CN109012751A - A kind of application with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene reaction - Google Patents

A kind of application with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene reaction Download PDF

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CN109012751A
CN109012751A CN201810942072.6A CN201810942072A CN109012751A CN 109012751 A CN109012751 A CN 109012751A CN 201810942072 A CN201810942072 A CN 201810942072A CN 109012751 A CN109012751 A CN 109012751A
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palladium
cabbeen
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CN109012751B (en
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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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    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391Physical properties of the active metal ingredient
    • B01J35/393Metal or metal oxide crystallite size
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0213Preparation of the impregnating solution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • CCHEMISTRY; METALLURGY
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a kind of applications with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene reaction.The catalyst includes alumina support and Cabbeen-palladium for being supported on carrier, and the catalyst passes through the preparation method included the following steps and is made: (1) in a solvent by ion liquid dissolving, obtaining ionic liquid solution;(2) powder potassium tert-butoxide or anhydrous sodium acetate are added into ionic liquid solution, stirs 1-3h at 60-150 DEG C to get Cabbeen solution is arrived;(3) palladium presoma is proportionally added in Cabbeen solution, stirs to get containing Cabbeen-palladium solution;(4) equably alumina support is poured into containing aluminium oxide is totally submerged and fully dispersed, the carrier room temperature immersion soaked by solution, then drying is obtained with Cabbeen-palladium structure catalyst.Catalyst of the present invention is applied in selective hydrogenation of acetylene reaction, has the characteristics that conversion of alkyne, ethylene selectivity are high.

Description

It is a kind of to be reacted with Cabbeen-palladium structure catalyst and its in selective hydrogenation of acetylene In application
(1) technical field
The present invention relates to a kind of with Cabbeen-palladium structure catalyst and its in preparing ethylene by selective hydrogenation of acetylene reaction Application.
(2) technical background
Ethylene is widely used in every field as important Organic Chemicals.The resulting ethylogen of industrial production Expect gas in, often containing 1% acetylene.The trace acetylene mixed in ethylene raw material gas can poison urging for subsequent ethylene polymerization Agent, and reduce the quality of polyethylene product.Therefore, the acetylene in unstripped gas is removed to 5ppm or less and is of great significance.
Frequently with the acetylene in solvent absorption, selective hydrogenation method removing ethylene raw in ethylene unit.It is inhaled with solvent Receipts method is compared, and catalysis selective hydrogenation compares absorption process, and pollution is small, while removing acetylene impurities, moreover it is possible to improve the production of ethylene Amount.However traditional catalyst used by industrial, when acetylene is in high conversion, the selectivity of ethylene is very low.This is because Ethylene is not desorbed in time during the reaction, caused by excessive hydrogenation.
Therefore, how to design the selective hydrocatalyst of acetylene that ethylene can be promoted to be desorbed has for improving selectivity Significance.Document (the .Promotional effect ofPd single atoms such as PEI G X onAu nanoparticles supported on silica for the selective hydrogenation of Acetylene in excess ethylene [J] .New Journal of Chemistry, 2014,38 (5): 2043- 2051.ZHOU H R etc., Pd/ZnO catalysts with different origins for high chemoselectivity in acetylene semi-hydrogenation[J].Chinese Journal OfCatalysis, 2016,37 (5): 692-699.) disclosure report, the small palladium particle of partial size is prepared, can effectively reduce ethylene Adsorption strength;Furthermore document (Liu Y etc., Highly efficient PdAg catalyst using a reducible Mg-Ti mixed oxide for selective hydrogenation of acetylene:Role of acidic and Basic sites [J] .Journal of Catalysis, 2017,348:135-145.Kim E etc., Pd catalyst promoted by two metal oxides with different reducibilities:Properties and performance in the selective hydrogenation ofacetylene☆[J].Applied Catalysis A General, 2014,471 (5): 80-83.) it points out again, the cloud density of palladium is improved, the desorption of ethylene can be promoted.
