CN105198689A - Method for preparing cis-pinane by adopting selective hydrogenation of alpha-pinene - Google Patents
Method for preparing cis-pinane by adopting selective hydrogenation of alpha-pinene Download PDFInfo
- Publication number
- CN105198689A CN105198689A CN201510727187.XA CN201510727187A CN105198689A CN 105198689 A CN105198689 A CN 105198689A CN 201510727187 A CN201510727187 A CN 201510727187A CN 105198689 A CN105198689 A CN 105198689A
- Authority
- CN
- China
- Prior art keywords
- pinene
- pinane
- catalyzer
- cis
- alpha
- 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.)
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Links
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 title claims abstract description 62
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 title claims abstract description 35
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- XOKSLPVRUOBDEW-DJLDLDEBSA-N (1r,4s,5r)-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound C[C@H]1CC[C@H]2C(C)(C)[C@@H]1C2 XOKSLPVRUOBDEW-DJLDLDEBSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 13
- 230000005291 magnetic effect Effects 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 229910003321 CoFe Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 230000004044 response Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229930006728 pinane Natural products 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing cis-pinane by adopting selective hydrogenation of alpha-pinene. According to the method, alpha-pinene and a magnetic catalyst react in a mass ratio being 50:(1-2.7) for 4.0-6.0 h at the reaction temperature of 140-180 DEG C and under hydrogen pressure of 4.0-6.0 MPa; cis-pinane is prepared, and after reaction, a catalyst phase and a product phase are recovered respectively through an external magnetic field. The catalyst phase does not require aftertreatment and is recycled directly. Under the process conditions, the conversion rate of alpha-pinene is higher than 99%, and the selectivity of cis-pinane is higher than 96%.
Description
Technical field
The present invention relates to a kind of method that cis-pinane is prepared in α-pinene selective hydrogenation, namely relate to the method that cis-pinane is prepared in the selective hydrogenation of a kind of magnetic catalyst catalysis α-pinene.
Technical background
Pinane obtains mainly through α-pinene shortening, is the important intermediate of the spices such as synthetic aromatic alcohol.Higher with cis-pinane reactive behavior in pinane, so α-pinene shortening prepares the purity of cis-pinane in the process of pinane and selectivity is just extremely important.At present, catalyzer for catalysis α-pinene hydrogenation synthesis cis-pinane mainly contains skeleton nickel (CN1191857, CN1262263), Pd/C (Wang Biyu etc., palladium carbon catalyst is used for the research [J] that α-pinene atmospheric hydrogenation prepares pinane. Fujian chemical industry, 1997,4:14-15), Ru/Al
2o
3metal catalysts such as (MarkSP, LawrencevilieNJ.Hydrogenationofpinenetosic-pinane [P] .US:4310714,1982-12-10).The selectivity of these catalyzer ubiquities to cis-pinane is low, poor catalyst stability, reuses the deficiencies such as difficulty.Therefore, research and develop the good selective hydrogenation catalyst of New Cycle use properties and become an important and problem demanding prompt solution.
In recent years, the research of magnetic nano-catalyst achieves larger progress.The advantage of magnetic nano-catalyst is mainly: heat energy is high, good mechanical stability, is applicable to scale operation, is a kind ofly magnetic recovery can have again the novel nano catalyzer of high catalytic activity; Magnetic nano-particle after modification can be stable be dispersed in the middle of catalyst system.The present invention proposes to adopt the selective hydrogenation of magnetic catalyst catalysis α-pinene to prepare the novel method of cis-pinane thus.
Summary of the invention
Cis-pinane is prepared in the environmentally friendly catalyst α-pinene selective hydrogenation that the object of the invention is to propose a kind of catalytic performance excellent, effectively can improve the selectivity of cis-pinane, and catalyzer has good repeat performance.
The present invention relates to a kind of method that cis-pinane is prepared in α-pinene selective hydrogenation, it is characterized in that α-pinene is 50: 1 ~ 2.7 with catalyst quality ratio, temperature of reaction 140 ~ 180 DEG C, react 4.0 ~ 6.0h under the condition of hydrogen pressure 4.0 ~ 6.0MPa and prepare cis-pinane, after reaction terminates, utilize externally-applied magnetic field to reclaim catalyzer phase and product phase respectively.Catalyzer, can direct reuse without the need to aftertreatment.
