranyl vernol, pohytol etc., in the present embodiment, every 1h～2h is to the reaction mixture sampling promoting the circulation of qi analysis of hplc of going forward side by side, α in reaction mixture, alpha, beta-unsaturated primary alcohol content is lower than at 20% o'clock, in the scope that satisfies air speed 0.003cm/s～0.06cm/s, reduce the adding speed of raw material, perhaps even can temporarily stop the adding of raw material, in the present embodiment, air speed can be chosen to be 0.003cm/s, 0.06cm/s or 0.045cm/s, when the present invention passes through to adjust follow-up raw material α, after the adding speed of β-unsaturated tertiary alcohols, still can not make the α in the reaction mixture, alpha, beta-unsaturated primary alcohol content reaches 20%～35%, then should take the technical measures of " adding catalyzer at interval in 8～24 hours down " with the catalyzer equivalent that adds first, present embodiment can be with the catalyzer of recovery and the raw material α of recovery, β-unsaturated tertiary alcohols feeds the bottom of reactor as follow-up raw material, above-mentioned α, β-unsaturated tertiary alcohols is a phantol, nerolidol, a kind of in geranyl linalool or the different vegetable alcohol, above-mentioned catalyzer comprises molybdate at least, tungstate, phosphomolybdate, Lin Wusuanyan, vanadate, metavanadate, a kind of in silicate or the metasilicate etc., that is: can be wherein a kind of, also can be the mixture more than 2 kinds or 2 kinds wherein, its proportioning can be any proportioning; And its corresponding salt mainly is corresponding inorganic or alkaline-earth metal salts such as an alkali metal salts such as organic ammonium salt, sodium salt, magnesium, for example: ammonium molybdate, Sodium orthomolybdate, potassium molybdate, magnesium molybdate, ammonium tungstate, sodium wolframate, potassium wolframate, magnesium wolframate, ammonium vanadate, ammonium meta-vanadate, sodium metavanadate, water glass, Starso, sodium phosphomolybdate, Tungstophosphoric acid, sodium salt etc.
Above-mentioned filtrate is distilled or the technical measures of rectifying can adopt method common in the prior art; for example: in nitrogen protection; distill under 100 ℃～300 ℃ and the 0.013kPa～90kPa condition; in still-process; when the still kettle temperature is low, collect earlier and obtain with unreacting material α; β-unsaturated tertiary alcohols is main cut; along with the temperature out that proceeds to of still-process obviously descends and distillates liquid velocity when obviously reducing; switch collector; the vacuum tightness continuation distillation that suitably improves the Heating temperature of still kettle or improve system simultaneously again; collection obtains with product α; alpha, beta-unsaturated primary alcohol is main cut; the distillation or the highly efficient distilling that carry out in case of necessity repeatedly can further improve product α, the purity of alpha, beta-unsaturated primary alcohol.
The device that is used to implement aforesaid method of the present invention, that is: a kind of be used to implement above-mentioned by α, β-unsaturated tertiary alcohols serialization prepares α, the device of the method for alpha, beta-unsaturated primary alcohol, by reactor 1, material storaging tank 2, receiving tank 3 and agitator 6 are formed, the import that is provided with constant flow pump 5 and constant flow pump 5 between reactor 1 and material storaging tank 2 is communicated with material storaging tank 2, the outlet of constant flow pump 5 is communicated with the bottom of reactor 1, the top of reactor 1 is communicated with receiving tank 3, the stirring rake 61 of above-mentioned agitator 6 is positioned at reactor 1, on reactor 1, be provided with temperature sensor, on reactor 1, be arranged with well heater 4.
