CN1202912C - Method for preparing load-type catalyst of modified cupric oxide - Google Patents
Method for preparing load-type catalyst of modified cupric oxide Download PDFInfo
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- CN1202912C CN1202912C CN 03140867 CN03140867A CN1202912C CN 1202912 C CN1202912 C CN 1202912C CN 03140867 CN03140867 CN 03140867 CN 03140867 A CN03140867 A CN 03140867A CN 1202912 C CN1202912 C CN 1202912C
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Abstract
The present invention relates to a method for preparing a cupric oxide supported catalyst and particularly a modified cupric oxide supported catalysts for synthesizing 4-terpineol. The method comprises the steps: porous carriers and deionized water are mixed into suspension, the water solution of cupric nitrate and sodium carbonate or the water solution of cupric chloride dihydrate and sodium carbonate is injected into the suspension simultaneously, and the injection rate is adjusted; ageing is carried out after the feed liquid is added, and precipitates are obtained, filtered, washed with water, pumped, dried, calcined and activated; cupric oxide supported catalysts are obtained and modified; and the compounds of elements of groups VA and VIA in the periodic table is added as modifiers in the process of agitation, and modified cupric oxide supported catalysts are obtained. Therefore, the method provides an effective method for preparing a modified cupric oxide supported catalystand has the advantages of high conversion rate and high selectivity, and the method can synthesize 4-terpineol from terpinolene 4, 8-epoxides in one step by way of catalytic hydrogenation.
Description
(1) technical field
The present invention relates to a kind of cupric oxide loaded catalyst, especially be suitable for the preparation method of the modified oxidized copper loaded catalyst of synthetic 4-terpinol.
(2) background technology
The 4-terpinol is a kind of special terpenol, it has very strong sterilization, sterilization, antisepsis, can suppress many ubiquity pathogenic cells and mould effectively, it is subject to people's attention day by day as important pharmaceutical intermediate again simultaneously, and demand constantly increases.The main method of producing at present the 4-terpinol has: the 1) isomerization reaction of 1,4 cineoles, but because raw material sources are limited, product postprocessing produces a large amount of waste water and can't industrialization in addition.2) terpinolene 4-8-epoxides isomerization/hydrogenation in the presence of copper oxide catalyst, weak point is to prepare the poor repeatability of copper oxide catalyst.
(3) summary of the invention
The present invention is intended to propose a kind ofly modify and improve, provide a kind of modified oxidized copper loaded catalyst with double-jet method (double-jet method) preparation cupric oxide loaded catalyst and to it, this catalyst is used for terpinolene 4, the synthetic 4-terpinol of one step of 8-epoxides hydrogenation, conversion ratio 85%, selectivity 75%.
Step of the present invention is as follows:
1) porous carrier and deionized water are mixed into suspension, simultaneously inject copper nitrate or copper chloride and aqueous sodium carbonate, regulate separately injection rate to keep neutralization degree of being to suspension;
2) feed liquid adds back ageing 1～8 hour, filters gained and precipitates, washes, drains;
3) 100～150 ℃ of dryings;
4) 250～500 ℃ of calcinings, activation 2～10 hours, get the cupric oxide loaded catalyst;
5) the gained catalyst is modified, addition element periodic table VA under agitation, VIA family element power supply subtype compound, or the mixture of this compound is made dressing agent more than 2 kinds, addition is catalyst by weight calculating: dressing agent=1000: (1～10) gets modified oxidized copper loaded catalyst.
By weight calculating, carrier: cupric oxide=1: (0.4～4) is preferably 1: (0.7～3) among the present invention.The porous carrier that uses among the present invention can be selected from silica gel, aluminium oxide, activated carbon, titanium oxide, diatomite or kaolin, or their mixture.Preferably be selected from silica gel, aluminium oxide or diatomite, or its mixture.Be preferably 4～10 hours said drying time.Preferably 300～400 ℃ of said calcining heats.The soak time of said Preparation of Catalyst preferably 4～8 hours.
The modified oxidized copper loaded catalyst of gained of the present invention can be used for synthetic 4-terpinol, and its method is to utilize terpinolene 4, the hydrogenation reaction of 8-epoxides, and concrete steps are:
With terpinolene 4,8-epoxides and above-mentioned prepared modified oxidized copper supported catalyst and solvent drop in the autoclave, the catalyst input amount is the 2%-6% of raw material weight, solvent: raw material=1: (1～6), Hydrogen Vapor Pressure 3-6Mpa, 120～200 ℃ of reaction temperatures, 8～10 hours reaction time, just make high-quality 4-terpinol, conversion ratio 85%, selectivity 75%.
