CN1054595C - Catalytic hydrogenation process preparing cis-pinane from pinene - Google Patents
Catalytic hydrogenation process preparing cis-pinane from pinene Download PDFInfo
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- CN1054595C CN1054595C CN97114323A CN97114323A CN1054595C CN 1054595 C CN1054595 C CN 1054595C CN 97114323 A CN97114323 A CN 97114323A CN 97114323 A CN97114323 A CN 97114323A CN 1054595 C CN1054595 C CN 1054595C
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- pinane
- firpene
- cis
- modifier
- nickel catalyst
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- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 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 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 10
- 230000008569 process Effects 0.000 title claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000003607 modifier Substances 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000809 Alumel Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000008399 tap water Substances 0.000 claims description 4
- 235000020679 tap water Nutrition 0.000 claims description 4
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 2
- 229930006728 pinane Natural products 0.000 abstract description 14
- 239000002304 perfume Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 abstract description 3
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 abstract description 3
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 abstract description 3
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229930006722 beta-pinene Natural products 0.000 abstract description 3
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 abstract description 3
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229930008394 dihydromyrcenol Natural products 0.000 abstract description 2
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 abstract description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 abstract 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 abstract 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 abstract 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 abstract 1
- 241000779819 Syncarpia glomulifera Species 0.000 abstract 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 abstract 1
- 229930007744 linalool Natural products 0.000 abstract 1
- 239000001739 pinus spp. Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229940036248 turpentine Drugs 0.000 abstract 1
- 239000000047 product Substances 0.000 description 6
- XOKSLPVRUOBDEW-IWSPIJDZSA-N (1r,4r,5r)-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound C[C@@H]1CC[C@H]2C(C)(C)[C@@H]1C2 XOKSLPVRUOBDEW-IWSPIJDZSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- -1 improve cis-content Chemical compound 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The present invention relates to a method for preparing cis-pinane by pinene hydrogenation. Alpha-pinene and beta-pinene in turpentine are used as raw materials prepared into pinane by catalytic hydrogenation, the pinane is an important intermediate for synthesizing main perfumes containing linalool, dihydromyrcenol, etc. In order to improve the quality of the pinane, the method increases the content of cis-isomers. The method aims to provide a novel framework nickel catalyst by preparing and modifying framework nickel catalysts, and the catalyst is used in the reaction of preparing high cis-pinane by pinene hydrogenation. The method can obtain conversion rate greater than 99%, and the content of a cis-pinane product in the pinane is greater than 95%.
Description
The invention belongs to the firpene catalytic hydrogenation and prepare the method for cis-pinane.
It with turps the attention that the technological line of raw material synthetic perfume is subjected to domestic and international perfume industry circle always, because natural perfume can not satisfy worldwide consumer need far away, and come synthetic perfume from petrochemical materials, long flow path, complex process, cost is higher, moreover oil is Nonrenewable resources, and supply is more and more nervous.China is a rosin resource big country in the world, produces ten thousand tons of rosin 35-40 per year, and ten thousand tons of turps 6-8 are that raw material can synthesize hundreds of important spices with turps, thereby comprehensive utilization turps just becomes the important channel of increasing economic efficiency.
Terebinthine major ingredient is α-Pai Xi and beta-pinene, but the two all catalytic hydrogenation make pinane, pinane is the important intermediate of key spices such as synthetic phantol and dihydromyrcenol, for the quality that improves pinane is the content of cis-isomeride, domestic and international chemical boundary does a lot of work aspect selecting catalyst, skeletal nickel catalyst is active higher a kind of catalyzer, the commercial catalysts of synthetic high-cis pinane, still concentrate in the improvement of skeleton nickel, mainly improve cis-content, but seldom see document and the report that uses the skeletal nickel catalyst of modified about the firpene hydrogenation by certain of skeleton nickel is modified.
The objective of the invention is provides a kind of novel skeletal nickel catalyst by preparation and modification to skeletal nickel catalyst, and this catalyzer uses in the firpene shortening can prepare the high-cis pinane.