The present invention is characterized in that described magnetic catalyst is M-SiO
2-APTES-Ru type catalyzer, wherein M-SiO
2in-APTES-Ru, Ru massfraction is 5% ~ 10%, M is Fe
3o
4, Fe
2o
3, ZnFe
2o
4, MnFe
2o
4, CoFe
2o
4in one, the APTES of the fixing Ru adopted is APTES.
Concrete steps are:
(1) α-pinene is prepared as to the typical case of cis-pinane and magnetic catalyst mass ratio is 50: 1 ~ 2.7, put in the autoclave with mechanical stirring, thermocouple thermometer, fill 4.0 ~ 6.0MPa hydrogen, heated and stirred reaction 4.0 ~ 6.0h at temperature of reaction 140 ~ 180 DEG C.Catalyzed reaction terminates rear solution and is cooled to room temperature, under the effect of externally-applied magnetic field, realizes being separated of catalyzer and product.Obtain product cis pinane.
(2) catalyzer that uses of method of the present invention is reusable, because catalyzer has paramagnetic properties, after reaction terminates, being separated of product and catalyzer phase directly can be completed in a kettle. under the effect of externally-applied magnetic field, namely catalyzer can be used for next step catalytic hydrogenation reaction without the need to any process, after reusing 10 times, catalytic performance has no obvious reduction.
The present invention, compared with conventional catalyst technique, is characterized in:
(1) catalyzer has efficient catalytic activity and selectivity.
(2) product postprocessing is simple, and gained by product is few.
(3) after hydrogenation reaction terminates, utilize externally-applied magnetic field can simple and effective make catalyzer and product separation, get final product reuse without any aftertreatment, after reusing 10 times, catalytic performance has no obvious reduction, recycles performance better.
Specific implementation method
Being described further method of the present invention below in conjunction with embodiment, is not limitation of the invention.
Embodiment 1: by 3.0g α-pinene and 0.1gFe
3o
4-SiO
2-APTES-Ru (wherein the massfraction of Ru is 8%) adds in stainless steel autoclave, and air in hydrogen exchange still, is then filled with 5.0MPa hydrogen, heated and stirred 5h at 150 DEG C, leaves standstill and is cooled to room temperature.Under the effect of externally-applied magnetic field, be separated mutually direct to product and catalyzer in still, the catalyzer after separation can direct reuse.α-pinene transformation efficiency is 98.2%, and the selectivity of cis-pinane is 96.4%.
Embodiment 2: by 3.0g α-pinene and 0.1gFe
3o
4-SiO
2-APTES-Ru (wherein the massfraction of Ru is 8%) adds in stainless steel autoclave, and air in hydrogen exchange still, is then filled with 5.0MPa hydrogen, heated and stirred 5h at 160 DEG C, leaves standstill and is cooled to room temperature.Under the effect of externally-applied magnetic field, be separated mutually direct to product and catalyzer in still, the catalyzer after separation can be directly used in lower secondary response.α-pinene transformation efficiency is 99.4%, and the selectivity of cis-pinane is 96.3%.
Embodiment 3: by 3.0g α-pinene and 0.1gFe
3o
4-SiO
2-APTES-Ru (wherein the massfraction of Ru is 8%) adds in stainless steel autoclave, and air in hydrogen exchange still, is then filled with 6.0MPa hydrogen, heated and stirred 5h at 160 DEG C, leaves standstill and is cooled to room temperature.Under the effect of externally-applied magnetic field, be separated mutually direct to product and catalyzer in still, the catalyzer after separation can be directly used in lower secondary response.α-pinene transformation efficiency is 99.5%, and the selectivity of cis-pinane is 96.2%.
