CN101928203A - Method for supercritically synthesizing leaf alcohol - Google Patents
Method for supercritically synthesizing leaf alcohol Download PDFInfo
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- CN101928203A CN101928203A CN2010102867041A CN201010286704A CN101928203A CN 101928203 A CN101928203 A CN 101928203A CN 2010102867041 A CN2010102867041 A CN 2010102867041A CN 201010286704 A CN201010286704 A CN 201010286704A CN 101928203 A CN101928203 A CN 101928203A
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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: suitable-3 hexen-1-ols (cis-3-Hexen-1-ol)], outward appearance is a 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.Leaf-alcohol after the dilution has the delicate fragrance of bright grass when cutting off, and gives a kind of pure and fresh, happy sensation of staying the Nature.Leaf-alcohol and derivative thereof are one of famous and precious spices of pandemic scent type, are using in synthetic perfume and the essence more than 40 kinds at least 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 almost is present in all green plantss, and the embodiment of body on smell of so-called symbol plant " green " is exactly leaf-alcohol.Though certainly since the dawn of human civilization, leaf-alcohol just becomes a link of human foods chain, just in tea oil, measured its existence up to 1895.In 1917, people found that again leaf-alcohol is present in the Japanese mint oil, and had determined that roughly its structure, Stol and Rouve determine that the structure of leaf-alcohol is suitable-blatter alcohol.Also found leaf-alcohol greatly when nineteen twenty is carried out the fermentation of black tea, Japanese chemist has also been found it about nineteen thirty in the bright leaf of tea.In many higher plants, found leaf-alcohol in succession, in Spanish jasmin, Xiao Hua jasmine, peppermint and locust tree etc.The content of leaf-alcohol can reach 50% in the leaf oil of acacia and mulberry tree, in the green tea nearly 30%.The natural extract method of leaf-alcohol can be by separation and Extraction in these plants, mainly is by extracting in the essential oil, and then with corresponding phthalic acid salt or allophanic acid reactant salt and purify, the cis-isomeride that obtains accounts for 95%.
The limited amount of the essential oil that extracts from plant own often contains miscellaneous compound again in the essential oil.Thereby desire extracts, is separated to quite difficulty of a certain concrete compound (as leaf-alcohol), and the yield of extracting is also atomic.Obviously, directly extract leaf-alcohol and can't satisfy demand to leaf-alcohol from natural phant, this also is extremely uneconomic in practice.
Chemosynthesis is the main method that present leaf-alcohol is produced.Existing document has been delivered tens of kinds of chemical synthesis process, and several suitability for industrialized production that realized are arranged.Take a broad view of many chemical synthesis process, the key of synthesizing leaf alcohol is how to improve yield and Stereoselective is introduced 3 one cis-double bondss.The method of introducing 3 one cis-double bondss mainly contains five kinds: the one, and the catalytic hydrogenation of 3-hexin-1-alcohol; The 2nd, the selective reduction of conjugation hexadienol; The 3rd, the reductive ring open of 3-chloro-2-ethyltetrahydrofuran; The 4th, the conversion of cis-form olefin derivative; The 5th, utilize the Witting reaction.All exist at present in the following shortcoming one or more in these methods: technology is long, yield is low, severe reaction conditions, big to equipment corrosion, materials safety is low.In addition, the Atom economy that weak point of also 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 defective that above-mentioned prior art exists, and a kind of synthetic method of leaf-alcohol is provided, and it is a raw material with positive amylene and formaldehyde, carries out condensation reaction, the single stage method synthesizing leaf alcohol under the condition of overcritical, no 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, after mixing in solvent, both enter in the serpentine reactor, at temperature of reaction 180-350 ℃, carry out condensation reaction under the super critical condition of reaction pressure 8-35MPa continuously, reaction product stops after 3-120 minute the outlet from serpentine reactor and flows out, enter in the flasher through high-pressure valve then, the low-boiling-point substance that flashes off is chilled to through condenser and flows in the light constituent susceptor below 40 ℃, residuum flows in the heavy constituent susceptor, and then the product that obtains of rectifying separation respectively, isolated solvent and unreacted positive amylene are directly applied mechanically.
According to the Green Chemistry definition, catalyzer also may pollute.So using non-toxic catalyst, improving catalyst activity minimizing consumption all is active measure.Certainly, can reach just without catalyzer that same reaction effect is optimal when having catalyzer to exist.
Overcritical is a physical phenomenon.Near stagnation 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 reacting under overcritical, catalyst-free condition.
In the 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 ℃, most preferably is 260-280 ℃; 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 special preferred alcohol, propane, triethylamine, pyridine, carbonic acid gas or their mixture.
The invention has the beneficial effects as follows: technology is brief, has only single step reaction, and the stable operation of serialization synthetic method, Atom economy is good, pollution is little; The serpentine reactor good heat-transfer, make simple, less investment, operational safety.
Detail of the present invention obtains describing in detail among the embodiment below, but embodiment should not be construed as qualification protection scope of the present invention.
Description of drawings
Fig. 1 is the used device synoptic diagram of the present invention.