Shortening provided by the invention prepares the method for high-cis pinane, comprises following step:
1). Preparation of catalysts and modification:
In temperature is in 30-40 ℃ the alkaline solution (NaOH content is 20-30%).Drop into alumel in batches, input amount is that alumel and solid caustic soda ratio are 1: 1-1.55 (weight), controlled temperature 30-40 ℃, stirred 0.5-1.0 hour after adding alloy, be warming up to 60-70 ℃ rapidly, and in 60-75 ℃ of insulation 3-4 hour, leave standstill the supernatant liquor that inclines then, add concentration and be about 10% NaOH solution, making the Ni-Al/NaOH weight ratio is 1: 0.2, stirred 1-1.5 hour, then nickel powder is transferred in the washing device, to neutral, tap water flow velocity is the 100ml/ branch with the tap water washing of flowing, and then with 95% washing with alcohol for several times, obtain skeletal nickel catalyst.Again above-mentioned catalyzer is modified, method is: with above-mentioned catalyzer under agitation, add transition metal chloride and make modifier, modifier also can be mixed by two or more transition metal chlorides and form, the modifier add-on is: the ratio of skeletal nickel catalyst and modifier is: 100: 1-10 (weight), after modifier adds, treat that the evolving gas amount reduces after, catalyzer is promptly modified and is finished.
2). the firpene catalytic hydrogenation reaction:
With above-mentioned 1). skeletal nickel catalyst that middle preparation is also modified and firpene drop into together and carry out hydrogenation reaction in the autoclave, the catalyzer input amount is the 3-5% of firpene weight, reaction pressure 2.0-3.0MPa, and temperature is 80-100 ℃, reacted 8-13 hour, and just made the high-cis pinane.Above-mentioned 1). in the catalyzer modification, can in Preparation of Catalyst, carry out, be about to drop in the firpene catalytic hydrogenation reaction still, also the catalyzer and the firpene raw material of modifier and unmodified can be dropped into the catalytic hydrogenation reaction that carries out catalyzer modification and firpene in the reactor together through the catalyzer after modifying.
Firpene provided by the invention prepares its firpene transformation efficiency of method of pinane greater than 99%, and the content of cis-pinane in pinane is greater than 95%, than using conventional skeletal nickel catalyst to exceed 3-5% in the product.
Embodiment 1 Preparation of catalysts
In the three-necked bottle that agitator and thermometer are housed, put into 240 ml water solution of dissolving 60 gram sodium hydroxide, under constantly stirring, be added in the alkali lye on a small quantity 50 gram alumeies in batches, temperature is controlled between 30-40 ℃, after whole alloys add, continue to stir 0.5 hour, be warming up to 60 ℃ then, keep 60-65 ℃ of temperature, stirred 3.5 hours, and left standstill the supernatant liquid that inclines then, add 100 ml water solution of dissolving 10 gram sodium hydroxide, at room temperature stirred 1 hour, then material is transferred in the washing device, carried out continuous washing, till being washed till litmus paper and being neutrality with the tap water of about 100 ml/min of flow velocity, leave standstill and make the catalyst sedimentation hypsokinesis liquid that anhydrates, obtain skeletal nickel catalyst 35 grams (weight in wet base) with 95% washing with alcohol again.Take by weighing catalyzer 2.5 grams (weight in wet base) of above-mentioned preparation, progressively add dissolving cupric chloride (CuCl
22H
2O) 5 milliliters of ethanolic solns of 0.1 gram, treat that gas evolution reduces after, this modified skeletal nickel catalyst uses for the firpene hydrogenation.
