CN101445427A - Method for selective hydrogenation reaction in heterogeneous catalysis of cinnamic aldehyde - Google Patents
Method for selective hydrogenation reaction in heterogeneous catalysis of cinnamic aldehyde Download PDFInfo
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- CN101445427A CN101445427A CNA2008101639572A CN200810163957A CN101445427A CN 101445427 A CN101445427 A CN 101445427A CN A2008101639572 A CNA2008101639572 A CN A2008101639572A CN 200810163957 A CN200810163957 A CN 200810163957A CN 101445427 A CN101445427 A CN 101445427A
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- phenylacrolein
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- water
- selective hydrogenation
- ethanol
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Abstract
An environment-friendly method for selective hydrogenation reaction in heterogeneous catalysis of cinnamic aldehyde is a heterogeneous catalytic hydrogenation system consisting of water, ethanol, cinnamic aldehyde and solid catalyst. Reaction steps comprise: the water, the ethanol, the cinnamic aldehyde and the inorganic carrier loaded Pt-Co catalyst are respectively added in a stainless steel reaction kettle according a volume ratio of 0-1.7 between the water and the ethanol, a mol ratio of (0.43-2.17)*10<3> between a reagent and the catalyst (measured according to Pt content), and a reaction concentration of 0.2-1.0mol/L; replacement is carried out for three times by means of using hydrogen; electronic stirring (with a rotating speed greater than 600r/min) is carried out; and reaction is carried out at a temperature ranging from 40 DEG C to 80 DEG C and under a hydrogen pressure ranging from 1MPa to 3MPa. The heterogeneous catalytic hydrogenation system of the invention is environment-friendly and remarkably improves the hydrogenation activity of the cinnamic aldehyde on the loaded Pt-Co catalyst and the selectivity of cinnamic aldehyde generation.
Description
Technical field
The present invention relates to α, the method for beta-unsaturated aldehyde selective hydrogenation reaction in heterogeneous catalysis system, particularly a kind of eco-friendly selective hydrogenation reaction in heterogeneous catalysis of cinnamic aldehyde.
Background technology
α, beta-unsaturated aldehyde is important chemical material and intermediate, and in its false add hydrogen product, the unsaturated alcohol that obtains as the selective hydrogenation of C=O key is the important source material and the intermediate of medicine, spices etc. especially, and the saturated aldehyde that the selective hydrogenation of C=C key obtains is the important intermediate for preparing medicines such as HIV.Because α, C=C and C=O form conjugated system in the beta-unsaturated aldehyde, make their hydrogenation be different from the hydrogenation of single C=C or C=O.Therefore, to α, the selective hydrogenation of beta-unsaturated aldehyde research has important significance for theories and prospects for commercial application.Though homogeneous catalytic hydrogenation has down the hydrogenation selectivity of C=C key preferably or C=O key, product is difficult to separate with catalyzer, and heterogeneous catalyst has become α, the main means of the selective hydrogenation of beta-unsaturated aldehyde.Heterogeneous catalyst can be realized separating of catalyzer and product easily, reduce catalyst stream and become estranged to the pollution of product, and catalyzer is reusable, has improved the utilization ratio of catalyzer, and this also meets the requirement of Search green chemistry.In environment protection intensive today day by day, be implemented in and carry out catalytic hydrogenation reaction under the eco-friendly condition (low temperature, low pressure, pollution-free) and have long-range and realistic meanings.
Phenylacrolein is α, representational compound in the beta-unsaturated aldehyde, and the hydrogenation of C=C key is easier to carry out in the phenylacrolein molecule, and C=O key selective hydrogenation relative difficult.People can make the active bigger preferential hydrogenation of unsaturated link(age) C=C key by regulating the number and the activity of absorption hydrogen usually; Equally also can make preferential activation adsorption of C=O key and hydrogenation, or make the C=C key form strong absorption and become torpescence by changing the adaptability structure of catalyzer, thus realization selective catalytic hydrogenation phenylacrolein.The catalyst system of phenylacrolein selective hydrogenation research mostly is loaded noble metal catalyst, different De Expensive metal catalyst is to α, the activity of beta-unsaturated aldehyde hydrogenation and selectivity have very big difference, usually monometallic Pd catalyzer helps the selective hydrogenation of C=C key, and monometallic Pt catalyzer has selectivity preferably to C=O key hydrogenation, be mainly phenylpropyl aldehyde as the hydrogenation products on the Pd/C catalyzer, highly selective can reach 95%; Hydrogenation products on the Pt/C catalyzer then is mainly styryl carbinol, and highly selective can reach 78%.But different carriers, auxiliary agent and reaction system etc. all have epochmaking influence to phenylacrolein selective hydrogenation performance, can significantly improve the hydrogenation selectivity of C=O key on supporting Pt or the Pd catalyzer as the interpolation of auxiliary agent Co, Sn, and the interpolation of auxiliary agent Ni can significantly improve the hydrogenation selectivity of C=C key on the Pt/CNTs catalyzer.
