CN101602005B - Catalyst for synthesizing 3,3-dimethylbutanol by hydrogenation of 3,3-dimethylbutyrate and preparation method thereof - Google Patents
Catalyst for synthesizing 3,3-dimethylbutanol by hydrogenation of 3,3-dimethylbutyrate and preparation method thereof Download PDFInfo
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- CN101602005B CN101602005B CN2009101122325A CN200910112232A CN101602005B CN 101602005 B CN101602005 B CN 101602005B CN 2009101122325 A CN2009101122325 A CN 2009101122325A CN 200910112232 A CN200910112232 A CN 200910112232A CN 101602005 B CN101602005 B CN 101602005B
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Abstract
The invention discloses a catalyst for synthesizing 3,3-dimethylbutanol by hydrogenation of 3,3-dimethylbutyrate and a preparation method thereof, relates to a catalyst, and provides a catalyst for synthesizing 3,3-dimethylbutanol by hydrogenation of 3,3-dimethylbutyrate and a preparation method thereof, and a method for preparing the 3,3-dimethylbutanol by using the catalyst. The catalyst is a support type palladium-copper bimetallic catalyst, and a carrier is SiO2. The preparation method for the catalyst comprises the following steps: mixing and heating ethylene glycol and acetyl acetone, then adding binitrodiammine-palladium and Cu(NO3)2.3H2O into the mixture, adding tetraethyl orthosilicate into the mixture, stirring the mixture and then adding water and ethanol to obtain viscous solution, keeping the viscous solution standing, converting the viscous solution into gel, drying the gel, suspending the gel in cyclohexane, introducing hydrogen into the gel to bubble and activate, and filtering and drying the gel to obtain the catalyst. The preparation method for the 3,3-dimethylbutanol adopts hydrogenation reaction and is carried in an autoclave with magnetic stirring in the presence of solvent.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind ofly with 3,3-acid dimethyl methyl esters is a raw material, and is synthetic 3 by catalytic hydrogenation, the Catalysts and its preparation method of 3-dimethyl butyrate alcohol.
Background technology
3, the 3-dimethyl butyrate alcohol is a kind of important fine-chemical intermediate, can be used for preparing 3, the 3-dimethyl butyraldehyde, and the latter is the synthetic sweet essential raw material of intense sweetener knob.Document disclosed 3, the preparation method of 3-dimethyl butyrate alcohol obtains 3 with sulfuric acid, isobutene and ethylene reaction, 3-dimethylbutyl sulfuric ester, and then hydrolysis promptly gets 3, the 3-dimethyl butyrate alcohol, yield counts 30%～50% (referring to U.S. Pat 7,348,459 and Chinese patent 200810005724.X) with isobutene.The said method severe reaction conditions, 3,3-dimethyl butyrate alcohol yield is lower, causes 3, and the preparation cost of 3-dimethyl butyrate alcohol is very high.And raw material isobutene and ethene all is gas, the inconvenience transportation, and this, is difficult to obtain away from the Fine Chemical Works of petrochemical plant many.In addition, produce a large amount of spent acid in the preparation process, also bigger to ambient influnence.
Summary of the invention
The object of the present invention is to provide a kind ofly 3, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, the Catalysts and its preparation method of 3-dimethyl butyrate alcohol.
Another object of the present invention is to provide that a kind of raw material sources are easy, production cost is low, yield is higher and environmental friendliness, adopt describedly 3, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, the Preparation of Catalyst 3 of 3-dimethyl butyrate alcohol, the method for 3-dimethyl butyrate alcohol.
Of the present invention 3, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the catalyst of 3-dimethyl butyrate alcohol is the palladium and the copper bimetallic catalyst of support type, and carrier is SiO
2, the mass fraction of each component is a palladium 0.01～0.1 in the catalyst, copper 0.01～0.05, silica 0.85～0.98.
