CN103058829A - Method for manufacturing carvacrol by carvone composite foot oil - Google Patents
Method for manufacturing carvacrol by carvone composite foot oil Download PDFInfo
- Publication number
- CN103058829A CN103058829A CN2012105712107A CN201210571210A CN103058829A CN 103058829 A CN103058829 A CN 103058829A CN 2012105712107 A CN2012105712107 A CN 2012105712107A CN 201210571210 A CN201210571210 A CN 201210571210A CN 103058829 A CN103058829 A CN 103058829A
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- karvon
- isothymol
- carvone
- pin oil
- reaction
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for manufacturing carvacrol by carvone composite foot oil. The method comprises the steps of enabling sodium hydrogen sulfite and carvone of the composite foot oil to be subjected to an additive reaction, generating water-soluble alpha-hydroxy sodium sulfonate, separating insoluble organic impurities, then heating the alpha-hydroxy sodium sulfonate together with alkali, hydrolyzing the alpha-hydroxy sodium sulfonate and the alkali to be the carvone, isomerizing and rectifying the carvone, and obtaining the carvacrol. The alkali is sodium hydroxide. The method for manufacturing the carvacrol by the carvone composite foot oil has the advantages of being temperate in reaction condition, convenient to operate and prone to industrialization. Waste water generated in various steps of the reaction is neutral. A sulfuric acid solution can be repeatedly used. A recovery rate of the carvone of the composite foot oil is more than 80 percent. The manufactured carvacrol is more than 9.5 percent in content and product quality indexes are higher than the perfume grade standard.
Description
Technical field
The present invention relates to produce from a kind of flavor compounds waste the method for another kind of flavor compounds, be specifically related to a kind of method of getting isothymol with synthetic pin oiling of Karvon legal system.
Background technology
(English name: Carvacrol), be a kind of colourless to flaxen thick liquid, molecular formula is C to isothymol
10H
12O, molecular weight are 150.22, fusing point 1oC, and boiling point 236oC, water insoluble, be dissolved in the organic solvents such as ethanol.
Isothymol has medicinal herbs, Xin Xiang, icy, sootiness, camphor, tobacco aroma and sootiness, Xin Xiang, medicinal herbs, the banksia rose, phenol taste.Having very strong bactericidal properties, be widely used in food flavour, foodstuff additive, oxidation inhibitor, sanitas etc., be usually used in toothpaste, collutory and the cosmeceutical, is a kind of spices with wide market outlook.
In the Karvon production process, the waste water of each operation can produce a large amount of synthetic pin oil after aeration, neutralizing treatment, wherein the content of Karvon reaches about 30%, but because of impurity many, even also being difficult to it is purified through rectifying repeatedly utilizes, greatly increased on the contrary energy consumption and affected the quality of the finished product, so generally all as offal treatment, so both cause waste, also brought comparatively serious environmental issue.A Karvon device of producing 1500 tons per year will produce 400 tons of synthetic pin oil, wherein Karvon significant quantity hundredweights every year, if can be with its effective recycling, make the higher isothymol of added value, with the decrease production cost, create larger economic and social benefit.
Summary of the invention
The object of the present invention is to provide a kind of method of getting isothymol with synthetic pin oiling of Karvon legal system, with the effective recycling waste, make the higher isothymol of added value, reduce production costs, create economic benefit, solve environmental issue.
The present invention is achieved through the following technical solutions:
A kind of method of producing isothymol with the synthetic pin oil of Karvon, with the Karvon generation addition reaction in sodium bisulfite and the synthetic pin oil, generate water miscible Alpha-hydroxy sodium sulfonate, be total to heat with alkali again after separating insoluble organic impurity, be hydrolyzed to Karvon, Karvon again through isomerization, rectifying and isothymol.Described alkali is sodium hydroxide.