Based on background above, the invention proposes small with a kind of partial size, the high palladium activated centre of cloud density is urged The preparation method of agent, the catalyst can obtain preferable acetylene reaction activity, and the ethylene choosing that reaction obtains at low temperature Selecting property is high, good stability.
(3) summary of the invention
The purpose of the present invention is to provide a kind of with Cabbeen-palladium structure catalyst and its anti-in selective hydrogenation of acetylene Application in answering, the catalyst have the characteristics that conversion of alkyne, ethylene selectivity are high.
Technical solution used in the present invention is illustrated below.
On the one hand, the present invention provides a kind of with Cabbeen-palladium structure catalyst, including alumina support and is supported on Cabbeen-palladium on carrier, the catalyst pass through the preparation method included the following steps and are made:
(1) in a solvent by ion liquid dissolving, ionic liquid solution is obtained;The ionic liquid is with -3 methyl of 1- ethyl Imidazoles, -3 methylimidazole of 1- propyl, -3 methylimidazole of 1- butyl, -3 methylimidazole of 1- amyl or bis- (the 2,6- diisopropyls of 1,3- Benzene) glyoxaline cation is cationic, using chloride ion, bromide ion or iodide ion as anion;The solvent is selected from tetrahydrofuran (THF), one of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO);
(2) powder potassium tert-butoxide or anhydrous sodium acetate are added into ionic liquid solution, at 60-150 DEG C (preferably 90 DEG C) Lower stirring 1-3h is completely dissolved solid to get Cabbeen solution is arrived;
(3) palladium presoma is proportionally added in Cabbeen solution, the palladium presoma is palladium acetate, palladium acetylacetonate Or dichloro diamino palladium, and 2-4h (preferably 4h) is stirred under 60-150 DEG C (preferably 120 DEG C), it obtains containing Cabbeen-palladium solution;
(4) equably alumina support is poured into containing in Cabbeen-palladium solution, aluminium oxide is made to be totally submerged and be filled by solution Dispersion, the carrier soaked impregnate 8-14h (preferably 12h) at room temperature, then dry under 110-130 DEG C (preferably 110 DEG C) 8-14h (12h) is obtained with Cabbeen-palladium structure catalyst.
The preparation method of catalyst of the present invention, Cabbeen-palladium are regarded as whole loads, and those skilled in the art can be with The additional amount of load capacity selection palladium compound and ionic liquid as needed.Preferably there is Cabbeen-palladium structure in the present invention The load capacity (i.e. the mass percent of palladium and carrier) of palladium is 0.04-0.2wt% in catalyst.
In the preparation of catalyst of the present invention, the ionic liquid, potassium tert-butoxide or anhydrous sodium acetate, palladium presoma Molar ratio is 1:1-1.2:0.5-2.The ionic liquid is preferably using chloride ion as anion;Most preferably ionic liquid is - 3 methylimidazole of chlorination 1- propyl.The solvent is preferably DMF.The palladium presoma is preferably palladium acetate.
In the present invention, the specific surface area of alumina support is preferably 58-420m2/g。
In step (4) of the present invention, if the aluminium oxide of addition can not be submerged containing Cabbeen-palladium solution, it can be added a certain amount of Solvent is completely submerged aluminium oxide.
In step (4) of the present invention, after aluminium oxide is added, preferably make aluminium oxide containing Cabbeen-palladium solution by ultrasonic treatment In be uniformly dispersed.
On the other hand, the present invention provides described there is Cabbeen-palladium structure catalyst to react in selective hydrogenation of acetylene In application first catalyst is restored with hydrogen before application, reduction temperature be 60-150 DEG C (preferably 100 DEG C), reduction Time is 1-3h.
Further, the condition of selective hydrogenation of acetylene is: reaction temperature is 50-160 DEG C (preferably 70-80 DEG C), reaction pressure Power is 0.1-1MPa (preferably normal pressure), air speed 4000-15000h-1
Compared with prior art, the beneficial effects of the present invention are:
(1) what is be prepared in the present invention has Cabbeen-palladium structure catalyst, and palladium nano-particles partial size is small, palladium electronics Cloud density is high, which can promote the desorption of ethylene in reaction process, to substantially increase the choosing of ethylene in the reaction Selecting property.
