CN1081950C - Method preparation of compound catalyst with selective preparation of dihydro-beta-irisone - Google Patents
Method preparation of compound catalyst with selective preparation of dihydro-beta-irisone Download PDFInfo
- Publication number
- CN1081950C CN1081950C CN98113345A CN98113345A CN1081950C CN 1081950 C CN1081950 C CN 1081950C CN 98113345 A CN98113345 A CN 98113345A CN 98113345 A CN98113345 A CN 98113345A CN 1081950 C CN1081950 C CN 1081950C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel
- alloy
- beta
- dihydro
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention belongs to a preparation method which selectively prepares a composite catalyst of dihydro-beta-ionone. The present invention adopts a nickel framework catalyst specially prepared and has the preparation steps that after nickel aluminum alloy is quickly digested by sodium hydroxide solution, alkali metal halide is used for processing, or metal nickel and metal aluminum added with the alkali metal halide beforehand are made into a definite number of the nickel aluminum alloy, and then, the nickel aluminum alloy is digested by the sodium hydroxide solution; the prepared catalyst, organic amine, beta-ionone and a solvent react together, the total yield of the product is not less than 70%, the reaction conversion rate is not less than 85%, and the reactive selectivity is larger than 90%.
Description
The present invention is the preparation method with composite catalyst of selective preparation of dihydro-beta-irisone.
Dihydro-practise to claim the sweet osmanthus king, and systematic naming method is 4-(2,6,6-trimethyl-1-cyclohexenyl group)-2-butanone, be present in the osmanthus essential oil and be the most critical component of osmanthus essential oil, and be extremely famous and precious high-grade spices.It is in occurring in nature storage rareness, and extraction is difficult for, so people adopt several different methods synthesizing dihydro-alpha, beta-lonone to satisfy ever-increasing needs.From the later stage seventies, countries such as Japan, Germany and the former Soviet Union reported the synthetic of dihydro-successively.In general, the main method of preparation dihydro-has: 1. semi-synthesis method: alpha, beta-lonone (2,6,6-trimethyl-cyclohexenyl group-1-butene-2-ketone) catalytic hydrogenation method, as, palladium loads on the rare earth oxide as catalyst reduction alpha, beta-lonone (Omarkulov, T.O.; Goncharova, S.V.; Porov, N.I., Vestn.Akad.Nauk.Kaz.SSR, 1989, (3), 63-6.cf, Chem.Abstr., 1989,111:233228f), or negative hydrogen catalyst is with metering method reduction-alpha, beta-lonone, as, selective reduction alpha, beta-lonones such as sodium hydrogen telluride (Yamashita, M.; Nishida, M.; Suemitsu, R., Sci.Eng.Rev.DoshishaUni., 1986,27 (2), 74-9.Cf.Chem.Abstr., 1987,106:214145g).2. complete synthesizing process: from 1,1, the 6-trimethylcyclohexanone sets out and prepares dihydro-β-ionol through multistep reaction, and the latter obtains dihydro alpha, beta-lonone (Schmidt, c. through the Jones oxidation; Chishti, N.H.; Breining, T., Synthesis, 1982, (5), 391-3.) etc.Consider that from raw material and operation the catalytic hydrogenation method in the first method is suitable for suitability for industrialized production most.
The architectural feature of alpha, beta-lonone is the interior carbon-carbon double bond of ring, the outer carbon-carbon double bond of ring and the two keys of carbon oxygen, and three two keys are in conjugate action.Will be in the alpha, beta-lonone molecule one of them two key of selective hydration, key is hydrogenation catalyst.People such as Omarkulov to different catalysts (as RaneyNi, Ni/Al
2O
3, Ni/SiO
2, Ni-Cr
2O
3/ C, Rh/Al
2O
3, rhodium black, palladium China ink, platinum black and other alloy catalyst etc.) study, find its selectivity order Ni＞Rh＞Pt＞Pd (Sokol ' shii, D.V., Omarkulov, T.O.; Shoshenkova, V.A.; Abishev, M.A.; Suyunbaev, U., Zh.Fiz.Khim., 1982,56 (5), 1290-2.Cf.Chem.Abstr.1982,97:127101s).From present result of study, no matter be that precious metal loaded catalyst or alloy catalyst are mainly obtaining the different mixture of degree of hydrogenation aspect the alpha, beta-lonone selective hydrogenation, therefore, the development about the selective hydrocatalyst of alpha, beta-lonone still is the key and the focus of synthesizing dihydro-alpha, beta-lonone.
The invention provides a kind of preparation method who is used for the composite catalyst of alpha, beta-lonone selective hydrogenation.