Produce the method for isothymol with the synthetic pin oil of Karvon, comprise following concrete preparation process:
(1) under agitation, dropping into mass concentration in the reactor is 40% sodium sulfite solution, be warming up to more than 70 ℃, dropping contains the synthetic pin oil of Karvon, the control temperature is at 70 ℃～80 ℃ in the dropping process, 70 ℃～80 ℃ insulation reaction, when Content of Carvone is lower than 0.5% in the organic phase, finish reaction after dripping off;
(2) thin up, dissolving are left standstill, and divide and go organic phase, and water extracts with toluene, gets Alpha-hydroxy sodium sulfonate solution;
(3) dropping into concentration in step (2) solution is 30% sodium hydroxide solution, stir, and temperature rising reflux reaction 2 hours, cooling is neutralized to neutrality with acid, leaves standstill, and the phase of minute anhydrating gets Karvon;
(4) adding concentration in the reactor is the sulphuric acid soln of 35-40%, stir, be warming up to backflow, drip the Karvon of step (3) gained, drip off rear continuation back flow reaction, when Content of Carvone is lower than 0.1% in the organic phase, finish reaction, cooling is left standstill, minute sub-cloud sulphuric acid soln, upper oil phase gets isothymol with extremely neutral with washing in the alkali.
Karvon in the synthetic pin oil and the mol ratio of sodium bisulfite are 1:1-1.2.
The mol ratio of Alpha-hydroxy sodium sulfonate and sodium hydroxide is 1:1-1.2.
The mass ratio of Karvon and sulphuric acid soln is 2-3:1.
Neutralization acid described in the step (3) is sulfuric acid or hydrochloric acid.
The present invention has following advantage:
(1) reaction conditions is gentle, and is easy to operate, is easy to industrialization.
(2) each step is reacted the middle wastewater that is that produces.
(3) sulphuric acid soln is reusable.
(4) rate of recovery of Karvon＞80% in the synthetic pin oil.
(5) the isothymol content of producing＞99.5%, product quality indicator is higher than the spices grade standard.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not had any restriction.
Embodiment one:
Under whipped state, in reactor, drop into 187.5kg water and 125kg sodium bisulfite, convert into concentration and be 40% sodium sulfite solution, stir, be warming up to 70 ℃, drip the synthetic pin oil that 500kg contains 30% Karvon, the control temperature is at 70 ℃～80 ℃ in the dropping process, 70 ℃～80 ℃ insulation reaction, every 1 hour sampling analysis, when Content of Carvone is lower than 0.5% in the organic phase, finish reaction after dripping off.Add the dilution of 300kg water, dissolving, leave standstill, divide and go organic phase, water toluene extracting twice, get approximately 730kg of Alpha-hydroxy sodium sulfonate solution.
Drop into 160kg concentration in the above-mentioned Alpha-hydroxy sodium sulfonate solution and be 30% sodium hydroxide solution, stir, temperature rising reflux reaction 2 hours, cooling, the sulphuric acid soln with 40% is neutralized to neutrality, leaves standstill, and divides the phase of anhydrating, and gets approximately 145kg of Karvon, Content of Carvone＞97%.
Preparation 48kg mass concentration is 40% sulphuric acid soln in reactor, stirs, and is warming up to backflow, drip the 145kg Karvon of above-mentioned gained, drip off rear control back flow reaction, every 1 hour sampling analysis, when Content of Carvone is lower than 0.1% in the organic phase, finish reaction, cooling, leave standstill, minute sub-cloud sulphuric acid soln (reusable), upper oil phase is with extremely neutral with washing in the sodium hydroxide solution, get approximately 142kg of isothymol crude product, isothymol content＞98%.
With the rectification under vacuum of above-mentioned isothymol crude product, get isothymol significant quantity 125kg, isothymol content＞99.5% in the finished product, the Karvon rate of recovery 83.3% in the synthetic pin oil.
Embodiment two:
Under whipped state, in reactor, drop into 156kg water and 104kg sodium bisulfite, convert into mass concentration and be 40% sodium sulfite solution, stir, be warming up to 70 ℃, drip the synthetic pin oil that 500kg contains 30% Karvon, the control temperature is at 70 ℃～80 ℃ in the dropping process, 70 ℃～80 ℃ insulation reaction, every 1 hour sampling analysis, when Content of Carvone is lower than 0.5% in the organic phase, finish reaction after dripping off.Add the dilution of 300kg water, dissolving, leave standstill, divide and go organic phase, water toluene extracting twice, get approximately 725kg of Alpha-hydroxy sodium sulfonate solution.
Drop into 135kg concentration in the above-mentioned Alpha-hydroxy sodium sulfonate solution and be 30% sodium hydroxide solution, stir, temperature rising reflux reaction 2 hours, cooling, the sulphuric acid soln with 40% is neutralized to neutrality, leaves standstill, and divides the phase of anhydrating, and gets approximately 142kg of Karvon, Content of Carvone＞97%.
