CN101928203B - Method for supercritically synthesizing leaf alcohol - Google Patents
Method for supercritically synthesizing leaf alcohol Download PDFInfo
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- CN101928203B CN101928203B CN201010286704.1A CN201010286704A CN101928203B CN 101928203 B CN101928203 B CN 101928203B CN 201010286704 A CN201010286704 A CN 201010286704A CN 101928203 B CN101928203 B CN 101928203B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for supercritically synthesizing leaf alcohol. The conventional methods have one or more of the following defects: long process, low yield, rigorous reaction conditions, high corrosion on equipment and low safety of raw materials. Besides, the conventional methods have a common defect of poor atom economy and a large amount of three wastes generated in the synthesis process. The method for supercritically synthesizing the leaf alcohol comprises the following steps of: uniformly mixing raw materials 1-pentene and formaldehyde in a solvent, adding the mixture into a snake tube reactor, and continuously performing condensation reaction under the supercritical condition; ensuring to enter a flash evaporator through a high pressure valve, cooling low-boiling-point substances flashed out to below 40 DEG C by using a condenser, flowing the low-boiling-point substances into a light component receiver, and flowing the residues into a heavy component receiver; and respectively rectifying and separating the obtained products. The method has the advantages of simple and short process, and only one step reaction; and the continuous synthesis method has the advantages of stable operation, good atom economy and light pollution.
Description
Technical field
The present invention relates to field of fine chemical, specifically a kind of method of overcritical compound essence spices leaf-alcohol.
Background technology
Leaf-alcohol (Leaf alcohol) [formal name used at school: cis-3 hexen-1-ols (cis-3-Hexen-1-ol)], outward appearance is colourless oil liquid, has the delicate fragrance fragrance of greenery, is slightly soluble in water, is dissolved in most of organic solvents such as ethanol.The delicate fragrance that leaf-alcohol after dilution has fresh grass while cutting off, gives a kind of pure and fresh, happy sensation of staying the Nature.Leaf-alcohol and derivative thereof are one of pandemic scent type rare spices, at least more than 40 kinds, in synthetic perfume and essence, apply at present, have become the symbol of world's fragrance industry Green Revolution.In view of the critical role of leaf-alcohol in spices, essence and the huge commercial value of bringing thus, the research of leaf-alcohol has caused attention both domestic and external already.
Leaf-alcohol is almost present in all green plantss, and the embodiment of the body of so-called symbol plant " green " on smell is exactly leaf-alcohol.Although certainly since the dawn of human civilization, leaf-alcohol just becomes a link of human foods chain, until within 1895, just measure its existence in tea oil.In 1917, people found that again leaf-alcohol is present in Japanese mint oil, and had determined that roughly its structure, Stol and Rouve determine that the structure of leaf-alcohol is cis-blatter alcohol.In the time that nineteen twenty is carried out the fermentation of black tea, also found leaf-alcohol greatly, about nineteen thirty, Japanese chemist has also been found it in the fresh leaf of tea.In succession in many higher plants, find leaf-alcohol, in Spanish jasmin, little Hua jasmine, peppermint and locust tree etc.In the leaf oil of acacia and mulberry tree, the content of leaf-alcohol can reach 50%, in green tea nearly 30%.The natural extract method of leaf-alcohol can, by separation and Extraction in these plants, be mainly by extracting in essential oil, and then with corresponding phthalic acid salt or allophanic acid reactant salt and purify, the cis-isomeride obtaining accounts for 95%.
The own limited amount of essential oil extracting from plant, often contains again miscellaneous compound in essential oil.Thereby wish extract, be separated to a certain concrete compound (as leaf-alcohol) quite difficulty, and extract yield also atomic.Obviously, directly from natural phant, extracting leaf-alcohol cannot meet the demand to leaf-alcohol, and this is also extremely uneconomic in practice.
Chemosynthesis is the main method that current leaf-alcohol is produced.Existing document has been delivered tens of kinds of chemical synthesis process, has several suitability for industrialized production that realized.Take a broad view of many chemical synthesis process, the key of synthesizing leaf alcohol is how to improve yield and Stereoselective introducing 3 one cis-double bondss.The method of introducing 3 one cis-double bondss mainly contains five kinds: the catalytic hydrogenation of the one, 3-hexin-1-alcohol; The 2nd, the selective reduction of conjugation hexadienol; The reductive ring open of the chloro-2-ethyltetrahydrofuran of the 3rd, 3-; The 4th, the conversion of cis-form olefin derivative; The 5th, utilize Witting reaction.In these methods, all exist at present one or more in following shortcoming: technique is long, yield is low, severe reaction conditions, large to equipment corrosion, materials safety is low.In addition, the Atom economy that also weak point of common existence is these synthetic methods is poor, and building-up process can produce a large amount of three wastes.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect that above-mentioned prior art exists, and a kind of synthetic method of leaf-alcohol is provided, and it is taking positive amylene and formaldehyde as raw material, overcritical, carry out condensation reaction, single stage method synthesizing leaf alcohol under without the condition of any catalyzer.
For this reason, the present invention adopts following technical scheme: a kind of method of supercritically synthesizing leaf alcohol, its step is as follows: the positive amylene of raw material is 2-20 with the mole dosage ratio of formaldehyde: 1, both enter in serpentine reactor after mixing in solvent, at temperature of reaction 180-350 DEG C, under the super critical condition of reaction pressure 8-35MPa, carry out continuously condensation reaction, reaction product stops the outlet from serpentine reactor after 3-120 minute and flows out, then enter in flasher through high-pressure valve, the low-boiling-point substance flashing off is chilled to 40 DEG C of following inflows in light constituent susceptor through condenser, residuum flows in heavy constituent susceptor, and then the product that rectifying separation obtains respectively, isolated solvent and unreacted positive amylene are directly applied mechanically.
According to Green Chemistry definition, catalyzer also may pollute.So using non-toxic catalyst, improving catalyst activity minimizing consumption is all positive measure.Certainly it is optimal, just reaching same reaction effect while having catalyzer to exist without catalyzer.
Overcritical is a physical phenomenon.At Near The Critical Point, the physicochemical property of material are undergone mutation, and have departed from thermodynamics, the kinetic property of normality.The present invention utilizes this principle exactly, has realized under overcritical, catalyst-free condition and having reacted.
In above-mentioned synthetic method, the residence time of reaction product is preferably 20-120 minute, most preferably is 30-60 minute; The positive amylene of raw material is preferably 4-20 with the mole dosage ratio of formaldehyde: 1, most preferably be 5-10: 1; Temperature of reaction is preferably 240-350 DEG C, most preferably is 260-280 DEG C; Reaction pressure is preferably 15-35MPa, most preferably is 18-20MPa.
The available solvent of the present invention has alcohols (methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol etc.), alkanes (propane, butane, Trimethylmethane, pentane, iso-pentane, hexane, hexanaphthene etc.), organic amine (methylamine, ethamine, diethylamine, triethylamine etc.), aromatics (toluene, ethylbenzene etc.), heterocyclic (pyridine, furans etc.), also have carbonic acid gas or their mixed solvent, wherein particularly preferably ethanol, propane, triethylamine, pyridine, carbonic acid gas or their mixture.
The invention has the beneficial effects as follows: technique is brief, only have single step reaction, stable operation, the Atom economy of serialization synthetic method be good, it is little to pollute; Serpentine reactor good heat-transfer, manufacture simple, less investment, operational safety.
Detail of the present invention is described in detail in embodiment below, but embodiment should not be construed as restriction protection scope of the present invention.
Brief description of the drawings
Fig. 1 is the present invention's device schematic diagram used.
In figure, A1, stock bottle; A2, heavy constituent susceptor; A3, light constituent susceptor; B1, B2, gauge line; C1, high-pressure metering pump; D1, serpentine reactor; E1, high-pressure valve; F1, flasher; G1, condenser; T1, thermometer; P1, tensimeter.
Embodiment
As shown in Figure 1, after the methanol solution of positive amylene/formaldehyde is even by the mixed in molar ratio of setting, add in stock bottle A1, raw material is pressed into gauge line B1 with purity nitrogen, in B2, squeeze into φ 4 × 1 through high-pressure metering pump C1, in the stainless steel serpentine reactor D1 of long 20 meters, temperature of reaction 180-350 DEG C, high pressure measurement pump discharge pressure 8-35MPa, reaction product residence time 3-120min, reaction product enters in flasher F1 through high-pressure valve E1, the low-boiling-point substance flashing off is chilled to 40 DEG C of following inflows in light constituent susceptor A3 through condenser G1, residuum flows in heavy constituent susceptor A2, and then the product that rectifying separation obtains respectively, isolated solvent and unreacted positive amylene are directly applied mechanically.
Embodiment 1-10
Overcritical, the methanol solution continuous reaction of positive amylene/formaldehyde under catalyst-free condition, the different residence time with the productive rate of blatter alcohol phase PARA FORMALDEHYDE PRILLS(91,95) in table 1.
The relation of table 1 residence time and the productive rate of blatter alcohol phase PARA FORMALDEHYDE PRILLS(91,95)
Reaction conditions: positive amylene: formaldehyde=6 (mol); Temperature, 280 DEG C; Pressure, 20MPa.
Example 11-20
The relation of the mol ratio of raw material and the productive rate of blatter alcohol phase PARA FORMALDEHYDE PRILLS(91,95), in table 2.
The relation of the mol ratio of table 2 raw material and the productive rate of blatter alcohol phase PARA FORMALDEHYDE PRILLS(91,95)
Reaction conditions: temperature, 280 DEG C; Pressure, 20MPa; The residence time, 30min.
Embodiment 21-30
Temperature of reaction with the productive rate of blatter alcohol phase PARA FORMALDEHYDE PRILLS(91,95) in table 3.
The relation of table 3 temperature of reaction and the productive rate of blatter alcohol phase PARA FORMALDEHYDE PRILLS(91,95)
Reaction conditions: positive amylene: formaldehyde=6 (mol); Pressure, 20MPa, the residence time, 30min.
Embodiment 31-39
Reaction pressure with the productive rate of blatter alcohol phase PARA FORMALDEHYDE PRILLS(91,95) in table 4.
The relation of table 4 reaction pressure and the productive rate of blatter alcohol phase PARA FORMALDEHYDE PRILLS(91,95)
Reaction conditions: positive amylene: formaldehyde=6 (mol); Temperature, 280 DEG C, the residence time, 30min.
The above, be only preferred embodiment of the present invention, not technology contents of the present invention done to any pro forma restriction.Any simple modification, equivalent variations and modification that every foundation technical spirit of the present invention is done above embodiment, all fall within the scope of protection of the present invention.
Claims (10)
1. the method for a supercritically synthesizing leaf alcohol, its step is as follows: the positive amylene of raw material is 2-20:1 with the mole dosage ratio of formaldehyde, both enter after mixing in solvent in a serpentine reactor, at temperature of reaction 180-350 DEG C, under the super critical condition of reaction pressure 8-35MPa, carry out continuously condensation reaction, reaction product stops the outlet from serpentine reactor after 3-120 minute and flows out, then enter in flasher through high-pressure valve, the low-boiling-point substance flashing off is chilled to 40 DEG C of following inflows in light constituent susceptor through condenser, residuum flows in heavy constituent susceptor, and then the product that rectifying separation obtains respectively.
2. the method for supercritically synthesizing leaf alcohol according to claim 1, is characterized in that isolated solvent and unreacted positive amylene directly apply mechanically.
3. the method for supercritically synthesizing leaf alcohol according to claim 1 and 2, the residence time that it is characterized in that reaction product is 20-120 minute.
4. the method for supercritically synthesizing leaf alcohol according to claim 3, the residence time that it is characterized in that reaction product is 30-60 minute.
5. the method for supercritically synthesizing leaf alcohol according to claim 1 and 2, is characterized in that the positive amylene of raw material and the mole dosage ratio of formaldehyde are 4-20:1.
6. the method for supercritically synthesizing leaf alcohol according to claim 5, is characterized in that the positive amylene of raw material and the mole dosage ratio of formaldehyde are 5-10:1.
7. the method for supercritically synthesizing leaf alcohol according to claim 1 and 2, is characterized in that temperature of reaction is 240-350 DEG C.
8. the method for supercritically synthesizing leaf alcohol according to claim 7, is characterized in that temperature of reaction is 260-280 DEG C.
9. the method for supercritically synthesizing leaf alcohol according to claim 1 and 2, is characterized in that reaction pressure is 15-35MPa.
10. the method for supercritically synthesizing leaf alcohol according to claim 9, is characterized in that reaction pressure is 18-20MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010286704.1A CN101928203B (en) | 2010-09-19 | 2010-09-19 | Method for supercritically synthesizing leaf alcohol |
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| CN201010286704.1A CN101928203B (en) | 2010-09-19 | 2010-09-19 | Method for supercritically synthesizing leaf alcohol |
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| CN101928203B true CN101928203B (en) | 2014-11-26 |
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| CN104130107B (en) * | 2014-08-06 | 2016-07-06 | 浙江新和成股份有限公司 | A kind of preparation method being synthesized 3-methyl-3-butene-1-alcohol by formaldehyde hemiacetal |
| CN108003018B (en) * | 2017-12-26 | 2021-01-15 | 浙江新和成股份有限公司 | Method and equipment for preparing cyclopentanol under supercritical condition |
| CN107935888B (en) * | 2017-12-26 | 2020-04-07 | 浙江新和成股份有限公司 | Method for preparing 3-aminopropionitrile under supercritical condition |
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| CN1762941A (en) * | 2004-10-20 | 2006-04-26 | 大连圣迈化学有限公司 | Leaf alcohol synthesis method |
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