How the selective reaction system is optimized reaction conditions, further improves the catalytic hydrogenation activity and the selectivity of phenylacrolein, is the problem that need study and solve.
Summary of the invention
The objective of the invention is selection and optimization, a kind of eco-friendly phenylacrolein catalytic selectivity hydrogenation reaction system is provided, improve the catalytic hydrogenation activity and the selectivity of phenylacrolein, realized the reaction process of green energy conservation reaction system.
The invention provides a kind of eco-friendly phenylacrolein catalytic selectivity process for selective hydrogenation, is the heterogeneous catalytic hydrogenation reaction system of forming with water-ethanol-phenylacrolein-solid catalyst.Water-ethanol is a solvent, water: the alcoholic acid volume ratio is: 0～1.7; Phenylacrolein is a reactant, and concentration is: 0.2～1.0mol/L; Inorganic carrier supporting Pt-Co is a catalyzer, and the content of Pt is 0.25～1.0wt%, and the content of Co is 0～0.68wt%; Reactions steps is: in stainless steel cauldron, by water: the alcoholic acid volume ratio is 0～1.7, reactant: the mol ratio of catalyzer (pressing the metering of Pt content) is (0.43～2.17) * 10
3, reactant concn is: 0.2～1.0mol/L, add entry, ethanol, phenylacrolein, inorganic carrier supporting Pt-Co catalyzer respectively, with hydrogen exchange three times, and electronic stirring (rotating speed〉600r/min), under 40～80 ℃ of temperature, hydrogen pressure 1～3MPa condition, reacted 1～4 hour.
Solvent of the present invention is a water-ethanol, water: the volume ratio of alcoholic acid is: 0～1.7, and optimum volume ratio is: 0.27～0.73.
Inorganic carrier of the present invention is TiO
2, γ-Al
2O
3, ZrO
2, CNTs (carbon nanotube) or AC (gac) a kind of.
The optimum content of Co is 0.1～0.34% in the catalyzer of the present invention, and the optimum content of Pt is 0.5～0.85wt%.
Top condition of the present invention is 60～80 ℃ of temperature, hydrogen pressure 2～3Mpa, 1.5～2.5 hours reaction times.
Phenylacrolein catalytic selectivity process for selective hydrogenation provided by the present invention, its advantage is: the selectivity that can significantly improve the hydrogenation activity and the generation styryl carbinol of phenylacrolein on the loaded Pt catalyst.Heterogeneous catalytic hydrogenation reaction system environmental friendliness of the present invention will have broad application prospects aspect synthetic in the selective hydrogenation of organic fine chemical catalysis.
Embodiment
Embodiment 1
The phenylacrolein catalytic hydrogenation reaction carries out in the stainless steel cauldron of 50mL, heating in water bath, magnetic agitation (1200r/min).TiO
2, γ-Al
2O
3, ZrO
2, CNTs (carbon nanotube) or AC (gac) load 0.5wt%Pt or 0.5wt%Pt-0.17wt%Co be catalyzer (0.36 gram), the cumulative volume of etoh solvent (or alcohol-water) and reactant phenylacrolein (8mmol, about 1mL) is 20mL.Air before the reaction in the usefulness hydrogen exchange reactor 3 times.Reaction conditions is: 70 ℃ of temperature of reaction, hydrogen pressure 2MPa and reaction times 1.5h.Reaction result sees Table the Catalytic Hydrogenation Properties of phenylacrolein on the 1 different carriers supporting Pt Co catalyzer
Annotate: CMA～phenylacrolein, HCMA～phenylpropyl aldehyde, HCMO～phenylpropyl alcohol, CMO～styryl carbinol, ACE～aldol(s)
Embodiment 2
With embodiment 1 identical operations, difference is: (1) changes the ratio of alcohol-water, and (2) use 0.5%Pt-0.17%Co/CNTs to be catalyzer.Reaction result is shown in Table 2.
The selection hydrogenation performance of phenylacrolein on the 0.5%Pt-0.17%Co/CNTs catalyzer in the reaction system of the different ethanol/water ratios of table 2
Embodiment 3
With embodiment 1 identical operations, difference is: (1) changes organic solvent (being respectively ethanol, propyl alcohol or propyl carbinol), and the volume ratio of organic solvent/water is 15/4; (2) use 0.5%Pt-0.17%Co/CNTs to be catalyzer.Reaction result is shown in Table 3.
Hydrogenation on cinnamic aldehyde Effect on Performance on the 0.5%Pt-0.17%Co/CNTs catalyzer in the reaction system of table 3 different solvents
Embodiment 4
With embodiment 1 identical operations, difference is: (1) uses 0.5%Pt-Co/CNTs to be catalyzer, changes the content of Co in the catalyzer; (2) solvent is 19mL ethanol-0mL water.Reaction result is shown in Table 4.