Preparation 71kg concentration is 35% sulphuric acid soln in reactor, stirs, and is warming up to backflow, drip the 142kg Karvon of above-mentioned gained, drip off rear control back flow reaction, every 1 hour sampling analysis, when Content of Carvone is lower than 0.1% in the organic phase, finish reaction, cooling, leave standstill, minute sub-cloud sulphuric acid soln (reusable), upper oil phase is with extremely neutral with washing in the sodium hydroxide solution, get approximately 140kg of isothymol crude product, isothymol content＞98%.
With the rectification under vacuum of above-mentioned isothymol crude product, get isothymol significant quantity 123kg, isothymol content＞99.5% in the finished product, the Karvon rate of recovery 82% in the synthetic pin oil.
Embodiment three:
Under whipped state, in reactor, drop into 171.6kg water and 114.4kg sodium bisulfite, convert into concentration and be 40% sodium sulfite solution, stir, be warming up to 70 ℃, drip the synthetic pin oil that 500kg contains 30% Karvon, the control temperature is at 70 ℃～80 ℃ in the dropping process, 70 ℃～80 ℃ insulation reaction, every 1 hour sampling analysis, when Content of Carvone is lower than 0.5% in the organic phase, finish reaction after dripping off.Add the dilution of 300kg water, dissolving, leave standstill, divide and go organic phase, water toluene extracting twice, get approximately 727kg of Alpha-hydroxy sodium sulfonate solution.
Drop into 147kg concentration in the above-mentioned Alpha-hydroxy sodium sulfonate solution and be 30% sodium hydroxide solution, stir, temperature rising reflux reaction 2 hours, cooling, the sulphuric acid soln with 40% is neutralized to neutrality, leaves standstill, and divides the phase of anhydrating, and gets approximately 143kg of Karvon, Content of Carvone＞97%.
Preparation 57.2kg concentration is 35% sulphuric acid soln in reactor, stirs, and is warming up to backflow, drip the 143kg Karvon of above-mentioned gained, drip off rear control back flow reaction, every 1 hour sampling analysis, when Content of Carvone is lower than 0.1% in the organic phase, finish reaction, cooling, leave standstill, minute sub-cloud sulphuric acid soln (reusable), upper oil phase is with extremely neutral with washing in the sodium hydroxide solution, get approximately 141kg of isothymol crude product, isothymol content＞98%.
With the rectification under vacuum of above-mentioned isothymol crude product, get isothymol significant quantity 124kg, isothymol content＞99.5% in the finished product, the Karvon rate of recovery 82.7% in the synthetic pin oil.
Claims (7)
1. produce the method for isothymol with the synthetic pin oil of Karvon, it is characterized in that: with the Karvon generation addition reaction in sodium bisulfite and the synthetic pin oil, generate water miscible Alpha-hydroxy sodium sulfonate, be total to heat with alkali again after separating insoluble organic impurity, be hydrolyzed to Karvon, Karvon again through isomerization, rectifying and isothymol.
2. a kind of method of producing isothymol with the synthetic pin oil of Karvon as claimed in claim 1, it is characterized in that: described alkali is sodium hydroxide.
3. a kind of method of producing isothymol with the synthetic pin oil of Karvon as claimed in claim 1 or 2 is characterized in that comprising following concrete preparation process:
(1) under agitation, dropping into mass concentration in the reactor is 40% sodium sulfite solution, be warming up to more than 70 ℃, dropping contains the synthetic pin oil of Karvon, the control temperature is at 70 ℃～80 ℃ in the dropping process, 70 ℃～80 ℃ insulation reaction, when Content of Carvone is lower than 0.5% in the organic phase, finish reaction after dripping off;
(2) thin up, dissolving are left standstill, and divide and go organic phase, and water extracts with toluene, gets Alpha-hydroxy sodium sulfonate solution;
(3) dropping into concentration in the Alpha-hydroxy sodium sulfonate solution of step (2) gained is 30% sodium hydroxide solution, stir, and temperature rising reflux reaction 2 hours, cooling is neutralized to neutrality with acid, leaves standstill, and the phase of minute anhydrating gets Karvon;
(4) adding concentration in the reactor is the sulphuric acid soln of 35-40%, stir, be warming up to backflow, drip the Karvon of step (3) gained, drip off rear continuation back flow reaction, when Content of Carvone is lower than 0.1% in the organic phase, finish reaction, cooling is left standstill, minute sub-cloud sulphuric acid soln, upper oil phase gets isothymol with extremely neutral with washing in the alkali.