Embodiment 2 firpene hydrogenation reactions
In 100 milliliters of autoclaves, add modification skeletal nickel catalyst 2.5 grams of firpene (α-Pai Xi 95.3%, amphene 1.5%, beta-pinene 2.9%) 50 grams and embodiment 1 preparation in the vacuum intake mode.Vacuumize in the still, feed hydrogen three times then to drive air in the still, logical again hydrogen starts and stirs also heating to 2.6MPa, when temperature rises to 60 ℃, begins to inhale hydrogen, and holding temperature is mended hydrogen to 3.0MPa at 80-85 ℃ when pressure drops to 2.0MPa.So repeatedly several times.React when suction hydrogen finished substantially in 8 hours, sampling detects with the GC instrument, and its composition is: firpene 0.5%, and cis-pinane 94.6%, trans pinane 3.1%, firpene transformation efficiency are 99.5%, the content of cis-pinane in pinane is 96.8%.
Embodiment 3 firpene hydrogenation reactions
Operation steps is with embodiment 2.Use FeCl
36H
2O modifies skeletal nickel catalyst, and the modification amount is 6%.It is 4% of firpene heavily that catalyzer is used, at pressure 2.0-3.0MPa, and temperature 80-85 ℃, reaction is 10 hours under the condition, and hydrogenation products consists of: firpene 0.3%, cis-pinane 94.4%, trans pinane 3.9%, firpene transformation efficiency are 99.7%, and the content of cis-pinane in pinane is 96.0%.
Embodiment 4 firpene hydrogenation reactions
Operation steps is with embodiment 2.Use NiCl
26H
2O modifies skeletal nickel catalyst, and the modification amount is 7%.Catalyst levels is 3.5% of a firpene.At pressure 2.0-3.0MPa, reaction is 8 hours under the temperature 80-85 ℃ of condition, and hydrogenation products consists of: firpene 0.4%, and cis-pinane 93.9%, trans pinane 3.5%, firpene transformation efficiency are 99.6%, the content of cis-pinane in pinane is 96.4%.
Embodiment 5 firpene hydrogenation reactions
Operation steps is with embodiment 2.Use CoCl
26H
2O is a modifier, and the modification amount is 5%.Catalyst levels is 3% of a firpene.At pressure 2.0-3.0MPa, reaction is 8 hours under the temperature 80-85 ℃ of condition, and hydrogenation products consists of: firpene 0.6%, and cis-pinane 93.2%, trans pinane 3.3%, firpene transformation efficiency are 99.3%, the content of cis-pinane in pinane is 96.6%.
Embodiment 6 firpene hydrogenation reactions
Operation steps is with embodiment 2.Use NiCl
26H
2O is a modifier, and the modification amount is 7%.Catalyst levels is 4.5% of a firpene.At pressure 2.0-3.0Mpa, carry out hydrogenation reaction under the temperature 80-90 ℃ of condition.When finish discharging each again charging behind the product, reaction adds the catalyzer of 0.5-1.0%, carried out hydrogenation reaction successively ten times, the result is as follows: reaction times 8-12 hour, hydrogenation products consists of: firpene 0.2-0.5%, cis-pinane 93.0%-94.8%, trans pinane 3.1-4.0%, the content of cis-pinane in pinane is 95.9-96.8%.
Claims (3)
1. a firpene catalytic hydrogenation prepares the method for cis-pinane, and this method is to use through preparation and the skeletal nickel catalyst modified, it is characterized in that the preparation method comprises the steps:
1) preparation of skeletal nickel catalyst and modification:
In concentration is in the alkaline solution of NaOH 20～30%, drop into alumel, input amount is that alumel and solid caustic soda part by weight are 1: 1～1.55, controlled temperature 30-40 ℃, stirred 0.5～1.0 hour after adding alloy, be warming up to 60-70 ℃, keep temperature, stirred 3-4 hour, leave standstill, the supernatant liquor that inclines adds concentration and is 10% NaOH solution, and making the Ni-Al/NaOH weight ratio is 1: 0.2, at room temperature stirred 1-1.5 hour, then nickel powder is transferred in the washing device, washs to neutrality, use 95% washing with alcohol again with mobile tap water, skeletal nickel catalyst that obtains and the muriate modifier that is dissolved in the ethanol are reacted, after evolving gas reduces, promptly make skeletal nickel catalyst, the modifier add-on is that skeletal nickel catalyst and modifier part by weight are 100: 1～10;
2) firpene catalytic hydrogenation reaction:
With prepared catalyzer in firpene and above-mentioned (1), drop in the autoclave, it is the 3-5% of firpene amount that catalyzer drops into weight, reaction pressure 2.0-3.0MPa, temperature 80-100 ℃, reacted 8-13 hour, make cis-pinane.
