CN102617288A - Method for preparing dihydromyrcenol through reaction distillation continuity - Google Patents
Method for preparing dihydromyrcenol through reaction distillation continuity Download PDFInfo
- Publication number
- CN102617288A CN102617288A CN2012100608766A CN201210060876A CN102617288A CN 102617288 A CN102617288 A CN 102617288A CN 2012100608766 A CN2012100608766 A CN 2012100608766A CN 201210060876 A CN201210060876 A CN 201210060876A CN 102617288 A CN102617288 A CN 102617288A
- Authority
- CN
- China
- Prior art keywords
- dihydromyrcenol
- water
- tower
- dihydromyrcene
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing dihydromyrcenol through reaction distillation continuity. Corrugated gauze filling materials and solid acid catalysts are filled in a reaction distillation tower, raw materials of dihydromyrcene, water and solvents are respectively preheated to 80 to 120 DEG C, 85 to 95 DEG C and 70 to 90 DEG C to be respectively fed from the upper part, the middle part and the lower part of a reaction section of the reaction distillation tower according to the flow rate ratio of (1-3): (1-3). The tower kettle temperature is controlled to be 105 to 120 DEG C, and the tower top condensing temperature is controlled to be 50 to 70 DEG C. An oil phase and a water phase are separated out from condensed liquid, partial oil phase reaches the tower top to flow back, and the water phase and the rest oil phase respectively return a raw material tank to be cyclically utilized. According to the method, the reaction and the distillation are simultaneously carried out, heat released by the reaction can be effectively utilized for heating materials, and a heat load of a tower kettle is reduced. The corrugated gauze filling materials in the reaction distillation tower and a tubular liquid distributor are favorable for improving the effective surfaces for mass transfer and heat transfer and improving the inter phase contact, dihydromyrcenol products with the purity being 95 percent are obtained from the tower bottom, and the reaction efficiency and the dihydromyrcenol conversion rate are higher.
Description
Technical field
The present invention relates to a kind of system method of dihydromyrcenol, particularly reactive distillation serialization and prepare the method for dihydromyrcenol.
Background technology
Dihydromyrcenol (2,6-dimethyl--7-octen-2-ol) is a kind of important terpene spices commonly used, is one of spices kind of consumption maximum in the world.Have the fresh fragrance of a flower and lime appearance fruital, be used for lime, oranges and tangerines type daily essence, consumption can reach 5%～20% in perfumed soap, washing composition.The method of producing at present dihydromyrcenol mainly contains two kinds of indirect hydration method and direct hydration methods.Suitability for industrialized production mainly adopts with dense H
2SO
4Be catalyzer, dihydromyrcene and formic acid esterification, the indirect hydration method of saponified; The transformation efficiency and the selectivity of this method are low, and dense H
2SO
4Serious to equipment corrosion, the waste water of discharging is prone to cause environmental pollution.Direct hydration method is under the effect of an acidic catalyst, and dihydromyrcene and water direct reaction generate dihydromyrcenol, and this method meets the notion of atom economy, has simple, the lower-cost advantage of flow process; But it mainly is batch operation that the direct hydration method that adopts is gone up in industry at present, and after promptly raw material got into the fixed-bed reactor reaction, product got into separating unit and carries out later separation.This technology transformation efficiency is higher, but still has the problem that technical process is long, the process integration degree is not high and cost of investment is bigger.
Summary of the invention
Complicated to existing technical process; Integrated level is low, cost of investment is high and the environmental pollution important disadvantages, the purpose of this invention is to provide that a kind of operational path is simple, the degree of coupling is high, energy consumption and equipment investment cost is lower and the technology of eco-friendly continuously processing dihydromyrcenol.