Hydrogenation on cinnamic aldehyde performance on the 0.5%Pt-Co/CNTs catalyzer of the different Co content of table 4
Embodiment 5
With embodiment 1 identical operations, difference is: (1) uses Pt-0.17%Co/CNTs to be catalyzer, changes the content of Pt in the catalyzer; (2) solvent is 19mL ethanol-0mL water; (3) temperature of reaction is 60 ℃.Reaction result is shown in Table 5.Hydrogenation on cinnamic aldehyde performance on the Pt-0.17%Co/CNTs catalyzer of the different Pt content of table 5
Embodiment 6
With embodiment 1 identical operations, difference is: (1) uses 0.5%Pt-0.17%Co/CNTs to be catalyzer; (2) solvent is 15mL ethanol-4mL water; (3) change temperature of reaction.Reaction result is shown in Table 6.
Hydrogenation on cinnamic aldehyde performance on the 0.5%Pt-0.17%Co/CNTs catalyzer under table 6 condition of different temperatures
Embodiment 7
With embodiment 1 identical operations, difference is: (1) uses 0.5%Pt-0.17%Co/CNTs to be catalyzer; (2) solvent is 19mL ethanol-0mL water; (3) change the reaction times.Reaction result is shown in Table 7.
Shortening phenylacrolein reactivity worth on the 0.5%Pt-0.17%Co/CNTs catalyzer under the table 7 differential responses time
Embodiment 8
With embodiment 1 identical operations, difference is: (1) uses 0.5%Pt-0.17%Co/CNTs to be catalyzer; (2) solvent is 19mL ethanol-0mL water; (3) temperature of reaction is 60 ℃; (4) change reaction pressure.Reaction result sees Table 8 not.
The different H of table 8
2Hydrogenation on cinnamic aldehyde reactivity worth on the 0.5%Pt-0.17%Co/CNTs catalyzer under the pressure condition
Claims (6)
1, a kind of eco-friendly phenylacrolein catalytic selectivity process for selective hydrogenation, it is the heterogeneous catalytic hydrogenation reaction system of forming with water-ethanol-phenylacrolein-solid catalyst, it is characterized in that: the employing water-ethanol is a solvent, phenylacrolein is a reactant, inorganic carrier supporting Pt-Co is a catalyzer, containing the Pt amount in the catalyzer is 0.25～1.0wt%, and containing the Co amount is 0～0.68wt%; Reactions steps is: in stainless steel cauldron, by water: the alcoholic acid volume ratio is 0～1.7, reactant: the mol ratio that catalyzer is pressed the metering of Pt content is (0.43～2.17) * 10
3, reactant concn is 0.2～1.0mol/L, adds entry, ethanol, phenylacrolein, inorganic carrier supporting Pt-Co catalyzer respectively, uses hydrogen exchange three times, electronic stirring was reacted 1～4 hour under 40～90 ℃ of temperature, hydrogen pressure 1～4MPa condition.
2, phenylacrolein catalytic selectivity process for selective hydrogenation according to claim 1, it is characterized in that: water: the alcoholic acid optimum volume ratio is: 0.27～0.73.
3, phenylacrolein catalytic selectivity process for selective hydrogenation according to claim 1, it is characterized in that: support of the catalyst is TiO
2, γ-Al
2O
3, ZrO
2, CNTs or AC a kind of.
4, phenylacrolein catalytic selectivity process for selective hydrogenation according to claim 1, it is characterized in that: the content of Co is 0.1～0.34% in the catalyzer, the content of Pt is 0.5～0.85wt%.
5, phenylacrolein catalytic selectivity process for selective hydrogenation according to claim 1, it is characterized in that: water: the alcoholic acid volume ratio is: 0.27～0.73.