2. according to the catalysis process described in the claim 1, it is characterized in that described catalyst modifier is a transition metal chloride, or the combination of two or more transition metal chloride is formed.
3. according to the catalysis process described in the claim 1, it is characterized in that to modify skeletal nickel catalyst earlier when described catalyst modifier is used, also modifier can be added in the reactor with firpene, modify simultaneously and hydrogenation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97114323A CN1054595C (en) | 1997-12-15 | 1997-12-15 | Catalytic hydrogenation process preparing cis-pinane from pinene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97114323A CN1054595C (en) | 1997-12-15 | 1997-12-15 | Catalytic hydrogenation process preparing cis-pinane from pinene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1191857A CN1191857A (en) | 1998-09-02 |
| CN1054595C true CN1054595C (en) | 2000-07-19 |
Family
ID=5172883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97114323A Expired - Fee Related CN1054595C (en) | 1997-12-15 | 1997-12-15 | Catalytic hydrogenation process preparing cis-pinane from pinene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1054595C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003835A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Method for preparing pinane by catalytic hydrogenation of turpentine |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239885B (en) * | 2007-02-09 | 2011-04-20 | 嘉兴香料厂 | Technique for synthesizing dihydromyrcenol |
| CN104844408B (en) * | 2015-01-21 | 2016-07-13 | 青岛科技大学 | A kind of it is catalyzed the australene Hydrogenation method for cis-pinane |
| CN105669344A (en) * | 2016-02-29 | 2016-06-15 | 常州大学 | Method for synthesizing cis-pinane by alpha-pinene continuous catalytic hydrogenation |
| CN107056572B (en) * | 2017-05-16 | 2019-12-06 | 潍坊学院 | Method for preparing cis-pinane by reducing alpha-pinene at normal temperature |
| CN111960911B (en) * | 2020-07-23 | 2022-05-13 | 青岛科技大学 | Method for preparing cis-pinane by hydrogenating alpha-pinene |
| CN112547095B (en) * | 2020-11-12 | 2022-04-15 | 复旦大学 | Catalyst for preparing cis-pinane by alpha-pinene hydrogenation and preparation method and application thereof |
| CN112707792A (en) * | 2020-12-25 | 2021-04-27 | 厦门中坤化学有限公司 | Method for increasing cis-dihydroterpineol content in terpineol hydrogenation reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018842A (en) * | 1976-05-27 | 1977-04-19 | Scm Corporation | Selective hydrogenation of α-pinene to cis-pinane |
| US4310714A (en) * | 1980-12-10 | 1982-01-12 | Union Camp Corporation | Hydrogenation of α-pinene to cis-pinane |
| EP0472853A1 (en) * | 1990-08-30 | 1992-03-04 | Hüls Aktiengesellschaft | Desactivated hydrogenation catalyst reactivation process |
-
1997
- 1997-12-15 CN CN97114323A patent/CN1054595C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018842A (en) * | 1976-05-27 | 1977-04-19 | Scm Corporation | Selective hydrogenation of α-pinene to cis-pinane |
| US4310714A (en) * | 1980-12-10 | 1982-01-12 | Union Camp Corporation | Hydrogenation of α-pinene to cis-pinane |
| EP0472853A1 (en) * | 1990-08-30 | 1992-03-04 | Hüls Aktiengesellschaft | Desactivated hydrogenation catalyst reactivation process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003835A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Method for preparing pinane by catalytic hydrogenation of turpentine |
| CN104003835B (en) * | 2014-05-04 | 2016-08-24 | 昆明理工大学 | A kind of method of Oleum Terebinthinae catalytic hydrogenation pinane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1191857A (en) | 1998-09-02 |
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