Preparation method provided by the invention is prepared into skeletal nickel catalyst with nickel alumin(i)um alloy through specially treated, maybe will be prepared into skeletal nickel catalyst through the nickel alumin(i)um alloy of specially treated, add compounding ingredients before the reaction, use the fixed bed reaction still, the alpha, beta-lonone selective hydrogenation is obtained the dihydro alpha, beta-lonone.Embodiment comprises as follows:
Method of modifying 1:
With the certain density aqueous slkali digestion certain hour of a certain amount of nickel alumin(i)um alloy, obtain skeletal nickel catalyst after the different solvents washing for several times in uniform temperature.The solvent of putting into the organic amine (as fatty amine, arylamine, nitrogen-containing heterocycle compound etc.) of the alkali halide (as chloride, bromide and the iodide etc. of lithium, sodium, potassium) of percentage by weight 1～25% and percentage by weight 25～50% by the weight of catalyst before using soaks and is no more than half an hour, obtains through handling or the composite catalyst of modification.
Method of modifying 2:
To be prepared into nickel alumin(i)um alloy under metallic nickel and metallic aluminium and alkali halide (with method of modifying 1) (adding) high temperature by 1～25% of whole weight.The latter digests certain hour after being ground into 30～60 purpose particles in uniform temperature and certain density aqueous slkali, different solvents obtains skeletal nickel catalyst after washing for several times respectively.Join in the reactor with the catalyst of constant weight with by the organic amine (with method of modifying 1) of catalyst weight percentage 25～50% during use and directly use.
Composite catalyst provided by the invention has improved the conversion ratio and the selectivity of reaction, and reaction conversion ratio is not less than 85%, and selectivity is greater than 90%.
Example one
20 gram nickel alumin(i)um alloies (nickel aluminium content ratio is 1: 1) are divided to join 300 milliliters of temperature in small batches be 90～95 ℃, weight concentration is in 10% the sodium hydroxide solution, to add back digestion 1 hour.After washing 5 times respectively with clear water and absolute ethyl alcohol rapidly, obtain skeletal nickel catalyst.In the ethanol that soaks 4 gram catalyst, add the triethylamine of the KI of catalyst weight percentage 2.5% and catalyst weight percentage 25% before using and place half an hour, obtain the catalyst that is suitable for into invention.
Example two
To be prepared into nickel alumin(i)um alloy and be ground into 40～60 purpose particles under 500 gram metallic nickels, 500 gram metallic aluminiums and 18 gram KI (with the method for modifying 1) high temperature.Divide small quantities of 20 gram nickel alumin(i)um alloies that add at 90～95 ℃, digestion is 1 hour in 300 milliliters of sodium hydroxide solutions of 10% weight concentration.After washing 5 times respectively with clear water and absolute ethyl alcohol rapidly after digestion is finished, obtain skeletal nickel catalyst.Modify by the triethylamine of 4 gram catalyst adding percentage by weights 25% before using.
Claims (4)
1. the method for making with composite catalyst of selective preparation of dihydro-beta-irisone is at first made skeletal nickel catalyst with nickel alumin(i)um alloy through handling, and modifies then, it is characterized in that the modification of catalyst comprises as follows respectively:
Method 1). nickel alumin(i)um alloy is in 90～95 ℃, aqueous slkali digestion is after 1 hour, obtain skeletal nickel catalyst through washing, add before this catalyst used to soak in the organic amine solution of the alkali halide of catalyst weight 1～25% and catalyst weight 25～50% and be no more than half an hour, make described composite catalyst;
Or method 2). the alkali halide of metallic nickel and metallic aluminium and weight alloy 1～25% is made nickel alumin(i)um alloy under heating condition, again with nickel alumin(i)um alloy in 90～95 ℃, aqueous slkali digestion is after 1 hour, obtain skeletal nickel catalyst through washing, during use, the organic amine of catalyst and catalyst weight 25～50% added in the reactor together directly use.
2. according to the catalyst method for making described in the claim 1, it is characterized in that described nickel alumin(i)um alloy nickel aluminium content ratio is 1: 1.
3. according to the catalyst method for making described in the claim 1, it is characterized in that described alkali halide is chloride, bromide and the iodide of lithium, sodium, potassium.
