CN102659517A - Method for continuously producing dihydromyrcenol by using tubular reactor - Google Patents
Method for continuously producing dihydromyrcenol by using tubular reactor Download PDFInfo
- Publication number
- CN102659517A CN102659517A CN2012101268719A CN201210126871A CN102659517A CN 102659517 A CN102659517 A CN 102659517A CN 2012101268719 A CN2012101268719 A CN 2012101268719A CN 201210126871 A CN201210126871 A CN 201210126871A CN 102659517 A CN102659517 A CN 102659517A
- Authority
- CN
- China
- Prior art keywords
- tubular reactor
- dihydromyrcenol
- dihydromyrcene
- phase
- 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
Abstract
The invention discloses a method for continuously producing dihydromyrcenol by using a tubular reactor. The method comprises the following steps: mixing dihydromyrcene, water and solvent in a mixer; after mixing, heating the mixture to 70-95 DEG C by a pre-heater and pouring the mixture into the tubular reactor; heating and controlling the reaction temperature in the tubular reactor at 100-120 DEG C by adopting a short circuit current; pouring a reaction product in the tubular reactor into a phase splitter; after splitting the phases by the phase splitter, further separating the upper-layer organic phase in a rectifying column; pouring the upper-layer organic phase into the rectifying column after splitting the phases by the phase splitter, causing the dihydromyrcenol as a heavy component to flow to a tower kettle; and extracting the dihydromyrcenol with purity above 95% by the tower kettle. The tubular reactor is adopted according to the method provided by the invention, for reducing liquid back-mixing, reducing energy consumption and avoiding the quick decrease of reaction rate in the later stage of reaction. A fin is arranged on the inner wall of the tubular reactor, for reinforcing the liquid flow, boosting the matter-transferring and heat-transferring of reaction, increasing the reaction rate and meanwhile avoiding the powdering of solid catalyst caused by stirring.
Description
Technical field
The present invention relates to working method, be specifically related to a kind of method of tubular reactor continuously processing 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, is the representative of " excess consumption " in the men's in modern times perfume.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 energy consumption is big, 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 batch stirred tank reactor reaction, product got into separating unit and carries out later separation.Batch stirred tank reactor is easy to make the solid catalyst efflorescence, and has arrived the decline of reaction late phase reaction speed, thereby causes the reaction times long, and production efficiency is lower.
Summary of the invention
Shortcoming such as the present invention is directed to that existing process energy consumption is high, production efficiency is low and environmental pollution is serious; A kind of method of tubular reactor continuously processing dihydromyrcenol is provided, adopts tubular reactor to substitute batch stirred tank reactor, reduce liquid dispersion; Cut down the consumption of energy; Avoid reacting the problem that late phase reaction speed descends rapidly, the fin reinforcing liquid-flow that the tubular reactor inwall is provided with promotes reaction mass transfer to conduct heat; Improve speed of reaction, the efflorescence that can also avoid stirring the solid catalyst that brings simultaneously.
Technical solution of the present invention is that this working method may further comprise the steps:
Step 1: dihydromyrcene, water and solvent get in the mixing tank and mix, and mix after preheater is heated to 70-95
oC gets into tubular reactor; Solvent is a kind of in acetic ester, methyl alcohol, ethanol, Virahol, butanols, ethylene glycol monobutyl ether, ethylene glycol bis butyl ether, dioxy six alkane; Wherein, the mass ratio of dihydromyrcene, water and solvent is 1: (1-3): (1-3);
Step 2: tubular reactor is the horizontal tube reactor drum, and inside is provided with fin, adopts the short-circuit current heating, and control reaction temperature is at 100-120
oSolid catalyst in the C, tubular reactor is provided with screen cloth with material high speed turbulence in reactor drum in the tubular reactor outlet, solid catalyst is trapped in the reactor drum internal recycle uses; Wherein, Solid catalyst is large hole cation exchanger resin or zeolite catalyst; Large hole cation exchanger resin is Purilite CT275, Purilite CT482, Purilite CT151DR, D72, D61, D001-C, Amberlyst 36, Amberlyst 35, Amberlyst 15, NKC-9, and zeolite catalyst is ZSM-5, mordenite;
Step 3: the reaction product of tubular reactor gets into phase splitter, and after the phase splitter phase-splitting, upper organic phase gets into rectifying tower further separates, and lower floor's water is back to mixing tank again and uses as feed cycle;
Step 4: BX500 ripple silk net filler is housed in the rectifying tower, and the upper organic phase after the phase splitter phase-splitting gets into rectifying tower; The azeotrope that solvent and dihydromyrcene form is a light constituent, flows to cat head, refluxes through overhead condenser condensation rear section, and extraction to mixing tank uses as feed cycle; Dihydromyrcenol is heavy constituent, flows to the tower still, the dihydromyrcenol of tower still extraction purity more than 95%.