Said dressing agent is periodic table of elements VA, VIA family element power supply subtype compound, or the mixture of two or more these compounds forms, and preferably is selected from triphenylphosphine, triphenyl phosphate, 2,4,6 triphenyl triazines or urea etc.
Carried out hydrogenation reaction again after both can having modified the cupric oxide loaded catalyst earlier when said catalyst modifier is used, also dressing agent can be added in the reactor with each reaction mass, the modification of catalyst and hydrogenation reaction are carried out simultaneously.
The invention provides a kind of effective ways that prepare modified oxidized copper loaded catalyst, and can one the step catalytic hydrogenation from terpinolene 4, the 8-epoxides synthesizes the 4-terpinol, its conversion ratio and selectivity are higher.
(4) specific embodiment
Embodiment 1. Preparation of Catalyst
In 500 milliliters of there-necked flasks that agitator and thermometer be housed, put into 2 gram diatomite and 150 ml deionized water, stirring at room makes suspension, in 2 250 ml beakers, dissolve 24.1 gram copper nitrates and 15 gram natrium carbonicum calcinatums solution respectively in 100 ml deionized water, simultaneously above two liquid are injected diatomaceous suspension with peristaltic pump, regulate above two liquid injection rates keeping neutralization, feed liquid adds after the back stirs ageing a few hours, filters washing.Gained is deposited in 120 ℃ of dryings promptly got the cupric oxide supported catalyst in 4 hours in 450 ℃ of calcinings, activation again after 4 hours.
Get this catalyst 10 grams, add the solution of 60 milligrams of triphenylphosphines, stir and promptly finished modification, hydrogen supply reaction use in 0.5 hour at 300 milliliters of ethanol.
Embodiment 2. terpinolene 4, the hydrogenation reaction of 8-epoxides
In 250 milliliters of autoclaves, add modified oxidized copper loaded catalyst 0.8 gram (embodiment 1 preparation), ethanol 25 grams, terpinolene 4,8-epoxides 15 grams (GC content 92%) lock kettle cover, with hydrogen exchange flushing 5 times, consume hydrogen 5Kg/cm at every turn
2, to guarantee that no air is residual in the system, start stirring then and be warming up to institute's fixed temperature, charge into hydrogen 30Kg/cm
2, when hydrogen pressure is absorbed and must replenishes immediately when reducing, coreaction finished GC testing result: terpinolene 4,8-conversion rate of epoxide 85%, 4-terpinol selectivity 75% in 8 hours.All the other accessory substances are: terpinolene about 3%.Oxygenatedchemicals about 9%.
Embodiment 3. terpinolene 4, the hydrogenation reaction of 8-epoxides
Operating procedure is with embodiment 2, but catalyst need not any modifier activation, at institute's fixed temperature, 30Kg/cm
2Hydrogen pressure reacted 8 hours down, GC testing result: terpinolene 4,8-conversion rate of epoxide 64%, 4-terpinol selectivity 40%.
Embodiment 4. terpinolene 4, the hydrogenation reaction of 8-epoxides
Operating procedure is with embodiment 2, but dressing agent uses 2,4, and 100 milligrams of 6-triphenyl triazines are at institute's fixed temperature, 30Kg/cm
2Hydrogen pressure reacted 8 hours down, GC testing result: terpinolene 4,8-conversion rate of epoxide 81%, 4-terpinol selectivity 76%.
Embodiment 5. Preparation of Catalyst
In being housed, 500 milliliters of there-necked flasks of agitator and thermometer add 4 gram diatomite and 100 ml deionized water, stirring at room makes suspension, in beaker, restrain copper chlorides with 100 ml waters dissolving, 1.5 gram barium nitrates and 17, another beaker dissolving sodium carbonate 18 grams, stir down metal salt solution and aqueous slkali are injected diatomite suspension simultaneously, regulate two liquid injection rates to keep neutralization, feed liquid adds the back and stirs ageing a few hours, filter, washing, gained is deposited in 100 ℃ of dryings 6 hours, again 480 ℃ of calcinings, activate 6 hours, promptly get the cupric oxide supported catalyst.
The hydrogenation reaction of embodiment 6. terpinolene 4,8 epoxides
In 250 milliliters of autoclaves, add cupric oxide supported catalyst 0.8 gram (embodiment 5), ethanol 30 grams, 2 milligrams in urea, terpinolene 4,8-epoxides 15 grams, operation is with embodiment 2, coreaction 8 hours, testing result conversion rate of epoxide 90%, 4-terpinol selectivity 73%.