(2) produced by the present invention that there is Cabbeen-palladium structure catalyst can obtain preferably at low temperature (70-80 DEG C) Acetylene reaction activity, and the ethylene selectivity that reaction obtains is high.
(4) Detailed description of the invention
Fig. 1 is scanning transmission electron microscope (STEM) photo of embodiment 7, is prepared as seen from the figure by this method Catalyst metals partial size it is small, it is scattered.
(5) specific embodiment
Illustrate the present invention with specific example below.It is important to point out that embodiment is served only for carrying out the present invention It further illustrates, but should not be understood as limiting the scope of the invention.
Embodiment 1
Claim -3 methylimidazole of 0.08g (0.5mmol) chlorination 1- propyl to be dissolved in 2mL dimethyl sulfoxide (DMSO), and is added Anhydrous sodium acetate 0.041g (0.5mmol), 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then are added into clear solution 0.22g (1.0mmol) palladium acetate is as palladium presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Acquired solution is turned It moves in 10mL volumetric flask, adds DMSO to corresponding scale, obtain Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMSO is added and is mixed with maceration extract, then Evenly by alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.By the aluminium oxide of wetting in room temperature immersion 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 2
Claim -3 methylimidazole of 0.16g (1.0mmol) chlorination 1- propyl to be dissolved in 2mL dimethyl sulfoxide (DMSO), and is added Anhydrous sodium acetate 0.082g (1.0mmol), 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then are added into clear solution 0.22g (1.0mmol) palladium acetate is as palladium presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Acquired solution is turned It moves in 10mL volumetric flask, adds DMSO to corresponding scale, obtain Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMSO is added and is mixed with maceration extract, then Evenly by alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.By the aluminium oxide of wetting in room temperature immersion 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 3
Claim -3 methylimidazole of 0.32g (2.0mmol) chlorination 1- propyl to be dissolved in 2mL dimethyl sulfoxide (DMSO), and is added Anhydrous sodium acetate 0.16g (2.0mmol), 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then are added into clear solution 0.22g (1.0mmol) palladium acetate is as palladium presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Acquired solution is turned It moves in 10mL volumetric flask, adds DMSO to corresponding scale, obtain Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMSO is added and is mixed with maceration extract, then Evenly by alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.By the aluminium oxide of wetting in room temperature immersion 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 4
- 3 methylimidazole of 0.32g (2.0mmol) chlorination 1- propyl is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as palladium presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.By gained Solution is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly Ground is by alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.By the aluminium oxide of wetting in room temperature immersion 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 5
Bis- (2, the 6- diisopropyl benzene) imidazolitm chlorides of 0.21g (0.5mmol) 1,3- are claimed to be dissolved in 4mLN, N- dimethyl formyl In amine (DMF), and potassium tert-butoxide 0.06g (0.6mmol) being added, 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then to 0.22g (1.0mmol) palladium acetate is added in clear solution as palladium presoma, 120 DEG C of agitating and heating 4h are molten to get Cabbeen-palladium Liquid.Acquired solution is transferred in 10mL volumetric flask, adds DMF to corresponding scale, obtains Cabbeen-palladium leaching that concentration is 0.001g/mL Stain liquid.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 6
Bis- (2, the 6- diisopropyl benzene) imidazolitm chlorides of 0.43g (1.0mmol) 1,3- are claimed to be dissolved in 4mLN, N- dimethyl formyl In amine (DMF), and potassium tert-butoxide 0.12g (1.1mmol) being added, 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then to 0.22g (1.0mmol) palladium acetate is added in clear solution as palladium presoma, 120 DEG C of agitating and heating 4h are molten to get Cabbeen-palladium Liquid.Acquired solution is transferred in 10mL volumetric flask, adds DMF to corresponding scale, obtains Cabbeen-palladium leaching that concentration is 0.001g/mL Stain liquid.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 7