Reactive distillation serialization of the present invention prepares the method for dihydromyrcenol, and ripple silk net filler and solid acid catalyst are housed in the reaction fractionating tower, and reaction fractionating tower is divided into tower still, stripping section, conversion zone and rectifying section from bottom to top; The preparation process of dihydromyrcenol may further comprise the steps:
(1) dihydromyrcene is preheated to 80～120 ℃, from the top charging of reaction fractionating tower conversion zone; With water preheat to 85～95 ℃, the middle part of input conversion zone; Solvent is preheated to 70～90 ℃, and from the underfeed of conversion zone, the mass flux ratio of dihydromyrcene, water and solvent is 1: (1～3): (1～3); 105～120 ℃ of control tower still temperature; Said solvent is one or more in acetone, acetic ester, methyl alcohol, ethanol, Virahol, butanols, ethylene glycol monobutyl ether, ethylene glycol bis butyl ether, dioxy six alkane;
After dihydromyrcene liquid is gone into tower, flow downward, simultaneously water is heated gasification with solvent, and to the rising of cat head direction, dihydromyrcene and water contact in that conversion zone is reverse, issues unboiled water in the effect of catalyzer and solvent and closes reaction; The azeotrope of unreacted dihydromyrcene, water and solvent continues to rise to rectifying section, discharges from cat head; Tower still extraction product dihydromyrcenol from reaction fractionating tower;
(2) after the azeotrope of said dihydromyrcene, water and solvent is discharged from cat head, be condensed to 50～70 ℃ through the condensing surface cooling.
(3) phlegma is fed phase splitter, tell oil phase and water, the part oil phase on upper strata is returned cat head, all the other oil phases are integrated with in the dihydromyrcene raw material, and lower layer of water is incorporated in the raw water mutually.
Said solid acid catalyst is large hole cation exchanger resin or zeolite catalyst.
Said large hole cation exchanger resin is Purilite CT275, Purilite CT482, Purilite CT151DR, D72, D61, D001-C,, Amberlyst 36, Amberlyst 35, Amberlyst 15 or NKC-9; Said zeolite catalyst is ZSM-5 or mordenite.
For preventing granules of catalyst with the flowing of gas-liquid phase logistics, catalyzer adopts non-woven fabrics, silica wool or wire cloth to be packaged into catalyst pack.
Be provided with liquid distributor in the cat head of said reaction fractionating tower.
As stated, the present invention adopts a reaction fractionating tower and phase splitter can realize the serialization production of dihydromyrcenol, and its superior effect embodies as follows:
(1) this method will be reacted with two PROCESS COUPLING of rectifying and in a device, carried out, and can effectively utilize the reaction liberated heat to add thermal material, alleviate the thermal load of tower still.The effective surface of ripple silk net filler in the reaction fractionating tower and the favourable raising mass transfer of tubular liquid sparger, heat transfer improves alternate contact, thereby improves the efficient of tower.Phase splitter is set simultaneously, avoids getting into the energy waste that causes in the tower again because of water.Compare with the existing processes route, this method has the simplification production technique, and the strengthening process mass-and heat-transfer cuts down the consumption of energy, and saves facility investment.Capable of reducing energy consumption more than 35%, save facility investment more than 50%.
(2) dihydromyrcene, water and solvent charging respectively in the reverse contact of conversion zone, has been strengthened mass-and heat-transfer.When reaction is carried out, remove product, promote reaction to carry out, improve the transformation efficiency of reaction, can obtain the dihydromyrcenol product of purity more than 95% towards the direction that generates product.
(3) adopt the strong acid type macropore cation resin to replace traditional liquid catalyst, reduced, reduced environmental pollution simultaneously corrosion on Equipment.
Description of drawings
Fig. 1 is the schematic flow sheet of reactive distillation continuous production dihydromyrcenol.
Fig. 2 is the liquid distributor structural representation.
Fig. 3 is the catalyst pack synoptic diagram.
Wherein: 1,2, the 3-head tank, 4,5, the 6-pump, 7-reaction fractionating tower, 8-condensing surface, 9-reboiler, 10-phase splitter, 11-catalyst pack, 11-1-granules of catalyst, 12-filler, 13-liquid distributor, 13-1-distribution piping.
Concrete real mode
Referring to Fig. 1, load BX500 ripple silk net filler 12 in the reaction fractionating tower 7; In conversion zone, catalyst pack 11 (being packaged with catalyst A mberlyst 36 strong acid type large hole cation exchanger resins) is mixed filling with BX500 ripple silk net filler 12.See Fig. 3, be packaged with granules of catalyst 11-1 in the catalyst pack interior 11, catalyst pack can be materials such as non-woven fabrics, silica wool or wire cloth.The top of reaction fractionating tower 7 is provided with liquid distributor 13, and Fig. 2 express liquid sparger 13 is provided with distribution piping 13-1.
