CN109012751B - Catalyst with carbene-palladium structure and application thereof in selective hydrogenation reaction of acetylene - Google Patents

Catalyst with carbene-palladium structure and application thereof in selective hydrogenation reaction of acetylene Download PDF

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CN109012751B
CN109012751B CN201810942072.6A CN201810942072A CN109012751B CN 109012751 B CN109012751 B CN 109012751B CN 201810942072 A CN201810942072 A CN 201810942072A CN 109012751 B CN109012751 B CN 109012751B
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李小年
徐逸琦
张群峰
黄伟民
许孝良
赵佳
丰枫
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a catalyst with a carbene-palladium structure and application thereof in selective hydrogenation reaction of acetylene. The catalyst comprises an alumina carrier and carbene-palladium loaded on the carrier, and is prepared by a preparation method comprising the following steps: (1) dissolving ionic liquid in a solvent to obtain an ionic liquid solution; (2) adding powder potassium tert-butoxide or anhydrous sodium acetate into the ionic liquid solution, and stirring at 60-150 ℃ for 1-3h to obtain a carbene solution; (3) adding a palladium precursor into the carbene solution according to a ratio, and stirring to obtain a solution containing carbene-palladium; (4) uniformly pouring the alumina carrier into a solution containing carbene-palladium, completely immersing and fully dispersing the alumina by the solution, impregnating the soaked carrier at room temperature, and then drying to obtain the catalyst with the carbene-palladium structure. The catalyst provided by the invention is applied to the selective hydrogenation reaction of acetylene, and has the characteristics of high acetylene conversion rate and high ethylene selectivity.

Description

Catalyst with carbene-palladium structure and application thereof in selective hydrogenation reaction of acetylene
(I) technical field
The invention relates to a catalyst with a carbene-palladium structure and application thereof in reaction for preparing ethylene by selective hydrogenation of acetylene.
(II) technical background
Ethylene is widely used in various fields as an important organic chemical raw material. The ethylene raw material gas obtained by industrial production often contains 1% of acetylene. Trace amount of acetylene mixed in the raw material gas of ethylene can poison the catalyst of the subsequent ethylene polymerization reaction and reduce the quality of polyethylene products. Therefore, the acetylene in the raw material gas is removed to be below 5ppm, which has important significance.
In the ethylene plant, acetylene in the ethylene raw material is usually removed by a solvent absorption method and a selective hydrogenation method. Compared with a solvent absorption method, the catalytic selective hydrogenation method has less pollution, and can improve the yield of ethylene while removing acetylene impurities. However, the conventional catalysts used in industry have low ethylene selectivity at high acetylene conversion. This is due to the over-hydrogenation, which is caused by the fact that ethylene is not desorbed in time during the reaction.
Therefore, how to design the acetylene selective hydrogenation catalyst capable of promoting ethylene desorption has important significance for improving selectivity. The literature (PEI G X et al. molar effect of Pd single atoms on Au nanoparticles supported on silica for the selective hydrogenation of ethylene [ J ]. New Journal of Chemistry 2014, 38 (5): 2043-2051, ZHOU H R et al, Pd/ZnO catalysts with differential orientations for high selectivity in ethylene reaction [ J ]. Chinese Journal of catalysis, 2016, 37 (5): 699.) discloses the preparation of palladium particles of small particle size, effective in reducing the adsorption strength of ethylene; furthermore, the literature (Liu Y et al, high affinity PdAg Catalysis using a reduced Mg-Ti mixed oxide for selective hydrogenation of ethylene: Role of acidic and basic sites [ J ]. Journal of Catalysis,2017,348:135-145.Kim E et al, Pd Catalysis protein by two metals with differential Catalysis: Properties and performance in the selective hydrogenation of ethylene [ J ]. Applied Catalysis A General,2014,471(5) (80-83.) further indicates that increasing the electron cloud density of palladium promotes ethylene desorption.
Based on the background, the invention provides a preparation method of a catalyst with a palladium active center with small particle size and high electron cloud density, the catalyst can obtain better acetylene reaction activity at low temperature, and ethylene obtained by the reaction has high selectivity and good stability.
Disclosure of the invention
The invention aims to provide a catalyst with a carbene-palladium structure and application thereof in selective hydrogenation reaction of acetylene, wherein the catalyst has the characteristics of high acetylene conversion rate and high ethylene selectivity.
The technical solution used in the present invention is specifically described below.
In one aspect, the invention provides a catalyst with a carbene-palladium structure, which comprises an alumina carrier and carbene-palladium loaded on the carrier, and the catalyst is prepared by a preparation method comprising the following steps:
(1) dissolving ionic liquid in a solvent to obtain an ionic liquid solution; the ionic liquid takes 1-ethyl-3 methylimidazole, 1-propyl-3 methylimidazole, 1-butyl-3 methylimidazole, 1-pentyl-3 methylimidazole or 1, 3-bis (2, 6-diisopropylbenzene) imidazole cation as cation and takes chloride ion, bromide ion or iodide ion as anion; the solvent is selected from one of Tetrahydrofuran (THF), N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO);
(2) adding powder potassium tert-butoxide or anhydrous sodium acetate into the ionic liquid solution, and stirring at 60-150 deg.C (preferably 90 deg.C) for 1-3h to completely dissolve the solid to obtain carbene solution;
(3) adding a palladium precursor into the carbene solution according to a proportion, wherein the palladium precursor is palladium acetate, palladium acetylacetonate or palladium dichlorodiammine, and stirring for 2-4h (preferably 4h) at 60-150 ℃ (preferably 120 ℃) to obtain a solution containing carbene-palladium;
(4) uniformly pouring the alumina carrier into the solution containing the carbene-palladium so that the alumina is completely immersed by the solution and is fully dispersed, soaking the soaked carrier for 8-14h (preferably 12h) at room temperature, and then drying the soaked carrier for 8-14h (12h) at 110-130 ℃ (preferably 110 ℃), thus obtaining the catalyst with the carbene-palladium structure.
In the preparation method of the catalyst, the carbene-palladium can be regarded as the whole load, and the addition amount of the palladium compound and the ionic liquid can be selected by a person skilled in the art according to the required load amount. In the present invention, it is preferable that the supported amount of palladium (i.e., the mass percentage of palladium to the carrier) in the catalyst having a carbene-palladium structure is 0.04 to 0.2 wt%.
In the preparation of the catalyst, the feeding molar ratio of the ionic liquid, potassium tert-butoxide or anhydrous sodium acetate to the palladium precursor is 1: 1-1.2: 0.5-2. The ionic liquid preferably takes chloride ions as anions; most preferably the ionic liquid is 1-propyl-3 methylimidazole chloride. The solvent is preferably DMF. The palladium precursor is preferably palladium acetate.
In the present invention, the specific surface area of the alumina carrier is preferably 58 to 420m2/g。
In the step (4) of the invention, if the solution containing carbene-palladium cannot submerge the added alumina, a certain amount of solvent can be added to ensure that the alumina is completely submerged.
In the step (4) of the present invention, after the alumina is added, the alumina is uniformly dispersed in the carbene-palladium containing solution, preferably by ultrasonic treatment.
On the other hand, the invention provides the application of the catalyst with the carbene-palladium structure in the selective hydrogenation reaction of acetylene, before the application, hydrogen is firstly used for reducing the catalyst, the reduction temperature is 60-150 ℃ (preferably 100 ℃), and the reduction time is 1-3 h.
Further, the conditions for selective hydrogenation of acetylene are: the reaction temperature is 50-160 deg.C (preferably 70-80 deg.C), the reaction pressure is 0.1-1MPa (preferably normal pressure), and the space velocity is 4000--1。
Compared with the prior art, the invention has the beneficial effects that:
(1) the catalyst with the carbene-palladium structure prepared by the invention has small palladium nanoparticle particle size and high palladium electron cloud density, and the active center can promote the desorption of ethylene in the reaction process, thereby greatly improving the selectivity of ethylene in the reaction.
(2) The catalyst with the carbene-palladium structure can obtain better acetylene reaction activity at low temperature (70-80 ℃), and the ethylene obtained by the reaction has high selectivity.
(IV) description of the drawings
FIG. 1 is a photograph of a Scanning Transmission Electron Microscope (STEM) of example 7, and it can be seen from the photograph that the catalyst metal particles prepared by this method are small in particle size and well dispersed.
(V) detailed description of the preferred embodiments
The invention is illustrated by the following specific examples. It should be noted that the examples are only for further illustration of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
Weighing 0.08g (0.5mmol) of 1-propyl-3-methylimidazole chloride, dissolving in 2mL of dimethyl sulfoxide (DMSO), adding 0.041g (0.5mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a palladium precursor into the clear solution, stirring at the temperature of 120 ℃, and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMSO was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an immersion method, transferring a metered carbene-palladium immersion liquid, adding a certain amount of DMSO, mixing with the immersion liquid, and uniformly mixing an alumina carrier (with a specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 2
Weighing 0.16g (1.0mmol) of 1-propyl-3-methylimidazole chloride, dissolving in 2mL of dimethyl sulfoxide (DMSO), adding 0.082g (1.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a palladium precursor into the clear solution, stirring at the temperature of 120 ℃, and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMSO was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an immersion method, transferring and taking a measured carbene-palladium immersion liquid, adding a certain amount of DMSO (dimethyl sulfoxide) and mixing with the immersion liquid, and uniformly mixing the aluminaSupport (specific surface area 384 m)2/g) pour the impregnation solution and sonicate. The wetted alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 3
Weighing 0.32g (2.0mmol) of 1-propyl-3-methylimidazole chloride, dissolving in 2mL of dimethyl sulfoxide (DMSO), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at a constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a palladium precursor into the clear solution, stirring at 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMSO was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an immersion method, transferring a metered carbene-palladium immersion liquid, adding a certain amount of DMSO, mixing with the immersion liquid, and uniformly mixing an alumina carrier (with a specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 4
Weighing 0.32g (2.0mmol) of 1-propyl-3-methylimidazole chloride, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a palladium precursor into the clear solution, stirring and heating at the temperature of 120 ℃ for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF, mixing with the impregnation solution, and uniformly mixing an alumina carrier (with a specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 5
Weighing 0.21g (0.5mmol) of 1, 3-bis (2, 6-diisopropylbenzene) imidazolium chloride, dissolving in 4mLN, N-Dimethylformamide (DMF), adding 0.06g (0.6mmol) of potassium tert-butoxide, stirring at constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate as a palladium precursor into the clear solution, stirring and heating at 120 ℃ for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 6
Weighing 0.43g (1.0mmol) of 1, 3-bis (2, 6-diisopropylbenzene) imidazolium chloride, dissolving in 4mLN, N-Dimethylformamide (DMF), adding 0.12g (1.1mmol) of potassium tert-butoxide, stirring at constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate as a palladium precursor into the clear solution, stirring and heating at 120 ℃ for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 7
Weighing 0.85g (2.0mmol) of 1, 3-bis (2, 6-diisopropylbenzene) imidazolium chloride, dissolving in 4mLN, N-Dimethylformamide (DMF), adding 0.24g (2.1mmol) of potassium tert-butoxide, stirring at constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate as a palladium precursor into the clear solution, stirring and heating at 120 ℃ for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12 hours and dried at 110 ℃ for 12 hours to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 8
Weighing 0.85g (2.0mmol) of 1, 3-bis (2, 6-diisopropylbenzene) imidazolium chloride, dissolving in 4mLN, N-Dimethylformamide (DMF), adding 0.24g (2.1mmol) of potassium tert-butoxide, stirring at constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.30g (1.0mmol) of palladium acetylacetonate as a palladium precursor into the clear solution, stirring and heating at 120 ℃ for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 9
Weighing 0.41g (2.0mmol) of brominated 1-propyl-3 methylimidazole, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a precursor into the clear solution, stirring at the temperature of 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF, mixing with the impregnation solution, and uniformly mixing an alumina carrier (ratio table)Area of 384m2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 10
Weighing 0.50g (2.0mmol) of 1-propyl-3-methylimidazole iodide, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a precursor into the clear solution, stirring at the temperature of 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 11
Weighing 0.29g (2.0mmol) of 1-ethyl-3-methylimidazole chloride, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a precursor into the clear solution, stirring at the temperature of 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 12
Weighing 0.35g (2.0mmol) of 1-butyl-3-methylimidazole chloride, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a precursor into the clear solution, stirring at the temperature of 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 13
Weighing 0.35g (2.0mmol) of 1-butyl-3-methylimidazole chloride, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a precursor into the clear solution, stirring at the temperature of 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 58 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 14
Weighing 0.35g (2.0mmol) of 1-butyl-3-methylimidazole chloride, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a precursor into the clear solution, stirring at the temperature of 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 10mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 420 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 15
Weighing 0.35g (2.0mmol) of 1-butyl-3-methylimidazole chloride, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a precursor into the clear solution, stirring at the temperature of 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 5mL volumetric flask and DMF was added to the corresponding scale to give a carbene-palladium impregnation solution with a concentration of 0.002 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 420 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.2 wt%.
Example 16
Weighing 0.35g (2.0mmol) of 1-butyl-3-methylimidazole chloride, dissolving in 2mL of N, N-Dimethylformamide (DMF), adding 0.16g (2.0mmol) of anhydrous sodium acetate, stirring at the constant temperature of 90 ℃ for 1h until the solid is completely dissolved, adding 0.22g (1.0mmol) of palladium acetate serving as a precursor into the clear solution, stirring at the temperature of 120 ℃ and heating for 4h to obtain the carbene-palladium solution. The resulting solution was transferred to a 25mL volumetric flask and DMF was added to the appropriate scale to give a carbene-palladium impregnation solution at a concentration of 0.001 g/mL.
Adopting an impregnation method, transferring a measured carbene-palladium impregnation solution, adding a certain amount of DMF (dimethyl formamide) to be mixed with the impregnation solution, and uniformly mixing an alumina carrier (with the specific surface area of 420 m)2/g) pour the impregnation solution and sonicate. To be moistenedThe supported alumina was impregnated at room temperature for 12h and dried at 110 ℃ for 12h to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.04 wt%.
Example 17
Referring to example 4, except that the stirring conditions in step (3) were changed to: the mixture was stirred at 60 ℃ for 4 hours under the same conditions as in example 4 to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 18
Referring to example 4, except that the stirring conditions in step (3) were changed to: the mixture was stirred at 150 ℃ for 2 hours under the same conditions as in example 4 to obtain a catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt%.
Example 19
Referring to example 4, except that the impregnation conditions of step (4) were changed to: the catalyst having a carbene-palladium structure with a palladium loading of 0.1 wt% was prepared by impregnation at room temperature for 8h followed by drying at 130 ℃ for 8h, otherwise as in example 4.
Comparative example 1
Palladium acetate is used as a precursor, and N, N-Dimethylformamide (DMF) is used as a solvent to prepare palladium solution with the concentration of 0.001 g/mL.
Adopting an immersion method, transferring metered palladium liquid, adding certain DMF, mixing with the immersion liquid, and uniformly mixing an alumina carrier (with the specific surface area of 384 m)2/g) pour the impregnation solution and sonicate. The wetted supported alumina was impregnated at room temperature for 12 hours and dried at 110 c for 12 hours to produce an alumina supported palladium catalyst having a palladium loading of 0.1 wt%.
The catalyst activity and selectivity of the prepared catalyst were evaluated according to the following methods:
0.3g of catalyst was placed in a small quartz tube reactor, the quartz tube was placed in a temperature-controllable heating furnace, and pure H was introduced before the reaction2Reducing for 1h at 100 ℃; after reduction, the reaction was carried out at a certain temperature (Table 1). The reaction gas composition (volume fraction): 0.33% acetylene, 0.66% hydrogen, 33% ethylene, and the balance nitrogen. The flow rate of the reaction gas was 50mL/min, and the reaction pressure was normal pressure. Reaction gas outletThe results of the catalyst evaluation are shown in table 1 below after the online detection by gas chromatography.
TABLE 1 evaluation results of acetylene selective hydrogenation reaction of alumina-supported ionic liquid-palladium catalyst
Figure BDA0001769319800000081
Figure BDA0001769319800000091

Claims (10)

1. A catalyst with a carbene-palladium structure comprises an alumina carrier and carbene-palladium supported on the carrier, and is prepared by a preparation method comprising the following steps:
(1) dissolving ionic liquid in a solvent to obtain an ionic liquid solution; the ionic liquid takes 1-ethyl-3 methylimidazole, 1-propyl-3 methylimidazole, 1-butyl-3 methylimidazole, 1-pentyl-3 methylimidazole or 1, 3-bis (2, 6-diisopropylbenzene) imidazole cation as cation and takes chloride ion, bromide ion or iodide ion as anion; the solvent is one selected from tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide;
(2) adding powder potassium tert-butoxide or anhydrous sodium acetate into the ionic liquid solution, and stirring at 60-150 deg.C for 1-3h to completely dissolve the solid to obtain carbene solution;
(3) adding a palladium precursor into the carbene solution according to a proportion, wherein the palladium precursor is palladium acetate, palladium acetylacetonate or palladium dichlorodiammine, and stirring for 2-4h at 60-150 ℃ to obtain a solution containing carbene-palladium;
(4) uniformly pouring the alumina carrier into a solution containing carbene-palladium to ensure that the alumina is completely immersed and fully dispersed by the solution, soaking the soaked carrier at room temperature for 8-14h, and then drying at the temperature of 110-130 ℃ for 8-14h to obtain the catalyst with the carbene-palladium structure.
2. The catalyst having a carbene-palladium structure as set forth in claim 1, wherein: the loading amount of palladium in the catalyst with the carbene-palladium structure is 0.04-0.2 wt%.
3. The catalyst having a carbene-palladium structure as set forth in claim 1, wherein: the feeding molar ratio of the ionic liquid, potassium tert-butoxide or anhydrous sodium acetate to the palladium precursor is 1: 1-1.2: 0.5-2.
4. The catalyst having a carbene-palladium structure as set forth in claim 1, wherein: the specific surface area of the alumina carrier is 58-420m2/g。
5. The catalyst having a carbene-palladium structure as set forth in any of claims 1 to 4, wherein: the ionic liquid takes chloride ions as anions; the solvent is N, N-dimethylformamide; the palladium precursor is palladium acetate.
6. The catalyst having a carbene-palladium structure as set forth in claim 5, wherein: the ionic liquid is chlorinated 1-propyl-3 methylimidazole.
7. The catalyst having a carbene-palladium structure as set forth in one of claims 1 to 4 or 6, characterized in that: in the step (4), if the solution containing carbene-palladium cannot immerse the added alumina, adding a certain amount of solvent to completely immerse the alumina; after the alumina is added, the alumina is evenly dispersed in the solution containing the carbene-palladium through ultrasonic treatment.
8. The application of the catalyst with carbene-palladium structure in the selective hydrogenation reaction of acetylene according to claim 1, wherein before the application, hydrogen is firstly used for reducing the catalyst, the reduction temperature is 60-150 ℃, and the reduction time is 1-3 h.
9. The use of claim 8, wherein: the conditions of the acetylene selective hydrogenation reaction are as follows: the reaction temperature is 50-16The reaction pressure is 0.1-1MPa at 0 ℃, and the space velocity is 4000--1。
10. The use of claim 9, wherein: the reaction temperature is 70-80 ℃, and the reaction pressure is normal pressure.
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