CN104844408A - Method for catalyzing hydrogenation of alpha-pinene to prepare cis-pinane - Google Patents
Method for catalyzing hydrogenation of alpha-pinene to prepare cis-pinane Download PDFInfo
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- CN104844408A CN104844408A CN201510030412.4A CN201510030412A CN104844408A CN 104844408 A CN104844408 A CN 104844408A CN 201510030412 A CN201510030412 A CN 201510030412A CN 104844408 A CN104844408 A CN 104844408A
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- pinene
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- 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 67
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 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 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 abstract 1
- 241000779819 Syncarpia glomulifera Species 0.000 abstract 1
- 239000001739 pinus spp. Substances 0.000 abstract 1
- 229920001155 polypropylene Polymers 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 229940036248 turpentine Drugs 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 230000009466 transformation Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003822 preparative gas chromatography Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 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 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 2
- 229930006728 pinane Natural products 0.000 description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 2
- 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 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 description 1
- 229930008394 dihydromyrcenol Natural products 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- 238000011177 media preparation Methods 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 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 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for catalyzing hydrogenation of alpha-pinene to prepare cis-pinane to efficiently prepare cis-pinane by virtue of a metal nanoparticle hydrosol with stable polymers and belongs to the field of preparation and application of catalysts. A catalyst adopted in the invention is a ruthenium nanoparticle hydrosol which is prepared by virtue of hydrogenation reduction in a water medium by taking P123 (a polyoxyethylene-polypropylene oxide-polyoxyethylene triblock copolymer) as a stabilizer. The ruthenium nanoparticle hydrosol with stable polymers can be used for catalyzing hydrogenation of alpha-pinene so as to prepare cis-pinane with high activity, high selectivity and high stability under a mild condition. According to the preparation method provided by the invention, the metal nanoparticle hydrosol with stable polymers is used for the catalytic hydrogenating process of alpha-pinene for the first time. Preparation of the catalyst and catalytic hydrogenation are mild in reaction condition, environmentally friendly and free of any organic solvents. The catalyst has a remarkable recycling performance, thereby providing an efficient method for high added value utilization of oil of turpentine.
Description
Technical field
The metal nanoparticle water-sol catalysis α-pinene hydrogenation that the present invention relates to a kind of polymer stabilizing efficiently prepares the method for cis-pinane, specifically a kind of ruthenium nano particle water-sol stable with P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer) is for catalyzer, catalysis α-pinene Hydrogenation, for the method for cis-pinane, belongs to the preparation and application field of catalyzer.
Background technology
α-pinene, as important renewable rosin class resource, can generate cis-pinane and trans pinane after hydrogenation reaction.Pinane reacts to synthesize terpene spices and the series of downstream products thereof such as phantol, Geraniol and dihydromyrcenol further.Wherein, the reactive behavior of cis-pinane, higher than trans pinane, therefore wishes that the pinane used on perfume industry is high as far as possible along inverse ratio, to avoid occurring the problems such as derived product separating-purifying difficulty.And if think the cis-pinane obtaining highly selective efficiently, key is the selection of α-pinene hydrogenation catalyst.
Often there is the problem such as the lower and easy coking of catalyzer of selectivity of severe reaction conditions, product in current industrial conventional Pd/C and Raney-Ni catalyzer.For many years, chemists constantly seek high-cis optionally catalyst system (CN1262263A; CN101884925A; CN102671711B; CN104003831A), but still have that catalyst system complexity, temperature of reaction and pressure are higher so far, the shortcoming such as environmental pollution is comparatively serious, catalyzer repeat performance is not good.
Glassware for drinking water has abundance, cheap, the pollution-free and feature such as not burn, and water is applied in organic reaction as " green medium " the important research direction having become Green Chemistry field.Research finds, under some specific reaction system, water can significantly improve speed of reaction and selectivity, and easily realize the separation of product and catalyzer recycle (J Am Chem Soc, 1980,102,7816-7817; Chem Soc Rev, 2006,35,68-82).And since the nineties in last century, the application of metal nanoparticle in catalytic hydrogenation reaction of polymer stabilizing is paid close attention to widely.Segmented copolymer P123 is as a kind of tensio-active agent of amphiphilic, soluble in water, the transition metal nanoparticles water-sol with synthesizing stable under room temperature condition in water medium can be promoted, and can realize under mild reaction conditions for alkene, α, the high reactivity of beta-unsaturated aldehyde ketone and nitrobenzene derivative and high-selective and hydrogenating (Langmuir, 2004,20,8426-8430; Journal of Colloid and Interface Science, 2014,415,117-126).But up to now, the transition metal nanoparticles water-sol system of this polymer stabilizing is adopted to be not reported as in catalyst α-pinene hydrogenation reaction at home and abroad document, this technique of exploitation initiative, is expected to for the synthesis of cis-pinane provides efficient, gentle, an eco-friendly new way.