Claims (9)
1, a kind of preparation method of modified oxidized copper loaded catalyst is characterized in that step is as follows:
1) porous carrier and deionized water are mixed into suspension, simultaneously inject copper nitrate and aqueous sodium carbonate, or copper chloride and aqueous sodium carbonate, regulate separately injection rate to keep neutralization degree of being to suspension;
2) feed liquid adds back ageing 1～8 hour, filters gained and precipitates, washes, drains;
3) 100～150 ℃ of dryings;
4) 250～500 ℃ of calcinings, activation 2～10 hours, get the cupric oxide loaded catalyst;
5) the gained catalyst is modified, addition element periodic table VA under agitation, VIA family element power supply subtype compound, or the mixture of this compound is made dressing agent more than 2 kinds, addition is catalyst by weight calculating: dressing agent=1000: 1～10 get modified oxidized copper loaded catalyst.
2, the preparation method of a kind of modified oxidized copper loaded catalyst as claimed in claim 1 is characterized in that by weight calculating carrier: cupric oxide=1: 0.4～4.
3, the preparation method of a kind of modified oxidized copper loaded catalyst as claimed in claim 2 is characterized in that the ratio of carrier and cupric oxide is 1: 0.7～3 by weight calculating.
4, the preparation method of a kind of modified oxidized copper loaded catalyst as claimed in claim 1 is characterized in that porous carrier is selected from silica gel, aluminium oxide, activated carbon, titanium oxide, diatomite or kaolin, or its mixture.
5, the preparation method of a kind of modified oxidized copper loaded catalyst as claimed in claim 4 is characterized in that porous carrier is selected from silica gel, aluminium oxide or diatomite, or its mixture.
6, the preparation method of a kind of modified oxidized copper loaded catalyst as claimed in claim 1 is characterized in that said calcining heat is 300～400 ℃.
7, the preparation method of a kind of modified oxidized copper loaded catalyst as claimed in claim 1, the soak time that it is characterized in that said Preparation of Catalyst is 4～8 hours.
8, the preparation method of a kind of modified oxidized copper loaded catalyst as claimed in claim 1 is characterized in that be 4～10 hours drying time.
9, the preparation method of a kind of modified oxidized copper loaded catalyst as claimed in claim 1 is characterized in that said dressing agent is selected from triphenylphosphine, triphenyl phosphate, 2,4,6 triphenyl triazine or urea.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03140867 CN1202912C (en) | 2003-06-02 | 2003-06-02 | Method for preparing load-type catalyst of modified cupric oxide |
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| CN 03140867 CN1202912C (en) | 2003-06-02 | 2003-06-02 | Method for preparing load-type catalyst of modified cupric oxide |
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| CN1202912C true CN1202912C (en) | 2005-05-25 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607206B (en) * | 2009-07-16 | 2012-05-30 | 复旦大学 | Method for increasing the activity of copper-based catalyst in water-gas shift reaction |
| GB201205764D0 (en) * | 2012-03-30 | 2012-05-16 | Johnson Matthey Plc | Catalyst and method of manufacture |
| KR20180003570A (en) | 2015-05-08 | 2018-01-09 | 바스프 아그로 비.브이. | A process for the preparation of terpinolene epoxide |
| US10538470B2 (en) | 2015-05-08 | 2020-01-21 | BASF Agro B.V. | Process for the preparation of limonene-4-ol |
| CN106554515B (en) * | 2015-09-28 | 2019-03-29 | 比亚迪股份有限公司 | Copper oxide coats diatomite composite material and plastics composite and plastic products and their preparation method comprising it |
| ES2787895T3 (en) | 2016-02-26 | 2020-10-19 | Basf Agro Bv | Procedure for the preparation of a mixture of terpene alcohols |
| EP3419954B1 (en) | 2016-02-26 | 2020-04-08 | BASF Agro B.V. | Process for preparing terpinene-4-ol |
| KR20190017926A (en) | 2016-06-15 | 2019-02-20 | 바스프 아그로 비.브이. | Epoxidation of tetrasubstituted alkenes |
| CN109311835A (en) | 2016-06-15 | 2019-02-05 | 巴斯夫农业公司 | The method of four substituted olefine of epoxidation |
| CN114682264A (en) * | 2022-04-11 | 2022-07-01 | 福州大学 | Catalyst for preparing 4-terpineol by epoxidizing terpinolene through hydrogenation, and preparation method and application thereof |
| CN115490923B (en) * | 2022-10-24 | 2023-12-08 | 河南瑞奇特化工有限公司 | Anti-precipitation extraction-resistant reactive anti-aging agent composition |
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