CN106542950B - A method of limonene is prepared by 3- carene - Google Patents
A method of limonene is prepared by 3- carene Download PDFInfo
- Publication number
- CN106542950B CN106542950B CN201610943278.1A CN201610943278A CN106542950B CN 106542950 B CN106542950 B CN 106542950B CN 201610943278 A CN201610943278 A CN 201610943278A CN 106542950 B CN106542950 B CN 106542950B
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- China
- Prior art keywords
- limonene
- carene
- terpinum
- sulfuric acid
- prepared
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
Abstract
The invention discloses a kind of methods for preparing limonene by 3- carene, include the following steps: step 1: under the conditions of by 3- carene existing for the sulfuric acid, being kept for 15 DEG C~35 DEG C of reaction temperature and terpinum is prepared；Step 2: under the conditions of by terpinum existing for the sulfuric acid, being kept for 0 DEG C~10 DEG C of reaction temperature and limonene is prepared；The purpose of the present invention is to provide a kind of methods for preparing limonene by 3- carene, limonene is prepared using cheap 3- carene in this method, high conversion rate and preparation flow is relatively simple, and preparation-obtained limonene is separated with other by-products and is relatively easy to.
Description
Technical field
The present invention relates to the carene deep process technology field 3- more particularly to a kind of sides that limonene is prepared by 3- carene
Method.
Background technique
3- carene chemical name is 3,7,7- trimethyl bicyclic [4,1,0] hept- 3- alkene, and molecular formula C10H16 is opposite to divide
Protonatomic mass is 136.24, is widely used as Material synthesis fragrance, pesticide and drug etc..Limonene alias limonene, limonene and double penta
Alkene etc., monoterpenes compound, colourless oil liquid have the lemonish fragrance of class.With good antibechic, eliminating the phlegm, bacteriostasis,
Compound limonene clinically can be used for cholagogue, dissolve stone, promotes digestive juice secretion and exclude enteral pneumatosis.
If the higher limonene of price can be prepared with price more cheap 3- carene by suitable technique,
Then there are extraordinary market prospects.
Summary of the invention
In view of the above deficiencies, the purpose of the present invention is to provide a kind of method for preparing limonene by 3- carene, the party
Limonene is prepared using cheap 3- carene in method, high conversion rate and preparation flow is relatively simple, and prepared
To limonene separate and be relatively easy to other by-products.
In order to solve the above technical problem, the present invention provides following technical schemes: one kind preparing limonene by 3- carene
Method, include the following steps:
Step 1: under the conditions of by 3- carene existing for the sulfuric acid, being kept for 15 DEG C~35 DEG C of reaction temperature and terpene two is prepared
Alcohol；
Step 2: under the conditions of by terpinum existing for the sulfuric acid, being kept for 0 DEG C~10 DEG C of reaction temperature and limonene is prepared.
Its specific preparation flow is as follows:
In the above-mentioned method for preparing limonene by 3- carene, the step 1 specifically: by 3- carene, quality
Percentage be 5%~35% aqueous sulfuric acid, according to 1:2 volume ratio mix, add mixed liquor weight 0.05%~
0.15% emulsifier is heated to 15 DEG C~35 DEG C, after being stirred to react 8 hours~16 hours, reaction solution static layering, and removal
Oil reservoir, filtering solution, obtained solid substance are terpinum.
Emulsifier can be conventional emulsifier in the present invention, but cannot select can be with the emulsifier of sulfuric acid reaction.Specifically
Emulsifier can choose are as follows: AEO-9 (fatty alcohol polyoxyethylene ether), polysorbate40, neopelex.
In the above-mentioned method for preparing limonene by 3- carene, terpinum is washed to pH value it is by repeatedly washing
7。
In the above-mentioned method for preparing limonene by 3- carene, the step 2 specifically: by gained terpinum,
The aqueous sulfuric acid that mass percent is 5%~35% mixes according to the mass ratio of 1:2, adds mixed liquor weight 0.05%
~0.15% emulsifier, reaction temperature are maintained at 0 DEG C~10 DEG C, and after being stirred to react 12 hours~20 hours, reaction solution is quiet
It is only layered, removes water layer, gained oil reservoir after rectifying, can obtain limonene again.
Compared with prior art, technical solution provided by the invention has the advantage that
This method provide can a kind of method that limonene is prepared by 3- carene, make 3- carene resource obtain further opening
Hair and utilization, conversion ratio is higher, and preparation flow is relatively simple.
Specific embodiment
With reference to embodiment, claim of the invention is described in further detail, but do not constituted pair
Any restrictions of the invention, the modification of any limited times made within the scope of the invention as claimed, still in power of the invention
In the claimed range of benefit.
Embodiment one:
The method that this 3- carene prepares limonene, including sequentially include the following steps:
By 3- carene, the aqueous sulfuric acid that mass percent is 5%, is mixed according to the volume ratio of 1:2, add mixed liquor
The emulsifier of weight 0.05% is heated to 20 DEG C, and after being stirred to react 8 hours, reaction solution static layering removes oil reservoir, gained
Containing suspending and precipitate solid material aqueous solution, the reaction was continued, and temperature is maintained at 5 DEG C, and after being stirred to react 12 hours, reaction solution is quiet
It is only layered, removes water layer, gained oil reservoir is again after rectifying to get limonene, wherein the yield of terpinum is 40% or more, lemon
The yield of lemon alkene is 10% or more.