Embodiment 4: by 3.0g α-pinene and 0.1gFe
3o
4-SiO
2-APTES-Ru (wherein the massfraction of Ru is 8%) adds in stainless steel autoclave, and air in hydrogen exchange still, is then filled with 5.0MPa hydrogen, heated and stirred 5h at 170 DEG C, leaves standstill and is cooled to room temperature.Under the effect of externally-applied magnetic field, be directly separated in still by product with catalyzer, the catalyzer after separation can be directly used in lower secondary response.α-pinene transformation efficiency is 99.6%, and the selectivity of cis-pinane is 96.1%.
Embodiment 5: by 3.0g α-pinene and 0.1gZnFe
2o
4-SiO
2-APTES-Ru (wherein the massfraction of Ru is 8%) adds in stainless steel autoclave, and air in hydrogen exchange still, is then filled with 5.0MPa hydrogen, heated and stirred 5h at 160 DEG C, leaves standstill and is cooled to room temperature.Under the effect of externally-applied magnetic field, be directly separated in still by product with catalyzer, the catalyzer after separation can be directly used in lower secondary response.α-pinene transformation efficiency is 99.3%, and the selectivity of cis-pinane is 96.1%.
Embodiment 6: by 3.0g α-pinene and 0.1gMnFe
2o
4-SiO
2-APTES-Ru (wherein the massfraction of Ru is 8%) adds in stainless steel autoclave, and air in hydrogen exchange still, is then filled with 5.0MPa hydrogen, heated and stirred 5h at 160 DEG C, leaves standstill and is cooled to room temperature.Under the effect of externally-applied magnetic field, be directly separated in still by product with catalyzer, the catalyzer after separation can be directly used in lower secondary response.α-pinene transformation efficiency is 99.4%, and the selectivity of cis-pinane is 96.3%.
Embodiment 7: by 3.0g α-pinene and 0.1gMnFe
2o
4-SiO
2-APTES-Ru (wherein the massfraction of Ru is 8%) adds in stainless steel autoclave, and air in hydrogen exchange still, is then filled with 6.0MPa hydrogen, heated and stirred 5h at 160 DEG C, leaves standstill and is cooled to room temperature.Under the effect of externally-applied magnetic field, be directly separated in still by product with catalyzer, the catalyzer after separation can be directly used in lower secondary response.α-pinene transformation efficiency is 99.5%, and the selectivity of cis-pinane is 96.1%.
Embodiment 8-17: catalyzer, with embodiment 1, is just changed into the catalyzer reclaimed in embodiment 1 by experiment condition and step, carry out ten recycling experiments, after reusing ten times, α-pinene transformation efficiency is 99.0%, and the selectivity of cis-pinane is 96.1%.
Claims (1)
1. the method for cis-pinane is prepared in a α-pinene selective hydrogenation, it is characterized in that m (α-pinene): m (catalyzer)=50: 1 ~ 2.7, temperature of reaction 140 ~ 180 DEG C, hydrogen pressure 4.0 ~ 6.0MPa, reaction times 4.0 ~ 6.0h; Wherein catalyzer is the magnetic catalyst of carried noble metal Ru, and structure is M-SiO
2the massfraction of-APTES-Ru, Ru is 5% ~ 10%, M is CoFe
2o
4, MnFe
2o
4, ZnFe
2o
4, Fe
3o
4, Fe
2o
3, in one, the APTES of the fixing Ru adopted is APTES; Utilize externally-applied magnetic field to reclaim catalyzer phase and product phase respectively after reaction terminates, catalyzer, can direct reuse without the need to aftertreatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510727187.XA CN105198689B (en) | 2015-10-30 | 2015-10-30 | A kind of method that α firpenes selective hydrogenation prepares cis-pinane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510727187.XA CN105198689B (en) | 2015-10-30 | 2015-10-30 | A kind of method that α firpenes selective hydrogenation prepares cis-pinane |
Publications (2)
| Publication Number | Publication Date |
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| CN105198689A true CN105198689A (en) | 2015-12-30 |