Of the present invention 3, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the Preparation of catalysts of 3-dimethyl butyrate alcohol adopts sol-gel process, and concrete steps are:
1) ethylene glycol and acetylacetone,2,4-pentanedione are mixed the back heating, stir, add dinitro diamino palladium [Pd (NH again
3)
2(NO
2)
2] and Cu (NO
3)
23H
2O continues to stir;
2) in above-mentioned system, add positive tetraethyl orthosilicate, add entry and ethanol after the stirring, get viscous solution, change gel into after leaving standstill;
3) with gel drying;
4) dried gel is suspended in the cyclohexane, feeds the activation of hydrogen bubbling, suction filtration then, drying promptly get 3, and the hydrogenation of 3-acid dimethyl methyl esters synthesizes 3, the catalyst of 3-dimethyl butyrate alcohol.
In step 1), press mass ratio, ethylene glycol: acetylacetone,2,4-pentanedione: dinitro diamino palladium [Pd (NH
3)
2(NO
2)
2]: Cu (NO
3)
23H
2O is preferably (32～40): (2～10): (0.2～2): (0.35～1.75), the temperature of described heating are preferably 70～90 ℃, and the temperature that described continuation is stirred is preferably 70～90 ℃, and the time of continuing to stir is preferably 1～10h.
In step 2) in, press mass ratio, positive tetraethyl orthosilicate: ethylene glycol: water: ethanol is preferably (27.25～30.45): (32～40): (4.5～8.5): (5～9), and the time of described stirring is preferably 1～5h, and the described time of leaving standstill is preferably 8～24h.
In step 3), described drying is preferably in 90～150 ℃ of following vacuum drying 6～24h.
In step 4), press mass ratio, cyclohexane: ethylene glycol is preferably (5～10): (32～40), and the temperature of described feeding hydrogen bubbling activation is preferably 80 ℃, the time that feeds the activation of hydrogen bubbling is preferably 1～5h, and described drying is vacuum drying 12～24h at room temperature preferably.
Adopt of the present inventionly 3, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, the catalyst of 3-dimethyl butyrate alcohol, and 3, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the method for 3-dimethyl butyrate alcohol is as follows:
Hydrogenation carries out having in the presence of the solvent, by mass percentage in the autoclave of band magnetic agitation, catalyst amount is 3,2%～20% of 3-acid dimethyl methyl esters, and reaction temperature is 120～180 ℃, Hydrogen Vapor Pressure is 1.0～5.0MPa, and the reaction time is 5～10h; Suitable solvent comprises alkane such as cyclohexane, normal heptane, presses mass ratio, solvent and 3, and the proportioning of 3-acid dimethyl methyl esters is (5～20): 1.
Solvent is the solubilizing reaction thing preferably, and can not be hydrogenated.
Raw material 3 of the present invention, 3-acid dimethyl methyl esters and hydrogen are cheap and easy to get, the catalyst activity height, selectivity is good, and 3,3-dimethyl butyrate alcohol yield height, cost is low, and is little to ambient influnence, and technology is easy, is easy to industrialization.
The specific embodiment
Following examples will the present invention is further illustrated.
Embodiment 1
Under the room temperature, 36g ethylene glycol and 6g acetylacetone,2,4-pentanedione are mixed, be heated to 80 ℃ then, under agitation add 1g dinitro diamino palladium [Pd (NH
3)
2(NO
2)
2] and 1gCu (NO
3)
23H
2O, keep 80 ℃ of temperature to stir 5h after, add the positive tetraethyl orthosilicate of 29g, stir 3h after, add behind 6.5g water and the 7g ethanol a viscous solution, change gel into after leaving standstill 12h.With this gel at 130 ℃ of following vacuum drying 12h.Dried gel is suspended in the 80g cyclohexane, under 80 ℃, normal pressure, feeds hydrogen bubbling activation 4h.Suction filtration then, vacuum drying 18h promptly gets catalyst under the room temperature.