4. a kind of method of producing isothymol with the synthetic pin oil of Karvon as claimed in claim 2, it is characterized in that: the Karvon in the synthetic pin oil and the mol ratio of sodium bisulfite are 1:1-1.2.
5. a kind of method of producing isothymol with the synthetic pin oil of Karvon as claimed in claim 2, it is characterized in that: the mol ratio of Alpha-hydroxy sodium sulfonate and sodium hydroxide is 1:1-1.2.
6. a kind of method of producing isothymol with the synthetic pin oil of Karvon as claimed in claim 2, it is characterized in that: the mass ratio of Karvon and sulphuric acid soln is 2-3:1.
7. a kind of method of producing isothymol with the synthetic pin oil of Karvon as claimed in claim 2, it is characterized in that: the neutralization acid described in the step (3) is sulfuric acid or hydrochloric acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210571210.7A CN103058829B (en) | 2012-12-26 | 2012-12-26 | Method for manufacturing carvacrol by carvone composite foot oil |
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| CN201210571210.7A CN103058829B (en) | 2012-12-26 | 2012-12-26 | Method for manufacturing carvacrol by carvone composite foot oil |
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| CN103058829A true CN103058829A (en) | 2013-04-24 |
| CN103058829B CN103058829B (en) | 2014-10-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130771A (en) * | 2015-08-03 | 2015-12-09 | 福建青松股份有限公司 | Technology utilizing byproduct namely dipentene in camphor synthesis to synthesize carvone and applications thereof |
| CN105646155A (en) * | 2016-01-22 | 2016-06-08 | 淮安万邦香料工业有限公司 | Method for synthesizing carvacrol with limonene epoxide foot oil |
| CN105693474A (en) * | 2016-01-22 | 2016-06-22 | 淮安万邦香料工业有限公司 | Method for synthetizing carvacrol through enediol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB584256A (en) * | 1942-07-13 | 1947-01-10 | Shell Dev | Production of phenolic compounds |
| CN101475448A (en) * | 2009-01-21 | 2009-07-08 | 淮安万邦香料工业有限公司 | Green synthesis of high-content carvacrol capable of replacing natural origanum |
| CN101475449A (en) * | 2009-01-21 | 2009-07-08 | 淮安万邦香料工业有限公司 | Method for preparing carvacrol by recycling carvone synthesis by-product |
-
2012
- 2012-12-26 CN CN201210571210.7A patent/CN103058829B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB584256A (en) * | 1942-07-13 | 1947-01-10 | Shell Dev | Production of phenolic compounds |
| CN101475448A (en) * | 2009-01-21 | 2009-07-08 | 淮安万邦香料工业有限公司 | Green synthesis of high-content carvacrol capable of replacing natural origanum |
| CN101475449A (en) * | 2009-01-21 | 2009-07-08 | 淮安万邦香料工业有限公司 | Method for preparing carvacrol by recycling carvone synthesis by-product |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130771A (en) * | 2015-08-03 | 2015-12-09 | 福建青松股份有限公司 | Technology utilizing byproduct namely dipentene in camphor synthesis to synthesize carvone and applications thereof |
| CN105646155A (en) * | 2016-01-22 | 2016-06-08 | 淮安万邦香料工业有限公司 | Method for synthesizing carvacrol with limonene epoxide foot oil |
| CN105693474A (en) * | 2016-01-22 | 2016-06-22 | 淮安万邦香料工业有限公司 | Method for synthetizing carvacrol through enediol |
| CN105646155B (en) * | 2016-01-22 | 2018-08-03 | 淮安万邦香料工业有限公司 | The method for synthesizing carvacrol with limonene epoxide foot oil |
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| CN103058829B (en) | 2014-10-15 |
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Address after: 223300 No. 216 Changjiang East Road, Huaiyin District, Jiangsu, Huaian Patentee after: Wanxiang Technology Co., Ltd. Address before: 223300 No. 216 Changjiang East Road, Huaiyin District, Jiangsu, Huaian Patentee before: Huaian Wanbang Aromatic Chemicals Co., Ltd. |
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