The present invention has following advantage:
(1) this working method adopts tubular reactor to substitute the batch stirred tank reactor in the traditional technology; The tubular reactor volume is little, specific surface area big, the heat transfer area of unit volume is big; Reduce liquid dispersion, its tube fluid flow pattern approaches perfect gas under the lower situation of flow velocity, and reactant speed of response in tubular reactor is fast, throughput is high; Cut down the consumption of energy, avoid reacting the problem that late phase reaction speed descends rapidly.
(2) the tubular reactor inwall is provided with fin, strengthens liquid-flow, and fluid is turbulence state in pipe; Promote reaction mass transfer to conduct heat, material reaction is abundant, and speed of reaction is fast; Transformation efficiency is improved, the efflorescence that can also avoid stirring the solid catalyst that brings simultaneously.
(3) phase splitter is set, avoids getting into the energy waste that causes in the rectifying tower again because of water.
(4) compare with the existing processes route, this working method is simplified production technique, and the strengthening process mass-and heat-transfer cuts down the consumption of energy, and saves facility investment, cuts down the consumption of energy more than 30%, saves facility investment more than 20%.
(5) adopt solid catalyst to replace traditional liquid catalyst, reduced corrosion on Equipment, reduced environmental pollution simultaneously, solid catalyst reclaims simple, can be recycled.
(6) solid catalyst in the tubular reactor is with material high speed turbulence in reactor drum, and reaction mass fully contacts with granules of catalyst, and speed of reaction and development of evil in febrile disease rate all improve.
Description of drawings
Fig. 1 is the schematic flow sheet of continuously processing dihydromyrcenol of the present invention.
Among the figure: 1 mixing tank, 2 preheaters, 3 tubular reactors, 4 screen clothes, 5 phase splitters, 6 rectifying tower.
?
Specific embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment are used to understand technical scheme, and can not be interpreted as it is the restriction to technical scheme.
Embodiment 1: dihydromyrcene, water, Virahol mass ratio are 1:1:1, after mixer mixing, are preheated to 80
oC gets into tubular reactor; In tubular reactor, add Amberlyst 36 strong acid type large hole cation exchanger resins as catalyzer, tubular reactor adopts short-circuit current heating, control reaction temperature 110
oC, reaction product is behind the screen filtration in tubular reactor exit, and catalyzer is trapped in and continues in the reactor drum to use, and filtrating gets into phase splitter; Filtrating is after the phase splitter phase-splitting, and water recycles as raw material in the pump input mixer, and upper organic phase gets into rectifying tower and further separates; The dihydromyrcene of rectifying tower top extraction and the mixture of solvent are delivered to mixing tank and are continued to use as raw material, tower still extraction product dihydromyrcenol, and purity is 95.1%.Transformation efficiency through calculating dihydromyrcene is 93%, and selectivity is 90%.
Embodiment 2: similar with embodiment 1 working method, dihydromyrcene, water, butanols mass ratio are 1:2:2, after mixer mixing, are preheated to 90
oC gets into tubular reactor; Add a certain amount of Amberlyst 15 strong acid type large hole cation exchanger resins, control reaction temperature 100 in the tubular reactor
oC, other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 95.6%.The dihydromyrcene transformation efficiency is 94%, and selectivity is 91%.
Embodiment 3: similar with embodiment 1 working method, dihydromyrcene, water, methanol quality are preheated to 85 than for 1:3:3
oAdd a certain amount of Amberlyst 35 strong acid type large hole cation exchanger resins, control reaction temperature 120 in the C, tubular reactor
oC, other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 96%.The dihydromyrcene transformation efficiency is 90%, and selectivity is 92%.
Embodiment 4: similar with embodiment 1 working method, dihydromyrcene, water, ethylene glycol monobutyl ether mass ratio are 1:1:1, after mixer mixing, are preheated to 95
oC gets into tubular reactor; Catalyzer adopts Purilite CT482 strongly acidic cation-exchange, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 96.2%.The dihydromyrcene transformation efficiency is 97%, and selectivity is 90%.