4. according to the catalyst method for making described in the claim 1, it is characterized in that described organic amine is fatty amine, arylamine and nitrogen-containing heterocycle compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113345A CN1081950C (en) | 1998-09-14 | 1998-09-14 | Method preparation of compound catalyst with selective preparation of dihydro-beta-irisone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113345A CN1081950C (en) | 1998-09-14 | 1998-09-14 | Method preparation of compound catalyst with selective preparation of dihydro-beta-irisone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1212902A CN1212902A (en) | 1999-04-07 |
| CN1081950C true CN1081950C (en) | 2002-04-03 |
Family
ID=5223084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113345A Expired - Fee Related CN1081950C (en) | 1998-09-14 | 1998-09-14 | Method preparation of compound catalyst with selective preparation of dihydro-beta-irisone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1081950C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142287B (en) * | 2017-05-12 | 2020-12-08 | 南京林业大学 | Artemisinic aldehyde double-bond reductase DBR1 and application of recombinant bacterium thereof in preparation of dihydro-beta-ionone |
| CN108329198B (en) * | 2018-04-13 | 2021-04-13 | 梧州学院 | Preparation method of tetrahydro ionone |
| CN110201663B (en) * | 2019-05-28 | 2020-06-30 | 浙江大学 | Application of selective hydrogenation catalyst as catalyst in hydrogenation reaction |
| CN111871429B (en) * | 2020-08-28 | 2022-07-12 | 万华化学集团股份有限公司 | Raney catalyst and preparation method thereof, and method for preparing gamma-ketene from alpha, gamma-dienone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1990A1 (en) * | 1919-10-23 | 1924-09-15 | Н.Н. Вознесенский | The method of preparation of consistent ointments |
| JPS6136239A (en) * | 1984-07-27 | 1986-02-20 | Ogawa Koryo Kk | Production of dihydro-beta-ionone |
| CN1117149A (en) * | 1994-06-10 | 1996-02-21 | 佳能株式会社 | Electrophotographic photosensitive member, electrophotographic apparatus including same and electrophotographic apparatus unit |
-
1998
- 1998-09-14 CN CN98113345A patent/CN1081950C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1990A1 (en) * | 1919-10-23 | 1924-09-15 | Н.Н. Вознесенский | The method of preparation of consistent ointments |
| JPS6136239A (en) * | 1984-07-27 | 1986-02-20 | Ogawa Koryo Kk | Production of dihydro-beta-ionone |
| CN1117149A (en) * | 1994-06-10 | 1996-02-21 | 佳能株式会社 | Electrophotographic photosensitive member, electrophotographic apparatus including same and electrophotographic apparatus unit |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1212902A (en) | 1999-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112076738B (en) | Boron-doped defective zinc oxide and preparation method and application thereof | |
| CN109772312A (en) | A kind of selection of m-xylene diamine plus hydrogen prepare the catalyst of 1,3- hexamethylene dimethylamine | |
| CN112569965B (en) | Double-transition metal hierarchical pore catalyst and preparation method and application thereof | |
| CN1081950C (en) | Method preparation of compound catalyst with selective preparation of dihydro-beta-irisone | |
| CN112495397A (en) | Activation regeneration method of Raney nickel catalyst used for producing m-xylylenediamine | |
| CN102675048B (en) | Method for synthesizing prenol by composite catalyst | |
| CN107537497A (en) | A kind of preparation method and application for being used to prepare the catalyst of adjacent methyl cyclohexanol | |
| CN110756198A (en) | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof | |
| CN104888794B (en) | Metal composition catalyst, preparation method thereof and application thereof in preparation of D, L-menthol | |
| CN101492433B (en) | Green synthesis of 2-methylte-trahydrofuran | |
| CN113042043A (en) | Ruthenium-based hydrogenation catalyst, aqueous solution of ruthenium-based hydrogenation catalyst, and preparation method and application of aqueous solution | |
| CN109678732B (en) | Method for continuously producing 5-amino-1-pentanol | |
| CN110256198B (en) | Production method of 1, 4-pentanediol | |
| CN102212314A (en) | Method for preparing water-white highly-hydrogenated rosin | |
| CN106946668A (en) | A kind of method that phenol hydrogenation prepares cyclohexanone | |
| CN1024536C (en) | Active non-uniform catalyzer for ordinary pressure water-gas methanides and its making method | |
| CN107497426B (en) | Preparation method and application of palladium/silver alloy nano catalyst | |
| CN112609202A (en) | Method for synthesizing natural product Xanthoisozoline B through electrocatalysis and product thereof | |
| CN102029155B (en) | Hydrogen producing catalyst | |
| CN110922310A (en) | Method for preparing hydroxy butanone by using cellulose | |
| CN111004091A (en) | Method for preparing 4,4,5,5, 5-penta-fluoropentanol | |
| DE2408436C3 (en) | Method for producing cubic boron nitride K.K. Komatsu Seisakusho, Tokyo | |
| CN114570376B (en) | Catalyst for synthesizing menthone and method for synthesizing menthone | |
| DE2519580A1 (en) | Methanising catalyst contg. nickel - pptd. from alcohol solns. with combined aq. alkali borohydride and aq. alkali carbonate solns. | |
| CN101209967A (en) | Method for preparing linalyl acetate from dehydrolinalool |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |