CN107983382B - Catalyst for selective hydrogenation of liquid-phase α -unsaturated aldehyde and preparation method thereof - Google Patents

Catalyst for selective hydrogenation of liquid-phase α -unsaturated aldehyde and preparation method thereof Download PDF

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CN107983382B
CN107983382B CN201711108307.3A CN201711108307A CN107983382B CN 107983382 B CN107983382 B CN 107983382B CN 201711108307 A CN201711108307 A CN 201711108307A CN 107983382 B CN107983382 B CN 107983382B
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CN107983382A (en
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黄富强
毕庆员
袁晓涛
尹国恒
黄谢意
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Shanghai Institute of Ceramics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J35/393—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases

Abstract

The invention relates to a catalyst for selective hydrogenation of liquid-phase α -unsaturated aldehyde and a preparation method thereof, wherein the preparation method comprises the steps of taking a graphite tube filled with metal M powder and precious metal powder as an anode, taking a graphite rod as a cathode, vacuumizing a reaction cavity, filling hydrogen into the reaction cavity, and carrying out arc discharge reaction, wherein M is at least one of Mo, Nb, W, Ti, Zr and Ta, and the precious metal powder is at least one of Ru, Pd, Au and Pt, so as to obtain the catalyst, and the parameters of the arc discharge reaction comprise that the distance between the anode and the cathode is 2-5 mm, the current is 40-100A, and the reaction time is 0.5-5 hours.

Description

Catalyst for selective hydrogenation of liquid-phase α -unsaturated aldehyde and preparation method thereof
Technical Field
The invention relates to a catalyst for selective hydrogenation of liquid-phase α -unsaturated aldehyde and a preparation method thereof, belonging to the technical field of chemical catalysts.
Background
α -unsaturated alcohols (RHC ═ CH-CH)2-OH) with unique molecular structure and physicochemical properties, such as crotyl alcohol, allyl alcohol, cinnamyl alcohol, furfuryl alcohol and the like, are important organic intermediates and chemical raw materials, in the fields of spices, essences, medicines and fine chemicalsThe production of α -unsaturated alcohol is still obtained by direct reduction of α -unsaturated aldehyde by strong reducing agent, but the method has the problems of harsh reaction conditions, difficult separation of product and reducing agent, and serious environmental pollution caused by generation of a large amount of three wastes, and the like, so how to improve the economic benefit and the environmental benefit of the industrial process, and the core is the effective design and the successful preparation of the catalyst-1Therefore, hydrogenation of C ═ C bonds is thermodynamically more favorable, and saturated aldehydes and saturated alcohols are easily produced, resulting in poor selectivity for unsaturated alcohols. Therefore, how to realize the directional conversion of C ═ O bonds and improve the selectivity of unsaturated alcohols is a significant challenge. The research shows that the nature of the metal determines the performance of the catalyst, Ir and Pt have the best selectivity to C ═ O bond, Au and Ag are the second ones, Co and Cu are the better C ═ O bond hydrogenation non-noble metal catalysts, Ni and Pd mainly show the C ═ C bond hydrogenation, and the selectivity to C ═ O bond hydrogenation is lower. Noble metals Pt and Au are the two most commonly used types of catalysts, and the catalyst taking the noble metals Pt and Au as active components not only has higher selectivity on unsaturated alcohol, but also has high reaction activity. Meanwhile, factors such as a carrier, an auxiliary agent, a preparation method, the size of metal particles, a precursor of active metal and the like have obvious influence on the performance of the catalyst.
There have been long efforts to develop highly active, highly selective and highly stable catalysts for selective hydrogenation of α -unsaturated aldehydes to α -unsaturated alcohols3The Co alloy nano catalyst can realize the high-efficiency conversion of cinnamaldehyde and citral, and the steric effect of long-chain amine groups can change the adsorption mode of unsaturated aldehyde on the surface of the catalyst, so that the hydrogenation of C-C bonds (Angew. chem. int. Ed.2012,51,3440.) can be effectively inhibited. Mesoporous carbon loaded Co prepared by high-temperature pyrolysis method3O4The nano catalyst can be used upSelective hydrogenation of furfural and hydroxymethylfurfural to yield unsaturated alcohols in high yield (angew. chem. int. ed.2016. 55,11101.). Au/SiC achieves highly selective hydrogenation of cinnamaldehyde under the action of visible light. electrons on Au particles resonate under illumination to generate high-energy thermoelectrons to inject into conduction bands of SiC, whereas electron-deficient Au particles can oxidize isopropanol to generate active hydrogen, and the negatively charged accumulation zone at the Au-SiC interface is favorable for activating the C ═ O bonds at the top of cinnamaldehyde molecules and preferentially undergo hydrogenation (j.am. chem. soc.2016,138, 9361.). obviously, how to efficiently regulate the preferential adsorption and activation of C ═ O bonds is one of the key scientific problems in achieving α -unsaturated aldehyde selective hydrogenation processes.
Chinese patent ZL 200910095384.9 discloses the name: a catalyst for gas-phase crotonaldehyde selective hydrogenation to crotyl alcohol and a preparation method thereof. The technology uses a Ce-M-O (M is Sm, Y and La) composite oxide to impregnate and load Pt nano particles (the content of Pt is 0.5-5 wt%) at room temperature as a catalyst. The catalyst can show high activity, selectivity and stability at a relatively low reaction temperature. However, the amount of Pt used in the catalyst is relatively high, and the selective conversion efficiency of gas-phase crotonaldehyde is not high overall.
Chinese patent CN 201310537743 discloses a preparation method of a catalyst for α -unsaturated aldehyde selective hydrogenation, which uses carbon-coated ferroferric oxide loaded noble metal nanoparticles such as Pt, Pd, Ru and the like with a core-shell structure as the catalyst, and has good activity and good cyclic usability in α -unsaturated aldehyde selective hydrogenation reaction.
Disclosure of Invention
The invention aims to solve the problems of harsh reaction conditions, low intrinsic activity, insufficient stability and the like of the existing catalyst for synthesizing unsaturated alcohol by selective hydrogenation of liquid-phase α -unsaturated aldehyde, and aims to provide a heterogeneous catalyst with high performance and high stability under mild conditions and a preparation method thereof.
In one aspect, the present invention provides a method for preparing a catalyst for selective hydrogenation of liquid phase α -unsaturated aldehydes, comprising:
taking a graphite tube filled with metal M powder and precious metal powder as an anode, taking a graphite rod as a cathode, and vacuumizing a reaction cavity, wherein M is at least one of Mo, Nb, W, Ti, Zr and Ta, and the precious metal powder is at least one of Ru, Pd, Au and Pt;
filling hydrogen into the reaction cavity, and then carrying out arc discharge reaction to obtain the catalyst, wherein the parameters of the arc discharge reaction comprise: the distance between the anode and the cathode is 2-5 mm, the current is 40-100A, and the reaction time is 0.5-5 hours.
The method comprises the steps of selecting a graphite tube filled with metal M powder (M can be Mo, Nb, W, Ti, Zr, Ta and the like) and precious metal powder (such as Au powder, Pt powder, Ru powder, Pd powder and the like) as an anode, selecting a graphite rod as a cathode, pumping a reaction cavity to be vacuum, filling hydrogen into the reaction cavity, and then carrying out arc discharge reaction (the distance between the anode and the cathode is 2-5 mm, the current is 40-100A, and the reaction time is 0.5-5 hours) to obtain the catalyst.
Preferably, the mass of the metal M powder and the noble metal powder is 1: (0.1-2%); or adding the metal M powder into a precursor aqueous solution containing noble metal elements, adding sodium borohydride, washing and drying to obtain mixed powder of the metal M powder and the noble metal powder.
Further, it is preferable that the molar concentration of the noble metal element in the noble metal element-containing precursor aqueous solution is 0.05 to 1mmol L-1。
Preferably, the molar ratio of the sodium borohydride to the noble metal powder is (5-20): 1.
preferably, the graphite tube has an outer diameter of 5-10 mm, an inner diameter of 3-6 mm, and a length of 8-20 cm.
Preferably, the graphite rod has a diameter of 5-10 mm and a length of 8-20 cm.
Preferably, the pressure of the hydrogen is 0.04 to 0.1 MPa.
Preferably, the vacuum degree of the vacuum is 2 to 10 Pa.
On the other hand, the invention also provides a catalyst for selective hydrogenation of liquid-phase α -unsaturated aldehyde, which is prepared by the preparation method, and the catalyst comprises a carrier and a precious metal active component loaded on the surface of the carrier, wherein the carrier is a carbide MC, M is at least one of Mo, Nb, W, Ti, Zr and Ta, the precious metal active component is at least one of Ru, Pd, Au and Pt, and the mass content of the active component is 0.1-2%, preferably 0.5-1%.
Preferably, the particle size of the noble metal active component is 0.5-6 nm.
Preferably, the particle size of the carrier is 10 to 200 nm.
The catalyst prepared by the method is used for synthesizing unsaturated alcohol by liquid-phase α -unsaturated aldehyde selective hydrogenation, has higher activity and stability under relatively mild conditions, and has the advantages of simple and quick preparation method, low cost and the like, and the catalyst is prepared at 100 ℃ under H2Under the pressure of 2MPa, the selectivity of Pt/MoC on the selective hydrogenation of crotonaldehyde to crotyl alcohol reaches 99 percent, and the conversion number (TOF) in unit time reaches 1216h-1The activity of the catalyst is far higher than that of the catalyst reported in the literature at present, and meanwhile, the catalyst shows good stability.
Drawings
FIG. 1 is a high resolution TEM micrograph of 0.5 wt% Pt-ZrC catalyst.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The catalyst consists of a carrier and an active component, wherein the carrier can be a carbide MC (M ═ Mo, Nb, W, Ti, Zr, Ta and the like), the active component can be at least one of nano-sized noble metals Ru, Pd, Au and Pt, preferably platinum or gold, the mass content of the noble metals can be 0.1-2%, and the catalyst can also be expressed as Pt-MC, Au-MC and the like.
The catalyst is prepared in one step by a simple, quick and low-cost arc discharge method, and the preparation method of the catalyst for liquid-phase α -unsaturated aldehyde selective hydrogenation provided by the invention is exemplarily described below.
And preparing mixed powder of metal M powder and noble metal powder. Directly mixing metal M powder and noble metal powder, wherein the mass ratio of the metal M powder to the noble metal powder can be 1: (0.1-2%). Or by adding metal M powder to an aqueous precursor solution containing a noble metal element, e.g. H2PtCl6Or/and HAuCl4And adding sodium borohydride into the aqueous solution, and washing and drying to obtain mixed powder of metal M powder and noble metal powder. The molar concentration of the noble metal element in the precursor aqueous solution containing the noble metal element can be 0.05-1 mmol L-1. Wherein the mass ratio of the metal M powder to the noble metal elements can be 1: (0.1-2%). The molar ratio of the sodium borohydride to the noble metal powder can be (5-20): 1.
as an example, 0.2-1 g (preferably 0.2-0.5 g) of metal M powder is dispersed in 50-500 mL of water, then a corresponding amount of chloroplatinic acid or chloroauric acid aqueous solution is added, stirring is carried out, sodium borohydride aqueous solution is added, stirring is carried out for 10min, then suction filtration and full washing are carried out, and then the precipitate is dried at the vacuum chamber temperature for 5-20 h, so as to obtain the mixed metal powder of metal M and platinum or gold. The volume of the chloroplatinic acid or chloroauric acid aqueous solution is 10-200 ml, and the concentration is 0.05-1 mmol L–1. The concentration volume of the sodium borohydride aqueous solution can be 50-500 ml, and the concentration is 0.1-2.5 mmol L–1。
And filling the mixed powder of the metal M powder and the noble metal powder into the graphite tube to form the anode. The outer diameter of the graphite tube can be 5-10 mm, the inner diameter can be 3-6 mm, and the length can be 8-20 cm.
The cathode graphite rod is fixed on a water-cooled copper base to be horizontally opposite to the anode material. The diameter of the graphite rod can be 5-10 mm, and the length can be 8-20 cm.
And vacuumizing the reaction cavity until the pressure is 2-10 Pa. And then filling hydrogen into the reaction cavity until the pressure is 0.04-0.1 MPa.
And then, enabling the anode and the cathode to be close to generate arc discharge and plasma, reacting for 0.5-5 h at the current of 40-100A, and adjusting the distance between the cathode and the anode to keep the distance between the cathode and the anode at 2-5 mm (for example, about 2mm) in the reaction process.
And finally, turning off a power supply, naturally settling the obtained product for 1-6 hours, and collecting the product to obtain the Pt-MC or Au-MC catalyst.
The catalyst has high activity, selectivity and stability under relatively mild conditions for liquid phase α -unsaturated aldehyde selective hydrogenation reaction, wherein all catalytic reactions are carried out in a high-pressure reaction kettle, a reaction substrate, a solvent and the catalyst are put into a 50mL high-pressure reactor with a built-in temperature control device and react for 5-20 h at a given temperature (60-160 ℃), a pressure (0.5-3 MPa) and uniform stirring (800rpm), a gas bag is used for collecting gas products and directly analyzing the gas products by gas chromatography, and the liquid products are added with an internal standard substance 1, 4-dioxane and then quantitatively analyzed by gas chromatography.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following embodiments of the present invention, the particle size of the M powder may be 1 to 100 μ M.
Example 1:
a certain amount of Mo powder (1g) was dispersed in 50mL of water, and then 0.2mmol L of Mo powder was added-1Aqueous chloroplatinic acid solution (25ml) of (5), stirring and adding 0.5mmol L of-1Stirring the aqueous solution of sodium borohydride (200ml) for 10min, filtering and fully washing, and drying the precipitate for 10h at the vacuum room temperature to obtain mixed metal powder of Mo and Pt. Filling the mixed metal powder into a graphite tube with the outer diameter of 10mm, the inner diameter of 5mm and the length of 16cm to form an anode, fixing a cathode graphite rod with the diameter of 6mm and the length of 14cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 5Pa, then filling hydrogen until the pressure is 0.05MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (3mm), reacting for 2h under the current of 50A, then turning off a power supply, naturally settling a reaction product for 2h, and collecting to obtain the Pt-MoC catalyst;
weighing 30mg of Pt-MoC catalyst, adding into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of crotonaldehyde, exhausting air, and introducing 2MPa of H2The reaction was carried out at 100 ℃ for 6 hours, and the results are shown in Table 1.
Example 2:
an amount of Nb powder (0.5g) was dispersed in 100mL of water, and then 0.05mmol L of Nb powder was added-1Aqueous chloroplatinic acid solution (105ml) of (5), stirring and adding 0.2mmol L of L-1Stirring the sodium borohydride aqueous solution (500ml) for 10min, filtering and fully washing, and drying the precipitate at the vacuum room temperature for 8h to obtain mixed metal powder of Nb and Pt. Filling the mixed metal powder into a graphite tube with an outer diameter of 10mm, an inner diameter of 5mm and a length of 20cm to form an anode, fixing a cathode graphite rod with a diameter of 6mm and a length of 20cm on a water-cooled copper base and horizontally opposite to the anode material, and vacuumizing a reaction cavity until the reaction cavity is pressedAfter the force is 4Pa, hydrogen is charged until the pressure is 0.08MPa, then the anode and the cathode are close to generate arc discharge and plasma (2mm), the power supply is closed after the reaction is carried out for 2h under the current of 60A, and the reaction product is naturally settled for 4h and collected to obtain the Pt-NbC catalyst;
weighing 20mg of Pt-NbC catalyst, adding the Pt-NbC catalyst into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of crotonaldehyde, exhausting air, and introducing 1.5MPa of H2The reaction was carried out at 140 ℃ for 5 hours, and the results are shown in Table 1.
Example 3:
a certain amount of W powder (0.5g) was dispersed in 300mL of water, and then 0.6mmol L of L was added-1Was added to the solution of palladium chloride (40ml), and stirred to a concentration of 0.3mmol L-1Stirring the sodium borohydride aqueous solution (400ml) for 10min, filtering and fully washing, and drying the precipitate for 5h at vacuum room temperature to obtain mixed metal powder of W and Pd. Filling the mixed metal powder into a graphite tube with the outer diameter of 10mm, the inner diameter of 5mm and the length of 16cm to form an anode, fixing a cathode graphite rod with the diameter of 6mm and the length of 14cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 10Pa, then filling hydrogen until the pressure is 0.04MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (4mm), reacting for 5h under the current of 80A, then turning off a power supply, naturally settling reaction products for 6h, and collecting to obtain the Pd-WC catalyst;
weighing 20mg Pd-WC catalyst, adding into a high-pressure reaction kettle containing 2mL ethanol and 0.5mL crotonaldehyde, exhausting air, and introducing 2MPa H2The reaction was carried out at 100 ℃ for 10 hours, and the results are shown in Table 1.
Example 4:
a certain amount of Ti powder (0.2g) was dispersed in 400mL of water, and then 0.3mmol L of Ti powder was added-1Was added to the solution of chloroplatinic acid (35ml), and stirred to a concentration of 1.5mmol L-1Stirring the aqueous solution of sodium borohydride (70ml) for 10min, filtering and fully washing, and drying the precipitate at the vacuum room temperature for 12h to obtain mixed metal powder of Ti and Pt. Filling the mixed metal powder into graphite tube with outer diameter of 10mm, inner diameter of 5mm and length of 16cm to form anodeFixing a cathode graphite rod with the diameter of 6mm and the length of 14cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 4Pa, then filling hydrogen until the pressure is 0.08MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (5mm), reacting for 5 hours at the current of 70A, then closing a power supply, naturally settling reaction products for 5 hours and collecting to obtain the Pt-TiC catalyst;
weighing 20mg of Pt-TiC catalyst, adding the Pt-TiC catalyst into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of crotonaldehyde, exhausting air, and introducing 3MPa of H2The reaction was carried out at 60 ℃ for 20 hours, and the results are shown in Table 1.
Example 5:
a certain amount of Zr powder (1g) was dispersed in 200mL of water, and then 0.2mmol L of Zr powder was added-1Was added to the solution of chloroplatinic acid (130ml), and stirred and added thereto at a concentration of 2mmol L-1Stirring the sodium borohydride aqueous solution (130ml) for 10min, filtering and fully washing, and drying the precipitate for 20h at the vacuum room temperature to obtain the mixed metal powder of Zr and Pt. Filling the mixed metal powder into a graphite tube with the outer diameter of 10mm, the inner diameter of 5mm and the length of 16cm to form an anode, fixing a cathode graphite rod with the diameter of 6mm and the length of 14cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 4Pa, then filling hydrogen until the pressure is 0.06MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (3mm), reacting for 5h under the current of 40A, then turning off a power supply, naturally settling a reaction product for 1h, and collecting to obtain the Pt-ZrC catalyst;
weighing 20mg of Pt-TiC catalyst, adding the Pt-TiC catalyst into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of cinnamaldehyde, exhausting air, and introducing 2MPa of H2The reaction was carried out at 150 ℃ for 10 hours, and the results are shown in Table 1.
Example 6:
a certain amount of Ta powder (0.6g) was dispersed in 200mL of water, followed by addition of 0.8mmol L-1Was added to the solution of chloroplatinic acid (40ml), and stirred and added thereto a 2mmol L concentration-1Stirring for 10min, filtering, washing, and vacuum drying to obtain precipitate at room temperatureAnd drying for 8h to obtain mixed metal powder of Ta and Pt. Filling the mixed metal powder into a graphite tube with the outer diameter of 10mm, the inner diameter of 5mm and the length of 16cm to form an anode, fixing a cathode graphite rod with the diameter of 6mm and the length of 14cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 4Pa, then filling hydrogen until the pressure is 0.05MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (3mm), reacting for 3h under the current of 80A, then turning off a power supply, naturally settling a reaction product for 5h, and collecting to obtain the Pt-TaC catalyst;
weighing 20mg of Pt-TaC catalyst, adding the Pt-TaC catalyst into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of cinnamaldehyde, exhausting air, and introducing 2MPa of H2The reaction was carried out at 140 ℃ for 10 hours, and the results are shown in Table 1.
Example 7:
a certain amount of Mo powder (0.2g) was dispersed in 100mL of water, and then 0.8mmol L of Mo powder was added-1Aqueous ruthenium chloride solution (25ml), stirred and added with 0.2mmol L-1Stirring the aqueous solution of sodium borohydride (500ml) for 10min, filtering and fully washing, and drying the precipitate for 10h at vacuum room temperature to obtain mixed metal powder of Mo and Ru. Filling the mixed metal powder into a graphite tube with the outer diameter of 10mm, the inner diameter of 5mm and the length of 16cm to form an anode, fixing a cathode graphite rod with the diameter of 6mm and the length of 14cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 2Pa, then filling hydrogen until the pressure is 0.06MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (2mm), reacting for 2h under the current of 60A, then turning off a power supply, naturally settling a reaction product for 2h, and collecting to obtain the Ru-MoC catalyst;
weighing 20mg of Ru-MoC catalyst, adding the catalyst into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of crotonaldehyde, exhausting air, and introducing 2MPa of H2The reaction was carried out at 100 ℃ for 10 hours, and the results are shown in Table 1.
Example 8:
an amount of Nb powder (0.5g) was dispersed in 100mL of water, and then 0.05mmol L of Nb powder was added-1Aqueous chloroauric acid solution (1)00ml), stirred and added with 0.2mmol L-1Stirring the sodium borohydride aqueous solution (500ml) for 10min, filtering and fully washing, and drying the precipitate at the vacuum room temperature for 8h to obtain mixed metal powder of Nb and Au. Filling the mixed metal powder into a graphite tube with the outer diameter of 10mm, the inner diameter of 5mm and the length of 20cm to form an anode, fixing a cathode graphite rod with the diameter of 6mm and the length of 20cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 4Pa, then filling hydrogen until the pressure is 0.08MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (4mm), reacting for 2h under the current of 70A, then turning off a power supply, naturally settling a reaction product for 3h, and collecting to obtain an Au-NbC catalyst;
weighing 20mg of Au-NbC catalyst, adding the Au-NbC catalyst into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of furfural, exhausting air, and introducing 2MPa of H2The reaction was carried out at 120 ℃ for 10 hours, and the results are shown in Table 1.
Example 9:
a certain amount of W powder (1g) was dispersed in 200mL of water, and then 0.4mmol L of L was added-1Aqueous chloroauric acid solution (65ml), stirring and adding 0.3mmol L-1Stirring the aqueous solution of sodium borohydride (450ml) for 10min, filtering and fully washing, and drying the precipitate at the vacuum room temperature for 5h to obtain mixed metal powder of W and Au. Filling the mixed metal powder into a graphite tube with the outer diameter of 10mm, the inner diameter of 5mm and the length of 16cm to form an anode, fixing a cathode graphite rod with the diameter of 6mm and the length of 14cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 5Pa, then filling hydrogen until the pressure is 0.06MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (5mm), reacting for 5h under the current of 80A, then turning off a power supply, naturally settling a reaction product for 4h, and collecting to obtain an Au-WC catalyst;
weighing 20mg of Au-WC catalyst, adding the Au-WC catalyst into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of acrolein, exhausting air, and introducing 2MPa of H2The reaction was carried out at 120 ℃ for 12 hours, and the results are shown in Table 1.
Example 10:
a certain amount of Ta powder (1g) was dispersed in 300mL of water, followed by addition of 0.6mmol L-1Aqueous chloroauric acid solution (85ml), stirring and adding 0.8mmol L-1Stirring the sodium borohydride aqueous solution (320ml) for 10min, filtering and fully washing, and drying the precipitate at the vacuum chamber temperature for 12h to obtain mixed metal powder of Ta and Au. Filling the mixed metal powder into a graphite tube with the outer diameter of 10mm, the inner diameter of 5mm and the length of 16cm to form an anode, fixing a cathode graphite rod with the diameter of 6mm and the length of 14cm on a water-cooled copper base and horizontally opposite to the anode material, vacuumizing a reaction cavity until the pressure is 4Pa, then filling hydrogen until the pressure is 0.05MPa, then enabling the anode and the cathode to be close to generate arc discharge and plasma (3mm), reacting for 4h under the current of 60A, then turning off a power supply, naturally settling a reaction product for 2h, and collecting to obtain the Au-TaC catalyst;
weighing 20mg of Au-TaC catalyst, adding into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of cinnamaldehyde, exhausting air, and introducing 2.5MPa of H2The reaction was carried out at 110 ℃ for 10 hours, and the results are shown in Table 1.
Example 11:
a defined amount of MoC powder (1g) was dispersed in 50mL of water, then 0.5mmol L was added-1Aqueous chloroplatinic acid solution (10ml) of (2) was stirred and added to a concentration of 0.1mmol L-1Stirring the sodium borohydride aqueous solution (500ml) for 10min, performing suction filtration and full washing, and drying the precipitate for 10h at the vacuum chamber temperature to obtain the Pt-MoC catalyst;
weighing 30mg of Pt-MoC catalyst, adding into a high-pressure reaction kettle containing 2mL of ethanol and 0.5mL of crotonaldehyde, exhausting air, and introducing 2MPa of H2The reaction was carried out at 100 ℃ for 6 hours, and the results are shown in Table 1.
Table 1 shows the performance of the catalysts prepared in examples 1 to 11 for the selective hydrogenation of α -unsaturated aldehyde to α -unsaturated alcohol:
Figure BDA0001462689640000091

Claims (8)

1. a method for preparing a catalyst for selective hydrogenation of α -unsaturated aldehydes in liquid phase, comprising:
taking a graphite tube filled with metal M powder and precious metal powder as an anode, taking a graphite rod as a cathode, and vacuumizing a reaction cavity, wherein M is at least one of Mo, Nb, W, Ti, Zr and Ta, and the precious metal powder is at least one of Ru, Pd, Au and Pt;
filling hydrogen into the reaction cavity, and then carrying out arc discharge reaction to obtain the catalyst, wherein the parameters of the arc discharge reaction comprise: the distance between the anode and the cathode is 2-5 mm, the current is 40-100A, and the reaction time is 0.5-5 hours;
the mass ratio of the metal M powder to the noble metal powder is 1: (0.1-2%); or adding metal M powder into a precursor aqueous solution containing noble metal elements, adding sodium borohydride, washing and drying to obtain mixed powder of the metal M powder and the noble metal powder;
the molar ratio of the sodium borohydride to the noble metal powder is (5-20): 1.
2. the method according to claim 1, wherein the molar concentration of the noble metal element in the aqueous solution of the precursor containing the noble metal element is 0.05 to 1mmol L-1The mass ratio of the metal M powder to the noble metal elements is 1: (0.1-2%).
3. The preparation method according to claim 1, wherein the graphite tube has an outer diameter of 5 to 10mm, an inner diameter of 3 to 6mm, and a length of 8 to 20 cm.
4. The preparation method according to claim 1, wherein the graphite rod has a diameter of 5 to 10mm and a length of 8 to 20 cm.
5. The method according to claim 1, wherein the pressure of the hydrogen gas is 0.04 to 0.1 MPa.
6. The method according to claim 1, wherein the degree of vacuum of the vacuum is 2 to 10 Pa.
7. A catalyst for selective hydrogenation of α -unsaturated aldehyde in liquid phase prepared by the preparation method according to any one of claims 1-6, wherein the catalyst comprises a carrier and a noble metal active component loaded on the surface of the carrier, the carrier is a carbide MC, wherein M is at least one of Mo, Nb, W, Ti, Zr and Ta, the noble metal active component is at least one of Ru, Pd, Au and Pt, and the mass content of the noble metal active component is 0.1-2%.
8. The catalyst according to claim 7, wherein the noble metal active component has a particle size of 0.5 to 6nm, and the carrier has a particle size of 10 to 200 nm.
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