Among the 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, the methanol solution of positive amylene/formaldehyde evenly adds among the stock bottle A1 back by the mixed in molar ratio of setting, with purity nitrogen raw material is pressed into gauge line B1, among the B2, squeeze into φ 4 * 1 through high-pressure metering pump C1, among long 20 meters the stainless steel serpentine reactor D1, temperature of reaction 180-350 ℃, high pressure measurement pump discharge pressure 8-35MPa, reaction product residence time 3-120min, reaction product enters among the flasher F1 through high-pressure valve E1, the low-boiling-point substance that flashes off is chilled to through condenser G1 and flows into below 40 ℃ among the light constituent susceptor A3, residuum flows among the heavy constituent susceptor A2, and then the product that obtains of rectifying separation 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 the catalyst-free condition, the different residence time and the blatter alcohol productive rate of PARA FORMALDEHYDE PRILLS(91,95) mutually see Table 1.
Table 1 residence time and blatter alcohol be the relation of the productive rate of PARA FORMALDEHYDE PRILLS(91,95) mutually
Reaction conditions: positive amylene: formaldehyde=6 (mol); Temperature, 280 ℃; Pressure, 20MPa.
Example 11-20
The mol ratio of raw material and blatter alcohol be the relation of the productive rate of PARA FORMALDEHYDE PRILLS(91,95) mutually, sees Table 2.
The mol ratio of table 2 raw material and blatter alcohol be the relation of the productive rate of PARA FORMALDEHYDE PRILLS(91,95) mutually
Reaction conditions: temperature, 280 ℃; Pressure, 20MPa; The residence time, 30min.
Embodiment 21-30
Temperature of reaction and the blatter alcohol productive rate of PARA FORMALDEHYDE PRILLS(91,95) mutually see Table 3.
Table 3 temperature of reaction and blatter alcohol be the relation of the productive rate of PARA FORMALDEHYDE PRILLS(91,95) mutually
Reaction conditions: positive amylene: formaldehyde=6 (mol); Pressure, 20MPa, the residence time, 30min.
Embodiment 31-39
Reaction pressure and the blatter alcohol productive rate of PARA FORMALDEHYDE PRILLS(91,95) mutually see Table 4.
Table 4 reaction pressure and blatter alcohol be the relation of the productive rate of PARA FORMALDEHYDE PRILLS(91,95) mutually
Reaction conditions: positive amylene: formaldehyde=6 (mol); Temperature, 280 ℃, the residence time, 30min.
The above only is preferred embodiment of the present invention, is not technology contents of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all falls within the scope of protection of the present invention any simple modification, equivalent variations and modification that above embodiment did.
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, enter in the serpentine reactor after both mix in solvent, at temperature of reaction 180-350 ℃, carry out condensation reaction under the super critical condition of reaction pressure 8-35MPa continuously, reaction product stops after 3-120 minute the outlet from serpentine reactor and flows out, enter in the flasher through high-pressure valve then, the low-boiling-point substance that flashes off is chilled to through condenser and flows in the light constituent susceptor below 40 ℃, residuum flows in the heavy constituent susceptor, and then the product that obtains of rectifying separation 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 ℃.
8. the method for supercritically synthesizing leaf alcohol according to claim 7 is characterized in that temperature of reaction is 260-280 ℃.
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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130107A (en) * | 2014-08-06 | 2014-11-05 | 浙江新和成股份有限公司 | Preparation method for synthesizing 3-methyl-3-butene-1-ol by using formaldehyde hemiacetal |
| CN107935888A (en) * | 2017-12-26 | 2018-04-20 | 浙江新和成股份有限公司 | A kind of method for preparing 3 aminopropionitriles at supercritical conditions |
| CN108003018A (en) * | 2017-12-26 | 2018-05-08 | 浙江新和成股份有限公司 | A kind of method and its equipment for preparing cyclopentanol at supercritical conditions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA850151A (en) * | 1970-08-25 | Mueller Herbert | Production of alk-3-en-1-ols | |
| 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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- 2010-09-19 CN CN201010286704.1A patent/CN101928203B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA850151A (en) * | 1970-08-25 | Mueller Herbert | Production of alk-3-en-1-ols | |
| CN1762941A (en) * | 2004-10-20 | 2006-04-26 | 大连圣迈化学有限公司 | Leaf alcohol synthesis method |
Non-Patent Citations (5)
| Title |
|---|
| A. T. BLOMQUIST等: "Thermal Condensation of Formaldehyde with Acyclic Olefins", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 79, no. 18, 20 September 1957 (1957-09-20) * |
| NEAL. O. BRACE: "The Uncatalyzed Thermal Additon of Formaldehyde to Olefins", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 77, no. 17, 5 September 1955 (1955-09-05) * |
| 潘斌等: "烯反应及其在有机合成中的应用", 《南昌高专学报》, no. 2, 15 June 2003 (2003-06-15), pages 66 - 67 * |
| 陆国元: "《有机反应与有机合成》", 30 June 2009, article "9.3.6 Alder(ene)反应", pages: 354-355 * |
| 黄明泉等: "叶醇的研究进展", 《北京工商大学学报（自然科学版）》, vol. 23, no. 2, 31 March 2005 (2005-03-31) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130107A (en) * | 2014-08-06 | 2014-11-05 | 浙江新和成股份有限公司 | Preparation method for synthesizing 3-methyl-3-butene-1-ol by using formaldehyde hemiacetal |
| CN107935888A (en) * | 2017-12-26 | 2018-04-20 | 浙江新和成股份有限公司 | A kind of method for preparing 3 aminopropionitriles at supercritical conditions |
| CN108003018A (en) * | 2017-12-26 | 2018-05-08 | 浙江新和成股份有限公司 | A kind of method and its equipment for preparing cyclopentanol at supercritical conditions |
| 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 |
| 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 |
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| CN101928203B (en) | 2014-11-26 |
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