Embodiment two:
The method that this 3- carene prepares limonene, including sequentially include the following steps:
By 3- carene, the aqueous sulfuric acid that mass percent is 20%, is mixed according to the volume ratio of 1:2, add mixing
The emulsifier of liquid weight 0.1% is heated to 30 DEG C, and after being stirred to react 12 hours, reaction solution static layering removes oil reservoir, institute
Suspension and precipitate solid material aqueous solution must be contained, the reaction was continued, and temperature is maintained at 5 DEG C, after being stirred to react 12 hours, reaction solution
Static layering removes water layer, and gained oil reservoir is again after rectifying to get limonene, wherein and the yield of terpinum is 70% or more,
The yield of limonene is 15% or more.
Embodiment three:
The method that this 3- carene prepares limonene, including sequentially include the following steps:
By 3- carene, the aqueous sulfuric acid that mass percent is 35%, is mixed according to the volume ratio of 1:2, add mixing
The emulsifier of liquid weight 0.15% is heated to 40 DEG C, and after being stirred to react 16 hours, reaction solution static layering removes oil reservoir, institute
Suspension and precipitate solid material aqueous solution must be contained, the reaction was continued, and temperature is maintained at 10 DEG C, after being stirred to react 20 hours, reacts molten
Liquid static layering, remove water layer, gained oil reservoir is again after rectifying to get limonene, wherein the yield of terpinum be 80% with
On, the yield of limonene is 20% or more.
Product includes limonene and terpinol and terpinolene in the embodiment of the present invention 1-3, this three can be easily separated,
A small amount of product uses rectifying column, and industrial products use rectifying column, due to the boiling point of each product it is different (177 DEG C of limonene boiling point,
221 DEG C of terpinol boiling point, 187 DEG C of terpinolene boiling point), tower top temperature is controlled, each product can be isolated.
Above-described is only presently preferred embodiments of the present invention, all made within the scope of the spirit and principles in the present invention
What modifications, equivalent substitutions and improvements etc., should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of method for preparing limonene by 3- carene, which comprises the steps of:
Step 1: under the conditions of by 3- carene existing for the sulfuric acid, being kept for 15 DEG C~35 DEG C of reaction temperature and terpinum is prepared；
Step 2: under the conditions of by terpinum existing for the sulfuric acid, being kept for 0 DEG C~10 DEG C of reaction temperature and limonene is prepared.
2. the method according to claim 1 for preparing limonene by 3- carene, which is characterized in that step 1 tool
Body are as follows: by 3- carene, the aqueous sulfuric acid that mass percent is 5%~35%, mix, add mixed according to the volume ratio of 1:2
The emulsifier for closing liquid weight 0.05%~0.15%, is heated to 15 DEG C~35 DEG C, after being stirred to react 8 hours~16 hours, reaction
Solution stand layering, removes oil reservoir, filtering solution, obtained solid substance is terpinum.
3. the method according to claim 2 for preparing limonene by 3- carene, which is characterized in that by repeatedly wash by
It is 7 that terpinum, which is washed to pH value,.
4. the method according to claim 1 for preparing limonene by 3- carene, which is characterized in that step 2 tool
Body are as follows: by gained terpinum, the aqueous sulfuric acid that mass percent is 5%~35%, mixed according to the mass ratio of 1:10, then plus
Enter the emulsifier of mixed liquor weight 0.05%~0.15%, reaction temperature is maintained at 0 DEG C~10 DEG C, is stirred to react 12 hours~20
After hour, reaction solution static layering removes water layer, and gained oil reservoir after rectifying, can obtain limonene again.
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| CN201610943278.1A CN106542950B (en) | 2016-10-26 | 2016-10-26 | A method of limonene is prepared by 3- carene |
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| CN201610943278.1A CN106542950B (en) | 2016-10-26 | 2016-10-26 | A method of limonene is prepared by 3- carene |
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| CN106542950A CN106542950A (en) | 2017-03-29 |
| CN106542950B true CN106542950B (en) | 2019-03-26 |
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| CN116172152A (en) * | 2023-02-23 | 2023-05-30 | 北京火星补给科技文化有限公司 | Process for preparing lemon raw juice by adding water-washed lemon oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778779A (en) * | 2004-11-18 | 2006-05-31 | 浙江工业大学 | 1-aryl (group) - 1 - ethylenialkene and production thereof |
| CN102482178A (en) * | 2009-07-16 | 2012-05-30 | 联邦科学和工业研究组织 | Cineole |
| CN103360199A (en) * | 2012-04-03 | 2013-10-23 | 日立造船株式会社 | Preparation method for isoprene and limonene |
-
2016
- 2016-10-26 CN CN201610943278.1A patent/CN106542950B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778779A (en) * | 2004-11-18 | 2006-05-31 | 浙江工业大学 | 1-aryl (group) - 1 - ethylenialkene and production thereof |
| CN102482178A (en) * | 2009-07-16 | 2012-05-30 | 联邦科学和工业研究组织 | Cineole |
| CN103360199A (en) * | 2012-04-03 | 2013-10-23 | 日立造船株式会社 | Preparation method for isoprene and limonene |
Non-Patent Citations (3)
| Title |
|---|
| AlPO4-Al2O3 Promoted Cyclodehydration of Diols;A. Costa et al;《Synthetic Communications》;19871231;第17卷(第11期);第1373-1376页 |
| Microbial Degradation of Monoter;Jens Harder et al;《Applied and Environmental Microbiology》;19951231;第61卷(第11期);第3804-3808页 |
| 固-液混合酸催化水合萜二醇合成松油醇的研究;班卫平等;《林产化学与工业》;20010331;第21卷(第1期);第75-79页 |
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