The operation steps for preparing Geraniol and vernol by the phantol serialization:
The first step: in reactor, add the phantol that is equivalent to reactor useful volume 1/10～1/2, add and be equivalent to the ammonium molybdate of this phantol quality 0.1%～1.0% as catalyzer, the controlling reactor temperature is 100 ℃～250 ℃, stirring reaction 1h～10h, to raw material phantol content drop to 62%～72% and the content of product Geraniol and vernol rise to 22%～32%;
Second step: follow-up raw material phantol is by material storaging tank, entering the mixed liquid of reaction that the bottom of reactor participates in having generated through constant flow pump continuously by the speed of air speed 0.003cm/s～0.06cm/s reacts together, liquid level improves gradually in the reactor, is overflowed by reactor head until reaction mixture to enter in the product receiving tank;
The 3rd step: every 1h～2h sampling is carried out gas chromatographic analysis 1 time, whether the composition of check reaction mixture is in α, the content of β-unsaturated tertiary alcohols is 60%～75% and α, the content of alpha, beta-unsaturated primary alcohol is in 20%～35% the scope, otherwise to satisfy air speed 0.003cm/s～0.06cm/s (in the present embodiment by the scale knob that shows the flow size on the constant flow pump, be equivalent to flow and be to regulate the speed that adds raw material in the scope of 0.1L/h～2L/h) and carry out the adjusting of speed of response, if so still can not achieve the goal well, then need to replenish and add the ammonium molybdate catalyzer to increase speed of response, the additional add-on of catalyzer is suitable with the first amount that adds, and the timed interval of adding catalyzer is about 8h～24h;
The 4th step: output is also collected the mixed solution process filtering separation that obtains continuously; the catalyzer of the filter residue that obtains for reclaiming; filtrate is in nitrogen protection; distill under 100 ℃～300 ℃ and the 0.013kPa～90kPa condition; collect the cut that obtains based on unreacted raw material phantol earlier; when temperature out obviously descends and distillates liquid velocity when obviously reducing; switch collector; suitably improve Heating temperature and continue distillation; collection obtains the cut based on product Geraniol and vernol, carries out repeatedly distillation or the rectifying purity that can further improve product Geraniol and vernol in case of necessity.Catalyzer ammonium molybdate that recovery obtains and raw material phantol can continue on for carrying out successive reaction.
In the aforesaid operations step, be total to successive reaction 83h, drop into the phantol 2617g of content 97.0%, four water ammonium molybdate 7.59g, obtain in the reaction mixture continuously, purpose product Geraniol and vernol total content are 22%～32%, the content of unreacting material phantol is 62%～72%, obtain mixed solution 2457.5g, mixed solution is through distillation, obtain Geraniol and vernol total content and be product 500g～650g of 95%, the once through yield of Geraniol vernol is 19%～25%, and the rate of recovery of phantol is 76%～83%.Because the raw material phantol that reclaims can be proceeded reaction, the raw material phantol except that operational losses and generation side reaction can all be utilized in theory.
The operation steps for preparing farnesol by the nerolidol serialization:
Operation steps is identical with embodiment 1, just changes the raw material phantol into nerolidol.Operational condition is also substantially the same manner as Example 1.Farnesol content is between 18%～36% in the mixture that successive reaction obtains, and unreacted raw material nerolidol content is 55%～73%, and it is farnesol product more than 96% that crude product obtains purity after through distillation and high vacuum rectification.The per pass conversion of nerolidol is 20%～40%, and the rate of recovery of nerolidol is 75%～85%.Because the raw material nerolidol that reclaims can be proceeded reaction, the raw material nerolidol except that operational losses and generation side reaction can all be utilized in theory.
Embodiment 5
The operation steps for preparing trans-Geranylgeraniol by the geranyl linalool serialization:
Operation steps is identical with embodiment 1, just changes the raw material phantol into geranyl linalool.Operational condition is also substantially the same manner as Example 1.Trans-Geranylgeraniol content is between 20%～35% in the mixture that successive reaction obtains, and unreacted raw material geranyl linalool content is 56%～70%, and it is trans-Geranylgeraniol more than 92% that crude product obtains purity after through distillation and high vacuum rectification.The per pass conversion of geranyl linalool is 20%～38%, and the rate of recovery of geranyl linalool is 70%～80%.Because the raw material geranyl linalool that reclaims can be proceeded reaction, the raw material geranyl linalool except that operational losses and generation side reaction can all be utilized in theory.
The operation steps for preparing pohytol by the different vegetable alcohol serialization:
Operation steps is identical with embodiment 1, changes the raw material phantol into different vegetable alcohol.Operational condition is also substantially the same manner as Example 1.Pohytol content is between 20%～32% in the mixture that successive reaction obtains, and unreacted raw material different vegetable alcohol content is 60%～70%, and it is pohytol product more than 92% that crude product obtains purity after through distillation and high vacuum rectification.The per pass conversion of different vegetable alcohol is 20%～36%, and the rate of recovery of different vegetable alcohol is 70%～80%.Because the raw material different vegetable alcohol that reclaims can be proceeded reaction, the raw material different vegetable alcohol except that operational losses and generation side reaction can all be utilized in theory.