In the autoclave of 500mL band magnetic agitation, add 20g3, the catalyst of 3-acid dimethyl methyl esters, 160g cyclohexane and the preparation of 2g present embodiment.Reaction system with hydrogen exchange 3 times, is charged into Hydrogen Vapor Pressure 3.0MPa, reaction 8h when 150 ℃ of temperature.The reactant mixture gas chromatographic analysis, the result shows, 3, the conversion ratio of 3-acid dimethyl methyl esters is 98.5%, 3, the selectivity of 3-dimethyl butyrate alcohol is 97.1%, 3,3-dimethyl butyrate alcohol yield 95.6%.
Embodiment 2
Under the room temperature, 32g ethylene glycol and 10g acetylacetone,2,4-pentanedione are mixed, be heated to 70 ℃ then, under agitation add 2g dinitro diamino palladium [Pd (NH
3)
2(NO
2)
2] and 0.35gCu (NO
3)
23H
2O, keep 70 ℃ of temperature to stir 10h after, add the positive tetraethyl orthosilicate of 28.65g, stir 5h after, add behind 8.5g water and the 5g ethanol a viscous solution, change gel into after leaving standstill 12h.With this gel at 150 ℃ of following vacuum drying 6h.Dried gel is suspended in the 90g cyclohexane, under 80 ℃, normal pressure, feeds hydrogen bubbling activation 5h.Suction filtration then, vacuum drying 12h promptly gets catalyst under the room temperature.
In the autoclave of 500mL band magnetic agitation, add 20g3, the catalyst of 3-acid dimethyl methyl esters, 160g cyclohexane and the preparation of 2g present embodiment.Reaction system with hydrogen exchange 3 times, is charged into Hydrogen Vapor Pressure 3.0MPa, reaction 8h when 150 ℃ of temperature.The reactant mixture gas chromatographic analysis, the result shows, 3, the conversion ratio of 3-acid dimethyl methyl esters is 98.7%, 3, the selectivity of 3-dimethyl butyrate alcohol is 95.1%, 3,3-dimethyl butyrate alcohol yield 93.9%.
Embodiment 3
Under the room temperature, 40g ethylene glycol and 2g acetylacetone,2,4-pentanedione are mixed, be heated to 90 ℃ then, under agitation add 0.2g dinitro diamino palladium [Pd (NH
3)
2(NO
2)
2] and 1.75gCu (NO
3)
23H
2O, keep 90 ℃ of temperature to stir 5h after, add the positive tetraethyl orthosilicate of 29.05g, stir 3h after, add behind 4.5g water and the 9g ethanol a viscous solution, change gel into after leaving standstill 12h.With this gel at 90 ℃ of following vacuum drying 24h.Dried gel is suspended in the 80g cyclohexane, under 80 ℃, normal pressure, feeds hydrogen bubbling activation 1h.Suction filtration then, vacuum drying 24h promptly gets catalyst under the room temperature.
In the autoclave of 500mL band magnetic agitation, add 20g3, the catalyst of 3-acid dimethyl methyl esters, 160g cyclohexane and the preparation of 2g present embodiment.Reaction system with hydrogen exchange 3 times, is charged into Hydrogen Vapor Pressure 3.0MPa, reaction 8h when 150 ℃ of temperature.The reactant mixture gas chromatographic analysis, the result shows, 3, the conversion ratio of 3-acid dimethyl methyl esters is 95.3%, 3, the selectivity of 3-dimethyl butyrate alcohol is 97.6%, 3,3-dimethyl butyrate alcohol yield 93.0%.
Embodiment 4
In the autoclave of 500mL band magnetic agitation, add 20g3, the catalyst of 3-acid dimethyl methyl esters, 100g cyclohexane and 0.4g embodiment 1 preparation.Reaction system with hydrogen exchange 3 times, is charged into Hydrogen Vapor Pressure 5.0MPa, reaction 10h when 180 ℃ of temperature.The reactant mixture gas chromatographic analysis, the result shows, 3, the conversion ratio of 3-acid dimethyl methyl esters is 96.8%, 3, the selectivity of 3-dimethyl butyrate alcohol is 95.3%, 3,3-dimethyl butyrate alcohol yield 92.3%.