Embodiment 5: similar with embodiment 2 working method, dihydromyrcene, water, dioxy six alkane mass ratioes are 1:2:2, after mixer mixing, are preheated to 75
oC gets into tubular reactor; Catalyzer adopts Purilite CT275 strongly acidic cation-exchange, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 96.7%.The dihydromyrcene transformation efficiency is 91%, and selectivity is 93%.
Embodiment 6: similar with embodiment 2 working method, dihydromyrcene, water, ethylene glycol bis butyl ether mass ratio are 1:3:3, are preheated to 70
oC, catalyzer adopt Purilite CT151DR strongly acidic cation-exchange, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 96.9%.The dihydromyrcene transformation efficiency is 94%, and selectivity is 90%.
Embodiment 7: similar with embodiment 3 working method, dihydromyrcene, water, dioxy six alkane mass ratioes are 1:1:1, are preheated to 70
oC, catalyzer adopts the NKC-9 strongly acidic cation-exchange, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 97.1%.The dihydromyrcene transformation efficiency is 89%, and selectivity is 93%.
Embodiment 8: similar with embodiment 3 working method, dihydromyrcene, water and butanols mass ratio are 1:2:2, are preheated to 95
oC, catalyzer adopts the D72 strongly acidic cation-exchange, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 97.7%.The dihydromyrcene transformation efficiency is 91%, and selectivity is 95%.
Embodiment 9: similar with embodiment 3 working method, dihydromyrcene, water and acetic ester mass ratio are 1:3:3, are preheated to 90
oC, catalyzer adopts the D61 strongly acidic cation-exchange, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 98.2%.The dihydromyrcene transformation efficiency is 93%, and selectivity is 90%.
Embodiment 10: similar with embodiment 1 working method, and, dihydromyrcene, water and ethanol mass ratio are 1:3:3, are preheated to 80
oC, catalyzer adopts the D001-CC strongly acidic cation-exchange, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 95.9%.The dihydromyrcene transformation efficiency is 93%, and selectivity is 90%.
Embodiment 11: similar with embodiment 1 working method, and, dihydromyrcene, water and ethanol mass ratio are 1:2:2, are preheated to 70
oC, catalyzer adopts mordenite, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 95.4%.The dihydromyrcene transformation efficiency is 93%, and selectivity is 90%.
Embodiment 12: similar with embodiment 1 working method, and, dihydromyrcene, water and ethanol mass ratio are 1:1:1, are preheated to 90
oC, catalyzer adopts ZSM-5, and other operation steps is with embodiment 1, and the purity of tower still dihydromyrcenol is 97.3%.The dihydromyrcene transformation efficiency is 93%, and selectivity is 90%.
Claims (1)
1. the method for tubular reactor continuously processing dihydromyrcenol is characterized in that this working method may further comprise the steps:
Step 1: dihydromyrcene, water and solvent get in the mixing tank and mix, and mix after preheater is heated to 70-95
oC gets into tubular reactor; Solvent is a kind of in acetic ester, methyl alcohol, ethanol, Virahol, butanols, ethylene glycol monobutyl ether, ethylene glycol bis butyl ether, dioxy six alkane; Wherein, the mass ratio of dihydromyrcene, water and solvent is 1: (1-3): (1-3);
Step 2: tubular reactor is the horizontal tube reactor drum, and inside is provided with fin, adopts the short-circuit current heating, and control reaction temperature is at 100-120
oSolid catalyst in the C, tubular reactor is provided with screen cloth with material high speed turbulence in reactor drum in the tubular reactor outlet, solid catalyst is trapped in the reactor drum internal recycle uses; Wherein, Solid catalyst is large hole cation exchanger resin or zeolite catalyst; Large hole cation exchanger resin is Purilite CT275, Purilite CT482, Purilite CT151DR, D72, D61, D001-C, Amberlyst 36, Amberlyst 35, Amberlyst 15, NKC-9, and zeolite catalyst is ZSM-5, mordenite;
Step 3: the reaction product of tubular reactor gets into phase splitter, and after the phase splitter phase-splitting, upper organic phase gets into rectifying tower further separates, and lower floor's water is back to mixing tank again and uses as feed cycle;