Before going into operation; Is 1 with dihydromyrcene, water, Virahol (or butanols or acetic ester) by mass ratio: (1～3): (1～3) adds reaction fractionating tower 7; Make the tower still have initial liquid level, start 9 pairs of tower still heating of reboiler, keep 105～120 ℃ of tower still temperature; Total reflux operation 2h, system gets into the operate continuously stage then.The dihydromyrcene of head tank 1 is heated to 95 ℃ through preheater, sends into the top opening for feed of reaction fractionating tower conversion zone through pump 4; The water of head tank 2 is preheated to 90 ℃ through preheater, sends into the middle part opening for feed of reaction fractionating tower 7 conversion zones through pump 5; The solvent Virahol of head tank 3 (butanols or acetic ester) is preheated to 80 ℃ through preheater, is sent into the underfeed mouth of 7 conversion zones of reaction fractionating tower by pump 6.The throughput ratio (mass rate) of control dihydromyrcene, water and Virahol is between 1: 1: 1 to 1: 3: 3.The cat head ejecta is through condensing surface 8 condensations, and keeping tower top temperature is 50-70 ℃, and phlegma is delivered to phase splitter 10, isolates oil phase and is back in the dihydromyrcene head tank 1, recycles as reaction raw materials; , through water pump 5 input water head tanks 2, recycle from phase device 10 separated lower-layer waters.When the oil phase material in the phase splitter 10 began to be back in the reaction fractionating tower 7, termination of pumping 6 promptly stopped solvent feed.From tower still extraction product dihydromyrcenol, purity is more than 95%.Transformation efficiency through calculating dihydromyrcene is 97%, and selectivity is 92%.
Embodiment 2:
Same with embodiment 1 working method, before going into operation, be 1 with dihydromyrcene, water, Virahol (or butanols or acetic ester) by mass ratio: (1～3): (1～3) adds reaction fractionating tower 7, adds Amberlyst 35 strong acid type large hole cation exchanger resins.The reaction fractionating tower reacting section catalyst is Amberlyst 35 strong acid type large hole cation exchanger resins, and dihydromyrcene, water and Virahol are preheated to 102 ℃, 93 ℃ and 75 ℃ respectively.Other operation steps is with embodiment 1.The purity of tower still dihydromyrcenol is 96%.The dihydromyrcene transformation efficiency is 95%, and selectivity is 93%.
Embodiment 3:
Similar with embodiment 1 working method, tower still adding dihydromyrcene, water, Virahol are 1: 1: 1 to 1: 3: 3 by mass ratio, add a certain amount of Amberlyst 15 strong acid type large hole cation exchanger resins.The reaction fractionating tower reacting section catalyst is Amberlyst 15 strong acid type large hole cation exchanger resins, and dihydromyrcene, water and Virahol are preheated to 100 ℃, 80 ℃ and 78 ℃ respectively.Other operation steps is with embodiment 1.The purity of tower still dihydromyrcenol is 95%.The dihydromyrcene transformation efficiency is 95%, and selectivity is 91%.
Embodiment 4:
Similar with embodiment 1 working method, catalyzer adopts Purilite CT275 strong acid type large hole cation exchanger resin, and dihydromyrcene, water and dioxy six alkane are preheated to 93 ℃, 87 ℃ and 70 ℃ respectively.Other operation steps is with embodiment 1.The purity of tower still dihydromyrcenol is 95%.The dihydromyrcene transformation efficiency is 95%, and selectivity is 93%.
Embodiment 5:
Similar with embodiment 1 working method, catalyzer adopts Purilite CT482 strong acid type large hole cation exchanger resin, and dihydromyrcene, water and dioxy six alkane are preheated to 108 ℃, 83 ℃ and 80 ℃ respectively.Other operation steps is with embodiment 1.The purity of tower still dihydromyrcenol is 95%.The dihydromyrcene transformation efficiency is 98%, and selectivity is 92%.
Embodiment 6:
Similar with embodiment 1 working method, catalyzer adopts Purilite CT151DR strong acid type large hole cation exchanger resin, and dihydromyrcene, water and butanone (ethanol or acetone) are preheated to 115 ℃, 95 ℃ and 70 ℃ respectively.Other operation steps is with embodiment 1.The purity of tower still dihydromyrcenol is 95%.The dihydromyrcene transformation efficiency is 95%, and selectivity is 91%.
Embodiment 7:
Similar with embodiment 1 working method, catalyzer adopts NKC-9 (D72, D61 or D001-CC) strong acid type large hole cation exchanger resin, and dihydromyrcene, water and butanone (ethanol or acetone) are preheated to 96 ℃, 89 ℃ and 77 ℃ respectively.Other operation steps is with embodiment 1.The purity of tower still dihydromyrcenol is 95%.The dihydromyrcene transformation efficiency is 90%, and selectivity is 92%.