6, phenylacrolein catalytic selectivity process for selective hydrogenation according to claim 1 is characterized in that: electronic mixing speed〉600r/min, 60～80 ℃ of temperature, reacted under the condition of hydrogen pressure 2～3MPa 1.5～2.5 hours.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513097A (en) * | 2011-11-01 | 2012-06-27 | 厦门大学 | Preparation method for synthesizing styrone platinum catalyst by selective hydrogenization of cinnamic aldehyde |
| CN104478664A (en) * | 2014-11-19 | 2015-04-01 | 浙江医药高等专科学校 | Multiphase selective hydrogenation reaction method for cinnamyl aldehyde |
| CN105148939A (en) * | 2015-09-15 | 2015-12-16 | 北京化工大学 | High-dispersion supported PtCo nano-alloy catalyst as well as preparation method and application thereof |
| CN106582635A (en) * | 2016-12-08 | 2017-04-26 | 上海华谊（集团）公司 | Catalyst for preparing unsaturated alcohol through selectively hydrogenating alpha and beta unsaturated aldehydes and preparation method for catalyst |
| CN106824221A (en) * | 2016-12-08 | 2017-06-13 | 上海华谊（集团）公司 | Catalyst of MAL selection Hydrogenation methallyl alcohol and preparation method thereof |
| CN107056566A (en) * | 2016-12-08 | 2017-08-18 | 上海华谊（集团）公司 | The method that α, β unsaturated aldehyde select Hydrogenation unsaturated alcohol |
| CN107285994A (en) * | 2016-04-13 | 2017-10-24 | 中国科学院大连化学物理研究所 | A kind of method that cinnamic acid selective hydrogenation synthesizes cinnamyl alcohol |
| CN108636455A (en) * | 2018-04-20 | 2018-10-12 | 北京工业大学 | It is a kind of using nucleocapsid MOF as the preparation and application of the carried noble metal base catalyst of reaction vessel |
| CN114573419A (en) * | 2022-02-09 | 2022-06-03 | 大连理工大学 | Alpha, beta-unsaturated aldehyde in-situ selective hydrogenation reaction process using water as cheap hydrogen donor |
| CN115337936A (en) * | 2022-10-18 | 2022-11-15 | 无锡威孚环保催化剂有限公司 | Preparation of PtCo/C catalyst and method for catalyzing selective hydrogenation of alpha, beta-unsaturated aldehyde by using PtCo/C catalyst |
| CN116273173A (en) * | 2022-12-08 | 2023-06-23 | 东南大学 | COF supported Ni-based catalyst and preparation and application thereof |
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2008
- 2008-12-30 CN CNA2008101639572A patent/CN101445427A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513097A (en) * | 2011-11-01 | 2012-06-27 | 厦门大学 | Preparation method for synthesizing styrone platinum catalyst by selective hydrogenization of cinnamic aldehyde |
| CN104478664A (en) * | 2014-11-19 | 2015-04-01 | 浙江医药高等专科学校 | Multiphase selective hydrogenation reaction method for cinnamyl aldehyde |
| CN105148939A (en) * | 2015-09-15 | 2015-12-16 | 北京化工大学 | High-dispersion supported PtCo nano-alloy catalyst as well as preparation method and application thereof |
| CN105148939B (en) * | 2015-09-15 | 2017-06-20 | 北京化工大学 | A kind of high-dispersion loading type PtCo nanometer alloy catalysts and its preparation method and application |
| CN107285994A (en) * | 2016-04-13 | 2017-10-24 | 中国科学院大连化学物理研究所 | A kind of method that cinnamic acid selective hydrogenation synthesizes cinnamyl alcohol |
| CN107285994B (en) * | 2016-04-13 | 2020-08-14 | 中国科学院大连化学物理研究所 | Method for synthesizing cinnamyl alcohol by selective hydrogenation of cinnamyl aldehyde |
| CN106582635A (en) * | 2016-12-08 | 2017-04-26 | 上海华谊（集团）公司 | Catalyst for preparing unsaturated alcohol through selectively hydrogenating alpha and beta unsaturated aldehydes and preparation method for catalyst |
| CN107056566A (en) * | 2016-12-08 | 2017-08-18 | 上海华谊（集团）公司 | The method that α, β unsaturated aldehyde select Hydrogenation unsaturated alcohol |
| CN106824221A (en) * | 2016-12-08 | 2017-06-13 | 上海华谊（集团）公司 | Catalyst of MAL selection Hydrogenation methallyl alcohol and preparation method thereof |
| CN108636455A (en) * | 2018-04-20 | 2018-10-12 | 北京工业大学 | It is a kind of using nucleocapsid MOF as the preparation and application of the carried noble metal base catalyst of reaction vessel |
| CN108636455B (en) * | 2018-04-20 | 2021-04-30 | 北京工业大学 | Preparation and application of supported noble metal-based catalyst taking core-shell MOF as reaction vessel |
| CN114573419A (en) * | 2022-02-09 | 2022-06-03 | 大连理工大学 | Alpha, beta-unsaturated aldehyde in-situ selective hydrogenation reaction process using water as cheap hydrogen donor |
| CN115337936A (en) * | 2022-10-18 | 2022-11-15 | 无锡威孚环保催化剂有限公司 | Preparation of PtCo/C catalyst and method for catalyzing selective hydrogenation of alpha, beta-unsaturated aldehyde by using PtCo/C catalyst |
| CN116273173A (en) * | 2022-12-08 | 2023-06-23 | 东南大学 | COF supported Ni-based catalyst and preparation and application thereof |
| CN116273173B (en) * | 2022-12-08 | 2024-04-19 | 东南大学 | COF supported Ni-based catalyst and preparation and application thereof |
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Open date: 20090603 |