| CN105198689B CN105198689B (en) | 2018-01-19 |
Family
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| CN201510727187.XA Expired - Fee Related CN105198689B (en) | 2015-10-30 | 2015-10-30 | A kind of method that α firpenes selective hydrogenation prepares cis-pinane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622328A (en) * | 2016-03-28 | 2016-06-01 | 青岛科技大学 | Method for preparing cis-pinane by alpha-pinene hydrogenation |
| CN107188775A (en) * | 2017-07-07 | 2017-09-22 | 青岛科技大学 | A kind of method that amphipathic molecule sieve load Ru nano particle catalysis α pinene hydrogenations prepare cis-pinane |
| CN109912374A (en) * | 2019-04-10 | 2019-06-21 | 青岛科技大学 | A kind of method that australene adds hydrogen to prepare cis-pinane |
| CN112980501A (en) * | 2021-02-24 | 2021-06-18 | 青岛科技大学 | One-pot preparation method of turpentine-based biomass high-energy-density fuel |
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| US5132270A (en) * | 1990-08-30 | 1992-07-21 | Huels Aktiengesellschaft | Ultrasound method of reactivating deactivated hydrogenation catalyts |
| CN101884925A (en) * | 2010-07-09 | 2010-11-17 | 桂林理工大学 | Catalyst for synthesizing pinane by hydrogenating alpha-pinene and preparation method |
| CN102125864A (en) * | 2010-12-16 | 2011-07-20 | 昆明理工大学 | Supported catalyst for hydrogenation of alpha-pinene and preparation method and uses thereof |
| CN102205245A (en) * | 2011-04-11 | 2011-10-05 | 天津市安凯特催化剂有限公司 | Method for improving selectivity of cis pinane prepared by alpha-pinene hydrogenation |
| CN104003831A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Method for preparing cis-pinane by asymmetric catalytic hydrogenation of alpha-pinene |
| CN104844408A (en) * | 2015-01-21 | 2015-08-19 | 青岛科技大学 | Method for catalyzing hydrogenation of alpha-pinene to prepare cis-pinane |
-
2015
- 2015-10-30 CN CN201510727187.XA patent/CN105198689B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132270A (en) * | 1990-08-30 | 1992-07-21 | Huels Aktiengesellschaft | Ultrasound method of reactivating deactivated hydrogenation catalyts |
| CN101884925A (en) * | 2010-07-09 | 2010-11-17 | 桂林理工大学 | Catalyst for synthesizing pinane by hydrogenating alpha-pinene and preparation method |
| CN102125864A (en) * | 2010-12-16 | 2011-07-20 | 昆明理工大学 | Supported catalyst for hydrogenation of alpha-pinene and preparation method and uses thereof |
| CN102205245A (en) * | 2011-04-11 | 2011-10-05 | 天津市安凯特催化剂有限公司 | Method for improving selectivity of cis pinane prepared by alpha-pinene hydrogenation |
| CN104003831A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Method for preparing cis-pinane by asymmetric catalytic hydrogenation of alpha-pinene |
| CN104844408A (en) * | 2015-01-21 | 2015-08-19 | 青岛科技大学 | Method for catalyzing hydrogenation of alpha-pinene to prepare cis-pinane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622328A (en) * | 2016-03-28 | 2016-06-01 | 青岛科技大学 | Method for preparing cis-pinane by alpha-pinene hydrogenation |
| CN107188775A (en) * | 2017-07-07 | 2017-09-22 | 青岛科技大学 | A kind of method that amphipathic molecule sieve load Ru nano particle catalysis α pinene hydrogenations prepare cis-pinane |
| CN109912374A (en) * | 2019-04-10 | 2019-06-21 | 青岛科技大学 | A kind of method that australene adds hydrogen to prepare cis-pinane |
| CN109912374B (en) * | 2019-04-10 | 2022-01-18 | 青岛科技大学 | Method for preparing cis-pinane by hydrogenating alpha-pinene |
| CN112980501A (en) * | 2021-02-24 | 2021-06-18 | 青岛科技大学 | One-pot preparation method of turpentine-based biomass high-energy-density fuel |
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| Publication number | Publication date |
|---|---|
| CN105198689B (en) | 2018-01-19 |
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