Embodiment 8:
Similar with embodiment 1 working method, catalyzer adopts NKC-9 (D72, D61 or D001-CC) strong acid type large hole cation exchanger resin, and dihydromyrcene, water and Virahol (butanols or acetic ester) are preheated to 110 ℃, 95 ℃ and 80 ℃ respectively.Other operation steps is with embodiment 1.The purity of tower still dihydromyrcenol is 95%.The dihydromyrcene transformation efficiency is 94%, and selectivity is 90%.
Claims (5)
1. the reactive distillation serialization prepares the method for dihydromyrcenol, it is characterized in that being equipped with in the reaction fractionating tower ripple silk net filler and solid acid catalyst, and reaction fractionating tower is divided into tower still, stripping section, conversion zone and rectifying section from bottom to top; The preparation process of dihydromyrcenol may further comprise the steps:
(1) dihydromyrcene is preheated to 80～120 ℃, from the top charging of reaction fractionating tower conversion zone; With water preheat to 85～95 ℃, the middle part of input conversion zone; Solvent is preheated to 70～90 ℃, and from the underfeed of conversion zone, the mass flux ratio of dihydromyrcene, water and solvent is 1: (1～3): (1～3); 105～120 ℃ of control tower still temperature; Said solvent is one or more in acetone, acetic ester, methyl alcohol, ethanol, Virahol, butanols, ethylene glycol monobutyl ether, ethylene glycol bis butyl ether, dioxy six alkane;
After dihydromyrcene liquid is gone into tower, flow downward, simultaneously water is heated gasification with solvent, and to the rising of cat head direction, dihydromyrcene and water contact in that conversion zone is reverse, issues unboiled water in the effect of catalyzer and solvent and closes reaction; The azeotrope of unreacted dihydromyrcene, water and solvent continues to rise to rectifying section, discharges from cat head; Tower still extraction product dihydromyrcenol from reaction fractionating tower;
(2) after the azeotrope of said dihydromyrcene, water and solvent is discharged from cat head, be condensed to 50～70 ℃ through the condensing surface cooling.
(3) phlegma is fed phase splitter, tell oil phase and water, just the part oil phase on upper strata returns cat head, and all the other oil phases are integrated with in the dihydromyrcene raw material, and lower layer of water is incorporated in the raw water mutually.
2. reactive distillation serialization according to claim 1 prepares the method for dihydromyrcenol, it is characterized in that said solid acid catalyst is large hole cation exchanger resin or zeolite catalyst.
3. reactive distillation serialization according to claim 2 prepares the method for dihydromyrcenol; It is characterized in that said large hole cation exchanger resin is Purilite CT275, Purilite CT482; Purilite CT151DR; D72, D61, D001-C,, Amberlyst 36, Amberlyst 35, Amberlyst 15 or NKC-9; Said zeolite catalyst is ZSM-5 or mordenite.
4. the method for preparing dihydromyrcenol according to claim 1 or 2 or 3 described reactive distillation serializations is characterized in that said catalyzer adopts non-woven fabrics, silica wool or wire cloth to be packaged into catalyst pack.