Summary of the invention
The object of the invention is the problems such as the lower and easy coking of catalyzer of selectivity in order to solve severe reaction conditions, cis-pinane in existing α-pinene hydrogenation technique, a kind of metal Ru Nanoparticles Hydrosol catalysis α-pinene hydrogenation reaction of polymer stabilizing is provided, efficiently prepares the method for cis-pinane in a mild condition.
According to the present invention, the metal Ru Nanoparticles Hydrosol catalyzer composition of the polymer stabilizing provided, function are as follows:
In water medium, with P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer, molecular weight: the micella 5800) formed is stablizer, prepares the ruthenium nano particle water-sol by the hydrogenating reduction of ruthenium salt.In this catalyst system, P123 not only can prevent ruthenium nano particle from assembling at the micella that water is formed, and can be used as amphipathic microreactor simultaneously, in catalyzed reaction to transformation efficiency and optionally improve play critical effect.
The concrete preparation method of metal Ru Nanoparticles Hydrosol catalyzer of polymer stabilizing provided by the invention is as follows:
In stainless steel cauldron, add P123 and the 2mL deionized water of 30mg, stirring at room temperature is even.Add the RuCl of 0.01mmol again
33H
2o, first uses H after fully stirring
2by air displacement in still for several times, the H of 0.5MPa is filled with afterwards
2, 60 DEG C are reacted 1 hour, obtain the black ruthenium Nanoparticles Hydrosol that P123 is stable.
The technical scheme of the metal Ru Nanoparticles Hydrosol catalysis α-pinene hydrogenation of polymer stabilizing provided by the invention is achieved in that
In the above-mentioned ruthenium nano particle water-sol system prepared, directly add a certain amount of α-pinene, be filled with the H of certain pressure
2carry out hydrogenation reaction.Reaction terminate after, the catalyzer water-sol and the layering of organic product phase, remove upper strata product mutually after, water-sol catalyst system then can directly be reused.
The mol ratio of technical scheme Raw α-pinene provided by the invention and ruthenium nano particle water-sol catalyzer is 200, and temperature of reaction is at 40 DEG C, and the reaction times is 2h, and reactive hydrogen atmospheric pressure is 0.7MPa.
The stable ruthenium nano particle water-sol catalysis α-pinene Hydrogenation of P123 provided by the invention compared with prior art has following feature for the method for cis-pinane:
(1) the invention provides a kind of take water as medium preparation and the method for stable alpha-pinene hydrogenation reacting metal catalyzer, simple and easy to do, clean cheapness;
(2) catalysis α-pinene hydrogen addition technology provided by the invention has very high catalytic activity and cis-pinane selectivity of product;
(3) catalysis α-pinene hydrogen addition technology provided by the invention does not need any organic solvent, and reaction conditions is gentle, environmental friendliness;
(4), in catalysis α-pinene hydrogen addition technology provided by the invention, water-sol catalyst system can directly be reused, and its catalytic performance is very stable.
Accompanying drawing explanation
fig. 1transmission electron microscope (TEM) photo of the ruthenium nano particle that the polymer P 123 prepared by embodiment 1 is stable and corresponding size distribution
figure.
fig. 2the x-ray photoelectron spectrum (XPS) of the ruthenium nano particle that the polymer P 123 prepared by embodiment 1 is stable
figure.
fig. 3for the laser confocal microscope (CLSM) of the micella microreactor formed in embodiment 2 reaction process irradiates
figure.
Embodiment
The following example is used for further illustrating the present invention, but does not thereby limit the invention.
The preparation of the ruthenium nano particle water-sol catalyzer of [embodiment 1] P123 polymer stabilizing
Join in stainless steel cauldron by 30mg P123 and 2mL water, stirring at room temperature is even.Add the RuCl of 0.01mmol again
33H
2o, first uses the H of 1MPa after fully stirring
2by air displacement in still 4 times, be filled with 0.5MPa H afterwards
2, 60 DEG C of reaction 1h, namely obtain the ruthenium nano particle water-sol catalyzer that P123 is stable.
accompanying drawing 1display, the ruthenium nano particle particle diameter prepared is at about 2.8nm, better dispersed.
accompanying drawing 2data show that the ruthenium nano particle major part (≈ 91.5%) prepared is zero-valent metal ruthenium, this be due to detect before sample making course expose in atmosphere, have a few part (≈ 8.5%) to be oxidized to ruthenium oxide.
2mmol α-pinene joins in the stainless steel cauldron of the 0.010mmol ruthenium nano particle water-sol catalyzer that the obtained P123 polymer stabilizing of embodiment 1 is housed (mol ratio of α-pinene and ruthenium nano particle is 200) by [embodiment 2], mix, with the hydrogen of 1MPa by air displacement in still 4 times, be filled with 0.7MPa H
2, stirring reaction 2h at 40 DEG C.After reaction terminates, collect upper strata product phase, adopt vapor-phase chromatography to carry out quantitative analysis.The transformation efficiency of α-pinene is 99.9%, and selectivity is 98.9%.
accompanying drawing 3laser confocal microscope (CLSM) irradiate characterization result and show, in embodiment 2 reaction process, the hydrogenation reaction of α-pinene is carried out in the micella microreactor of P123 hydrosol polymer formation, and its micella microreactor size is at about 700nm.
Product, with embodiment 2, after reaction terminates, is removed by [embodiment 3-26] experiment condition and reactions steps mutually, and the water-sol catalyzer of bottom then adds 2mmol α-pinene mutually, repeats the experimental procedure of embodiment 2, has carried out repeating experiment for 24 times.Catalyzer is after recycling 14 times, and the transformation efficiency of α-pinene is still 98.1%; After reusing 24 times, the transformation efficiency of α-pinene is 95.6%, and the selectivity of cis-pinane is 98.8%.
30mg P123 and 2mL methyl alcohol join in stainless steel cauldron by [comparative example 1], and stirring at room temperature is even.Add the RuCl of 0.01mmol again
33H
2o, first uses the H of 1MPa after fully stirring
2by air displacement in still 4 times, be filled with 0.5MPa H afterwards
2, 60 DEG C of reaction 1h, obtain comparative catalyst 1.
2mmol α-pinene is joined in the stainless steel cauldron that the obtained comparative catalyst 1 of comparative example 1 is housed (mol ratio of α-pinene and ruthenium nano particle is 200), mix, with the hydrogen of 1MPa by air displacement in still 4 times, be filled with 0.7MPaH
2, stirring reaction 2h at 40 DEG C.After reaction terminates, collect upper strata product phase, adopt vapor-phase chromatography to carry out quantitative analysis.The transformation efficiency of α-pinene is 33.2%, and selectivity is 98.5%.
[comparative example 2] is by the RuCl of 0.01mmol
33H
2o and 2mL water joins in stainless steel cauldron, first uses the H of 1MPa after fully stirring
2by air displacement in still 4 times, be filled with 0.5MPa H afterwards
2, 60 DEG C of reaction 1h, obtain comparative catalyst 2.
2mmol α-pinene is joined in the stainless steel cauldron that the obtained comparative catalyst 2 of comparative example 2 is housed (mol ratio of α-pinene and ruthenium nano particle is 200), mix, with the hydrogen of 1MPa by air displacement in still 4 times, be filled with 0.7MPaH
2, stirring reaction 2h at 40 DEG C.After reaction terminates, collect upper strata product phase, adopt vapor-phase chromatography to carry out quantitative analysis.The transformation efficiency of α-pinene is 21.7%, and selectivity is 93.5%.
Claims (3)
1. the metal nanoparticle water-sol catalysis α-pinene Hydrogenation of a polymer stabilizing is for the method for cis-pinane, it is characterized in that catalyzer is for stablizer with P123 (polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer), by the ruthenium nano particle water-sol that hydrogenating reduction method is prepared in water medium, direct efficient catalytic α-pinene hydrogenation in a mild condition, highly selective, high stability prepare cis-pinane.
2. a preparation method for the metal Ru Nanoparticles Hydrosol catalyzer of P123 polymer stabilizing according to claim 1, is characterized in that preparation process is as follows:
In stainless steel cauldron, add P123 and deionized water, stirring at room temperature is even.Add a certain amount of RuCl again
33H
2o, first uses H after fully stirring
2by air displacement in still 4 times, be filled with 0.5MPa H afterwards
2, 60 DEG C of reaction 1h, obtain the black ruthenium Nanoparticles Hydrosol catalyzer that P123 is stable.
3. the metal Ru Nanoparticles Hydrosol catalyzer of the P123 polymer stabilizing described in a claim 1 or 2, at organic solvent-free, the mol ratio of raw material α-pinene and ruthenium nano particle water-sol catalyzer is 200, temperature of reaction 40 DEG C, reaction times 2h, under the mild reaction conditions of hydrogen pressure 0.7MPa, direct hydrogenation prepares cis-pinane.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198689A (en) * | 2015-10-30 | 2015-12-30 | 青岛科技大学 | Method for preparing cis-pinane by adopting selective hydrogenation of alpha-pinene |
| CN105418355A (en) * | 2015-11-21 | 2016-03-23 | 青岛科技大学 | Method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation in aqueous medium |
| CN105566027A (en) * | 2016-02-22 | 2016-05-11 | 青岛科技大学 | Method of preparing cis-pinane by means of catalytic alpha-pinene hydrogenation under normal temperature and pressure |
| CN105622328A (en) * | 2016-03-28 | 2016-06-01 | 青岛科技大学 | Method for preparing cis-pinane by alpha-pinene hydrogenation |
| CN105642279A (en) * | 2015-12-25 | 2016-06-08 | 北京化工大学 | Water-soluble nanoparticle catalyst and application thereof |
| CN105753653A (en) * | 2016-03-29 | 2016-07-13 | 青岛科技大学 | Method for preparing fatty alcohol |
| CN106316747A (en) * | 2016-08-15 | 2017-01-11 | 青岛科技大学 | Method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation by means of palladium-nickel bimetallic catalyst |
| CN106345456A (en) * | 2016-08-22 | 2017-01-25 | 青岛科技大学 | Method for preparing aniline through aqueous-phase catalysis nitrobenzene 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 |
| CN107519867A (en) * | 2017-09-14 | 2017-12-29 | 江西省科学院应用化学研究所 | A kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of α firpenes selective hydrogenation synthesizing cis pinane |
| CN111545195A (en) * | 2020-05-19 | 2020-08-18 | 福州大学 | Recyclable Ru nano catalyst, preparation method thereof and application thereof in preparation of cis-pinane |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198689B (en) * | 2015-10-30 | 2018-01-19 | 青岛科技大学 | A kind of method that α firpenes selective hydrogenation prepares cis-pinane |
| CN105198689A (en) * | 2015-10-30 | 2015-12-30 | 青岛科技大学 | Method for preparing cis-pinane by adopting selective hydrogenation of alpha-pinene |
| CN105418355A (en) * | 2015-11-21 | 2016-03-23 | 青岛科技大学 | Method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation in aqueous medium |
| CN105642279A (en) * | 2015-12-25 | 2016-06-08 | 北京化工大学 | Water-soluble nanoparticle catalyst and application thereof |
| CN105566027A (en) * | 2016-02-22 | 2016-05-11 | 青岛科技大学 | Method of preparing cis-pinane by means of catalytic alpha-pinene hydrogenation under normal temperature and pressure |
| CN105566027B (en) * | 2016-02-22 | 2018-07-17 | 青岛科技大学 | Under a kind of normal temperature and pressure catalysis australene Hydrogenation for cis-pinane method |
| CN105622328A (en) * | 2016-03-28 | 2016-06-01 | 青岛科技大学 | Method for preparing cis-pinane by alpha-pinene hydrogenation |
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| CN105753653B (en) * | 2016-03-29 | 2018-12-21 | 青岛科技大学 | A method of preparing fatty alcohol |
| CN106316747A (en) * | 2016-08-15 | 2017-01-11 | 青岛科技大学 | Method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation by means of palladium-nickel bimetallic catalyst |
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| CN107519867A (en) * | 2017-09-14 | 2017-12-29 | 江西省科学院应用化学研究所 | A kind of preparation method of the ruthenium catalyst for titanium dioxide loaded of α firpenes selective hydrogenation synthesizing cis pinane |
| CN107519867B (en) * | 2017-09-14 | 2020-05-15 | 江西省科学院应用化学研究所 | Preparation method of ruthenium-supported titanium dioxide catalyst for synthesizing cis-pinane by selective hydrogenation of α -pinene |
| CN111545195A (en) * | 2020-05-19 | 2020-08-18 | 福州大学 | Recyclable Ru nano catalyst, preparation method thereof and application thereof in preparation of cis-pinane |
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