Embodiment 5
In the autoclave of 500mL band magnetic agitation, add 20g3, the catalyst of 3-acid dimethyl methyl esters, 400g cyclohexane and 4g embodiment 1 preparation.Reaction system with hydrogen exchange 3 times, is charged into Hydrogen Vapor Pressure 1.0MPa, reaction 5h when 120 ℃ of temperature.The reactant mixture gas chromatographic analysis, the result shows, 3, the conversion ratio of 3-acid dimethyl methyl esters is 93.8%, 3, the selectivity of 3-dimethyl butyrate alcohol is 97.5%, 3,3-dimethyl butyrate alcohol yield 91.5%.
Embodiment 6
In the autoclave of 500mL band magnetic agitation, add 20g3, the catalyst of 3-acid dimethyl methyl esters, 160g normal heptane and 2g embodiment 1 preparation.Reaction system with hydrogen exchange 3 times, is charged into Hydrogen Vapor Pressure 3.0MPa, reaction 8h when 150 ℃ of temperature.The reactant mixture gas chromatographic analysis, the result shows, 3, the conversion ratio of 3-acid dimethyl methyl esters is 97.2%, 3, the selectivity of 3-dimethyl butyrate alcohol is 97.0%, 3,3-dimethyl butyrate alcohol yield 94.3%.
Claims (9)
1.3 the hydrogenation of 3-acid dimethyl methyl esters synthesizes 3, the Preparation of catalysts method of 3-dimethyl butyrate alcohol, it is characterized in that, described 3,3-acid dimethyl methyl esters hydrogenation synthetic 3, the catalyst of 3-dimethyl butyrate alcohol is the palladium and the copper bimetallic catalyst of support type, and carrier is SiO
2, the mass fraction of each component is a palladium 0.01～0.1 in the catalyst, copper 0.01～0.05, silica 0.85～0.98; Described preparation method may further comprise the steps:
1) ethylene glycol and acetylacetone,2,4-pentanedione are mixed the back heating, stir, add dinitro diamino palladium [Pd (NH again
3)
2(NO
2)
2] and Cu (NO
3)
23H
2O continues to stir;
2) in above-mentioned system, add positive tetraethyl orthosilicate, add entry and ethanol after the stirring, get viscous solution, change gel into after leaving standstill;
3) with gel drying;
4) dried gel is suspended in the cyclohexane, feeds the activation of hydrogen bubbling, suction filtration then, drying promptly get 3, and the hydrogenation of 3-acid dimethyl methyl esters synthesizes 3, the catalyst of 3-dimethyl butyrate alcohol.
2. as claimed in claim 13, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the Preparation of catalysts method of 3-dimethyl butyrate alcohol is characterized in that pressing mass ratio in step 1), ethylene glycol: acetylacetone,2,4-pentanedione: dinitro diamino palladium [Pd (NH
3)
2(NO
2)
2]: Cu (NO
3)
23H
2O is (32～40): (2～10): (0.2～2): (0.35～1.75).
3. as claimed in claim 13, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the Preparation of catalysts method of 3-dimethyl butyrate alcohol is characterized in that in step 1), and the temperature of described heating is 70～90 ℃.
4. as claimed in claim 13, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the Preparation of catalysts method of 3-dimethyl butyrate alcohol is characterized in that in step 1), and the temperature that described continuation is stirred is 70～90 ℃, and the time of continuing to stir is 1～10h.
5. as claimed in claim 13,3-acid dimethyl methyl esters hydrogenation synthetic 3, the Preparation of catalysts method of 3-dimethyl butyrate alcohol, it is characterized in that in step 2) in, press mass ratio, positive tetraethyl orthosilicate: ethylene glycol: water: ethanol is (27.25～30.45): (32～40): (4.5～8.5): (5～9).