Claims (6)
1. a serialization prepares α, and the method for alpha, beta-unsaturated primary alcohol is characterized in that:
The first step: in reactor, add a kind of in phantol, nerolidol, geranyl linalool or the different vegetable alcohol be equivalent to reactor useful volume 1/10～1/2 as raw material, add the catalyzer that is equivalent to this raw materials quality 0.1%～1.0%, the controlling reactor temperature is 100 ℃～250 ℃, stirring reaction 1h～10h, drop to 60%～75% and product α to material content, the content of alpha, beta-unsaturated primary alcohol rises to 20%～35%, and above-mentioned catalyzer is the salt of VB or the acid of group vib transition metal high price;
Second step: by the speed of air speed 0.003cm/s～0.06cm/s will be identical with raw material follow-up raw material phantol, nerolidol, a kind of reaction mixture that feeds the bottom of reactor and participate in having generated in geranyl linalool or the different vegetable alcohol reacts together, liquid level improves gradually in the reactor, overflow by reactor head and with its collection until reaction mixture, again the liquid of collecting is filtered, the catalyzer of the filter residue that obtains for reclaiming, filtrate can obtain α, alpha, beta-unsaturated primary alcohol and phantol respectively through distillation or rectifying, nerolidol, a kind of in geranyl linalool or the different vegetable alcohol.
2. serialization according to claim 1 prepares α, the method of alpha, beta-unsaturated primary alcohol, it is characterized in that every 1h～2h is to the reaction mixture sampling promoting the circulation of qi analysis of hplc of going forward side by side, α in reaction mixture, alpha, beta-unsaturated primary alcohol content is lower than at 20% o'clock, reduces the adding speed of raw material in the scope that satisfies air speed 0.003cm/s～0.06cm/s.
3. serialization according to claim 2 prepares α, and the method for alpha, beta-unsaturated primary alcohol is characterized in that adding in 8～24 hours at interval the catalyzer with the catalyzer equivalent that adds first again.
4. described serialization prepares α according to claim 1, the method of alpha, beta-unsaturated primary alcohol is characterized in that a kind of bottom that feeds reactor as follow-up raw material in raw material phantol, nerolidol, geranyl linalool or the different vegetable alcohol of the catalyzer that will reclaim and recovery.
5. serialization according to claim 1 prepares α, the method of alpha, beta-unsaturated primary alcohol is characterized in that catalyzer comprises the mixture of a kind of in molybdate, tungstate, phosphomolybdate, Lin Wusuanyan, vanadate, metavanadate, silicate or the metasilicate etc. or two kinds and above composition at least.
6. one kind is used to implement the described serialization of claim 1 and prepares α, the device of the method for alpha, beta-unsaturated primary alcohol, it is characterized in that by reactor (1), material storaging tank (2), receiving tank (3) and agitator (6) are formed, the import that is provided with constant flow pump (5) and constant flow pump (5) between reactor (1) and material storaging tank (2) is communicated with material storaging tank (2), the outlet of constant flow pump (5) is communicated with the bottom of reactor (1), the top of reactor (1) is communicated with receiving tank (3), the stirring rake (61) of above-mentioned agitator (6) is positioned at reactor (1), on reactor (1), be provided with temperature sensor, on reactor (1), be arranged with well heater (4).
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| CN114874072B (en) * | 2022-05-20 | 2023-06-23 | 广西民族师范学院 | Preparation method of geranylgeraniol |
| CN116003219B (en) * | 2022-12-21 | 2024-07-02 | 江苏宏邦化工科技有限公司 | Method for synthesizing nerol geraniol by synergistic catalysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4006193A (en) * | 1972-03-13 | 1977-02-01 | Kuraray Co., Ltd. | Isomerization of the unsaturated alcohols |
| CN1434012A (en) * | 2003-02-21 | 2003-08-06 | 中国科学院广州化学研究所 | Process for synthesizing geraniol/nerol from linalool |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4006193A (en) * | 1972-03-13 | 1977-02-01 | Kuraray Co., Ltd. | Isomerization of the unsaturated alcohols |
| CN1434012A (en) * | 2003-02-21 | 2003-08-06 | 中国科学院广州化学研究所 | Process for synthesizing geraniol/nerol from linalool |
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