Step 4: BX500 ripple silk net filler is housed in the rectifying tower, and the upper organic phase after the phase splitter phase-splitting gets into rectifying tower; The azeotrope that solvent and dihydromyrcene form is a light constituent, flows to cat head, refluxes through overhead condenser condensation rear section, and extraction to mixing tank uses as feed cycle; Dihydromyrcenol is heavy constituent, flows to the tower still, the dihydromyrcenol of tower still extraction purity more than 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101268719A CN102659517A (en) | 2012-04-27 | 2012-04-27 | Method for continuously producing dihydromyrcenol by using tubular reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101268719A CN102659517A (en) | 2012-04-27 | 2012-04-27 | Method for continuously producing dihydromyrcenol by using tubular reactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102659517A true CN102659517A (en) | 2012-09-12 |
Family
ID=46769130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101268719A Pending CN102659517A (en) | 2012-04-27 | 2012-04-27 | Method for continuously producing dihydromyrcenol by using tubular reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659517A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285612A (en) * | 2013-01-09 | 2013-09-11 | 天津大学 | No-compressor heat-pump rectifying device and operation method thereof |
| CN105505521A (en) * | 2015-12-15 | 2016-04-20 | 江苏高科石化股份有限公司 | Method for preparing silicon-based biological lubricant base oil by adopting pipeline-type recycle reactor |
| EP3509737A4 (en) * | 2016-09-08 | 2020-08-19 | P2 Science, Inc. | Methods for the continuous alkoxylation and derivatization of terpenes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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
- 2012-04-27 CN CN2012101268719A patent/CN102659517A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 俞忠华等: "二氢月桂烯水合制备二氢月桂烯醇的研究进展", 《江西科学》 * |
| 杨恩芳等: "水合法制备二氢月桂烯醇催化剂应用研究", 《化工技术与开发》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285612A (en) * | 2013-01-09 | 2013-09-11 | 天津大学 | No-compressor heat-pump rectifying device and operation method thereof |
| CN105505521A (en) * | 2015-12-15 | 2016-04-20 | 江苏高科石化股份有限公司 | Method for preparing silicon-based biological lubricant base oil by adopting pipeline-type recycle reactor |
| EP3509737A4 (en) * | 2016-09-08 | 2020-08-19 | P2 Science, Inc. | Methods for the continuous alkoxylation and derivatization of terpenes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8721842B2 (en) | Catalytic reaction-rectification integrated process and specialized device thereof | |
| TWI612031B (en) | Method and device for co-production of cyclohexanol and alkanol | |
| CN105693470B (en) | A kind of method of the alcohol of 3 methyl of continuous production, 3 butylene 1 | |
| RU2734548C1 (en) | Method for continuous production of 2-methylallyl alcohol | |
| CN104370722B (en) | Preparation and the refining method of butanone | |
| CN107501042B (en) | Method for preparing isopropanol by hydrolyzing isopropyl acetate | |
| CN101020838A (en) | Biodiesel oil preparing process and apparatus | |
| CN105061167A (en) | Method for preparing hydroxy neovaleraldehyde by condensing formaldehyde and isobutyraldehyde | |
| CN102633588B (en) | Method for preparing high-purity isobutene from raffinate C4 by means of separation | |
| CN102659517A (en) | Method for continuously producing dihydromyrcenol by using tubular reactor | |
| CN102001936A (en) | Continuous production method of propyl acetate | |
| CN109867596B (en) | Method for continuously producing 3-methyl-3-pentene-2-ketone by reactive distillation | |
| CN104370740A (en) | Production method of isobornyl acetate | |
| CN105461515A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN109748791B (en) | Energy-saving method for producing dimethyl adipate | |
| CN105753667B (en) | A kind of method that isoborneol continuous dehydrogenation prepares camphor | |
| CN105384629B (en) | A kind of energy-conserving and environment-protective production technology of the different monooctyl ester of lactic acid | |
| CN103951548A (en) | Preparation method of intermediate for synthesizing anise camphor | |
| CN102093180A (en) | Method for continuously producing unsaturated aldehyde compound | |
| CN105585468B (en) | A method of cyclopentanone is prepared by raw material of cyclopentene | |
| CN105130814B (en) | A kind of method that pyrovinic acid catalysis prepares diethyl sebacate | |
| CN113620773A (en) | Method for preparing bromoalkane by catalytic distillation | |
| CN108569957B (en) | Device and method for extracting 2-naphthyl methyl ether from 2-naphthol, methanol, 2-naphthyl methyl ether and p-toluenesulfonic acid and recovering components | |
| CN103588622A (en) | Method for synthesizing 2-methallyl alcohol through continuous hydrolysis reaction | |
| CN102617288A (en) | Method for preparing dihydromyrcenol through reaction distillation continuity |
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: 20120912 |