6. as claimed in claim 13, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the Preparation of catalysts method of 3-dimethyl butyrate alcohol is characterized in that in step 2) in, the time of described stirring is 1～5h, the described time of leaving standstill is 8～24h.
7. as claimed in claim 13, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the Preparation of catalysts method of 3-dimethyl butyrate alcohol is characterized in that in step 3), and described drying is at 90～150 ℃ of following vacuum drying 6～24h.
8. as claimed in claim 13,3-acid dimethyl methyl esters hydrogenation synthetic 3, the Preparation of catalysts method of 3-dimethyl butyrate alcohol, it is characterized in that in step 4), press mass ratio, cyclohexane: ethylene glycol is (5～10): (32～40), and the temperature of described feeding hydrogen bubbling activation is 80 ℃, the time that feeds the activation of hydrogen bubbling is 1～5h, and described drying is vacuum drying 12～24h at room temperature.
9. adopt according to claim 13, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, the catalyst of 3-dimethyl butyrate alcohol, and 3, the hydrogenation of 3-acid dimethyl methyl esters is synthetic 3, and the method for 3-dimethyl butyrate alcohol is characterized in that its concrete steps are as follows:
Hydrogenation carries out having in the presence of the solvent, by mass percentage in the autoclave of band magnetic agitation, catalyst amount is 3,2%～20% of 3-acid dimethyl methyl esters, and reaction temperature is 120～180 ℃, Hydrogen Vapor Pressure is 1.0～5.0MPa, and the reaction time is 5～10h; Solvent is cyclohexane, normal heptane, presses mass ratio, solvent and 3, and the proportioning of 3-acid dimethyl methyl esters is (5～20): 1.
Priority Applications (1)
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|---|---|---|---|
| CN2009101122325A CN101602005B (en) | 2009-07-17 | 2009-07-17 | Catalyst for synthesizing 3,3-dimethylbutanol by hydrogenation of 3,3-dimethylbutyrate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101122325A CN101602005B (en) | 2009-07-17 | 2009-07-17 | Catalyst for synthesizing 3,3-dimethylbutanol by hydrogenation of 3,3-dimethylbutyrate and preparation method thereof |
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| CN101602005B true CN101602005B (en) | 2011-05-25 |
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| CN102631928B (en) * | 2012-03-28 | 2014-03-19 | 厦门大学 | Catalyst for synthesizing 3, 3-dimethylbutyraldehyde and preparation method of catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7348459B2 (en) * | 1999-07-02 | 2008-03-25 | The Nutrasweet Company | Process for the preparation of 3,3-dimethylbutanal |
| CN101411990A (en) * | 2008-11-12 | 2009-04-22 | 复旦大学 | Method for preparing catalyst used in method for preparing ethanediol by dimethyl oxalate hydrogenation |
| CN101455976A (en) * | 2008-12-16 | 2009-06-17 | 上海焦化有限公司 | Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof |
-
2009
- 2009-07-17 CN CN2009101122325A patent/CN101602005B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7348459B2 (en) * | 1999-07-02 | 2008-03-25 | The Nutrasweet Company | Process for the preparation of 3,3-dimethylbutanal |
| CN101411990A (en) * | 2008-11-12 | 2009-04-22 | 复旦大学 | Method for preparing catalyst used in method for preparing ethanediol by dimethyl oxalate hydrogenation |
| CN101455976A (en) * | 2008-12-16 | 2009-06-17 | 上海焦化有限公司 | Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Carlos A. Leony Leon, et al.Adsorption and catalytic properties of Pd/SiO2,Cu/SiO2, and Pd-Cu/SiO2 systems III. Carbon monoxide and benzene hydrogenation over Pd-Cu/SiO2 catalysts.《Applied Catalysis》.1991,第69卷305-321. * |
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