5. reactive distillation serialization according to claim 4 prepares the method for dihydromyrcenol, it is characterized in that being provided with liquid distributor in the cat head of reaction fractionating tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100608766A CN102617288A (en) | 2012-03-09 | 2012-03-09 | Method for preparing dihydromyrcenol through reaction distillation continuity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100608766A CN102617288A (en) | 2012-03-09 | 2012-03-09 | Method for preparing dihydromyrcenol through reaction distillation continuity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102617288A true CN102617288A (en) | 2012-08-01 |
Family
ID=46557560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100608766A Pending CN102617288A (en) | 2012-03-09 | 2012-03-09 | Method for preparing dihydromyrcenol through reaction distillation continuity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102617288A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3509737A4 (en) * | 2016-09-08 | 2020-08-19 | P2 Science, Inc. | Methods for the continuous alkoxylation and derivatization of terpenes |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6058930A (en) * | 1983-09-09 | 1985-04-05 | Yasuhara Yushi Kogyo Kk | Production of dihydromyrcenol |
| CN101684065A (en) * | 2009-07-21 | 2010-03-31 | 厦门中坤化学有限公司 | Efficient energy-saving process for continuously processing dihydromyrcenol |
| CN101921176A (en) * | 2010-08-10 | 2010-12-22 | 福州大学 | Novel method for producing dihydromyrcenol |
| CN102173978A (en) * | 2011-03-11 | 2011-09-07 | 浙江新化化工股份有限公司 | Dihydromyrcenol fixed bed hydration continuous production method |
| CN201990612U (en) * | 2011-03-16 | 2011-09-28 | 广西梧州松脂股份有限公司 | Device for preparing dihydromyrcenol through continuous rectification-reaction processes |
-
2012
- 2012-03-09 CN CN2012100608766A patent/CN102617288A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6058930A (en) * | 1983-09-09 | 1985-04-05 | Yasuhara Yushi Kogyo Kk | Production of dihydromyrcenol |
| CN101684065A (en) * | 2009-07-21 | 2010-03-31 | 厦门中坤化学有限公司 | Efficient energy-saving process for continuously processing dihydromyrcenol |
| CN101921176A (en) * | 2010-08-10 | 2010-12-22 | 福州大学 | Novel method for producing dihydromyrcenol |
| CN102173978A (en) * | 2011-03-11 | 2011-09-07 | 浙江新化化工股份有限公司 | Dihydromyrcenol fixed bed hydration continuous production method |
| CN201990612U (en) * | 2011-03-16 | 2011-09-28 | 广西梧州松脂股份有限公司 | Device for preparing dihydromyrcenol through continuous rectification-reaction processes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3509737A4 (en) * | 2016-09-08 | 2020-08-19 | P2 Science, Inc. | Methods for the continuous alkoxylation and derivatization of terpenes |
| US11008271B2 (en) | 2016-09-08 | 2021-05-18 | P2 Science, Inc. | Methods for the continuous alkoxylation and derivatization of terpenes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475440B (en) | Method for continuous production of n-butyl chloride | |
| CN101337884B (en) | Method for preparing 2-Butoxyethyl acetate by continuous esterification reaction | |
| CN101367724B (en) | Method and apparatus for synthesis of isopropyl acetate | |
| CN101337885A (en) | Method for preparing 1-Methoxy-2-propyl acetate by continuous esterification reaction | |
| CN102093178A (en) | Method for continuously producing unsaturated aldehyde compound by using reaction and rectification | |
| CN102659513A (en) | Process for producing alcohol and selectively co-producing 2-butanol by utilizing acetate and matching process system thereof | |
| CN104370740B (en) | Compounding acetic isoborneol ester production method | |
| CN107501042A (en) | A kind of method that isopropanol is prepared by isopropyl acetate ester hydrolysis | |
| CN101921176B (en) | Novel method for producing dihydromyrcenol | |
| CN102173978B (en) | Dihydromyrcenol fixed bed hydration continuous production method | |
| CN102134191B (en) | Process method for producing ethyl acetate by catalytic rectification | |
| CN101085711B (en) | Method for synthesizing ethyl benzene and diethyl benzene | |
| CN102875328B (en) | Catalyzing rectifying technology for synthesizing sec-butyl alcohol through ester exchange method and production equipment of catalyzing rectifying technology | |
| CN104311390A (en) | Method for synthesizing sec-butyl alcohol | |
| CN102093180B (en) | Method for continuously producing unsaturated aldehyde compound | |
| CN102617288A (en) | Method for preparing dihydromyrcenol through reaction distillation continuity | |
| CN105693687B (en) | High-efficiency reactive distillation method and device for glycol acetal/ketone reaction | |
| CN102584518B (en) | Industrial production method and production device of isobutene | |
| CN102659517A (en) | Method for continuously producing dihydromyrcenol by using tubular reactor | |
| CN101423454B (en) | Method for preparing tert-butanol by extraction of carbon 4 hydrocarbon containing isobutene | |
| CN202193744U (en) | Dimethoxymethane production device | |
| CN102304011B (en) | Method for producing 1,2,4-trimethylbenzene by C9 aromatic hydrocarbon isomerization | |
| CN101362672A (en) | Apparatus and method for continuously preparing trimethyl benzene and tetramethylbenzene in single tower by heavy aromatic hydrocarbon one step method | |
| CN105753667A (en) | Method for preparing camphor through continuous dehydrogenation of isoborneol | |
| CN100443461C (en) | Method for separating sec-butyl acetate, acetic acid and heavy hydrocarbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120801 |