Bis- (2, the 6- diisopropyl benzene) imidazolitm chlorides of 0.85g (2.0mmol) 1,3- are claimed to be dissolved in 4mLN, N- dimethyl formyl In amine (DMF), and potassium tert-butoxide 0.24g (2.1mmol) being added, 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then to 0.22g (1.0mmol) palladium acetate is added in clear solution as palladium presoma, 120 DEG C of agitating and heating 4h are molten to get Cabbeen-palladium Liquid.Acquired solution is transferred in 10mL volumetric flask, adds DMF to corresponding scale, obtains Cabbeen-palladium leaching that concentration is 0.001g/mL Stain liquid.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12 hours, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 8
Bis- (2, the 6- diisopropyl benzene) imidazolitm chlorides of 0.85g (2.0mmol) 1,3- are claimed to be dissolved in 4mLN, N- dimethyl formyl In amine (DMF), and potassium tert-butoxide 0.24g (2.1mmol) being added, 90 DEG C of constant temperature stirring holding 1h to solid are completely dissolved, then to 0.30g (1.0mmol) palladium acetylacetonate is added in clear solution as palladium presoma, 120 DEG C of agitating and heating 4h are to get Cabbeen- Palladium solution.Acquired solution is transferred in 10mL volumetric flask, adds DMF to corresponding scale, obtains the Cabbeen-that concentration is 0.001g/mL Palladium steeping liq.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 9
- 3 methylimidazole of 0.41g (2.0mmol) bromination 1- propyl is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 10
- 3 methylimidazole of 0.50g (2.0mmol) iodate 1- propyl is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 11
- 3 methylimidazole of 0.29g (2.0mmol) chlorination 1- ethyl is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 12
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 13
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 58m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 14
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten Liquid is transferred in 10mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 420m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.1wt% with Cabbeen-palladium structure catalyst.
Embodiment 15
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten Liquid is transferred in 5mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.002g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 420m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.2wt% with Cabbeen-palladium structure catalyst.
Embodiment 16
0.35g (2.0mmol) 1-butyl-3-methylimdazoliuim chloride is claimed to be dissolved in 2mL n,N-Dimethylformamide (DMF), And anhydrous sodium acetate 0.16g (2.0mmol) is added, the stirring of 90 DEG C of constant temperature keeps 1h to be completely dissolved to solid, then to clear solution Middle addition 0.22g (1.0mmol) palladium acetate is as presoma, and 120 DEG C of agitating and heating 4h are to get Cabbeen-palladium solution.Gained is molten Liquid is transferred in 25mL volumetric flask, is added DMF to corresponding scale, is obtained Cabbeen-palladium steeping liq that concentration is 0.001g/mL.
Using infusion process, Cabbeen-palladium maceration extract of metering is pipetted, and certain DMF is added and is mixed with maceration extract, then uniformly By alumina support (specific surface area 420m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is soaked in room temperature Stain 12h, and the dry 12h at 110 DEG C, obtaining palladium load capacity is 0.04wt% with Cabbeen-palladium structure catalyst.
Embodiment 17
Referring to embodiment 4, difference is that the stirring condition by step (3) becomes: in 60 DEG C of stirring 4h, other conditions are the same as real Example 4 is applied, it is 0.1wt% with Cabbeen-palladium structure catalyst that palladium load capacity, which is made,.
Embodiment 18
Referring to embodiment 4, difference is that the stirring condition by step (3) becomes: in 150 DEG C of stirring 2h, other conditions are same Embodiment 4, it is 0.1wt% with Cabbeen-palladium structure catalyst that palladium load capacity, which is made,.
Embodiment 19
Referring to embodiment 4, difference is that the immersion condition by step (4) becomes: in room temperature immersion 8h, then at 130 DEG C Lower dry 8h, for other conditions with embodiment 4, it is 0.1wt% with Cabbeen-palladium structure catalyst that palladium load capacity, which is made,.
Comparative example 1
Using palladium acetate as presoma, n,N-Dimethylformamide (DMF) is used as solvent, and preparation concentration is 0.001g/mL's Palladium liquid.
Using infusion process, the palladium liquid of metering is pipetted, and certain DMF is added and is mixed with maceration extract, it then uniformly will oxidation Alumina supporter (specific surface area 384m2/ g) pour into maceration extract, and ultrasound.The Supported alumina of wetting is small in room temperature immersion 12 When, and the dry 12h at 110 DEG C, obtain the alumina load palladium catalyst that palladium load capacity is 0.1wt%.
Catalyst obtained is subjected to catalyst activity and selective evaluation according to following method:
0.3g catalyst is placed in small-sized quartz tube reactor, quartz ampoule is placed in the heating furnace of controllable temperature, instead Ying Qian is passed through pure H21h is restored at 100 DEG C;After reduction, (table 1) is reacted at a certain temperature.Reaction gas group becomes (volume fraction): 0.33% acetylene, 0.66% hydrogen, 33% ethylene, surplus nitrogen.The flow velocity of reaction gas is 50mL/min, instead Answering pressure is normal pressure.Reaction gas outlet connects gas-chromatography on-line checking, and the evaluation result of catalyst see the table below shown in 1.
1 alumina load ionic liquid of table-palladium catalyst selective hydrogenation of acetylene reaction evaluating result

Claims (10)

1. it is a kind of with Cabbeen-palladium structure catalyst, it is described including alumina support and the Cabbeen-palladium being supported on carrier Catalyst passes through the preparation method included the following steps and is made:
(1) in a solvent by ion liquid dissolving, ionic liquid solution is obtained;The ionic liquid is with -3 methyl miaow of 1- ethyl Azoles, -3 methylimidazole of 1- propyl, -3 methylimidazole of 1- butyl, -3 methylimidazole of 1- amyl or 1,3- bis- (2,6- diisopropyl benzenes) Glyoxaline cation is cation, using chloride ion, bromide ion or iodide ion as anion;The solvent is selected from tetrahydrofuran, N, N- One of dimethylformamide, dimethyl sulfoxide;
(2) powder potassium tert-butoxide or anhydrous sodium acetate are added into ionic liquid solution, 1-3h is stirred at 60-150 DEG C to be made admittedly Body is completely dissolved to arrive Cabbeen solution;
(3) palladium presoma is proportionally added in Cabbeen solution, the palladium presoma is palladium acetate, palladium acetylacetonate or two Chlorine diamino palladium, and 2-4h is stirred at 60-150 DEG C, it obtains containing Cabbeen-palladium solution;
(4) equably alumina support is poured into containing in Cabbeen-palladium solution, is totally submerged aluminium oxide by solution and sufficiently divides It dissipates, the carrier soaked impregnates 8-14h at room temperature, and then the dry 8-14h at 110-130 DEG C, obtains with Cabbeen-palladium knot The catalyst of structure.
2. having Cabbeen-palladium structure catalyst as described in claim 1, it is characterised in that: described that there is Cabbeen-palladium structure Catalyst in palladium load capacity be 0.04-0.2wt%.
3. having Cabbeen-palladium structure catalyst as described in claim 1, it is characterised in that: the ionic liquid, the tert-butyl alcohol The molar ratio of potassium or anhydrous sodium acetate, palladium presoma is 1:1-1.2:0.5-2.
4. having Cabbeen-palladium structure catalyst as described in claim 1, it is characterised in that: the specific surface of alumina support Product is 58-420m2/g。
5. there is Cabbeen-palladium structure catalyst as described in one of Claims 1 to 4, it is characterised in that: the ionic liquid Body is using chloride ion as anion;The solvent is N,N-dimethylformamide;The palladium presoma is palladium acetate.
6. having Cabbeen-palladium structure catalyst as claimed in claim 5, it is characterised in that: the ionic liquid is chlorine Change -3 methylimidazole of 1- propyl.
7. there is Cabbeen-palladium structure catalyst as described in one of Claims 1 to 4 or 6, it is characterised in that: step (4) In, if the aluminium oxide of addition can not be submerged containing Cabbeen-palladium solution, a certain amount of solvent is added, is completely submerged aluminium oxide; After aluminium oxide is added, aluminium oxide is set to be uniformly dispersed in containing Cabbeen-palladium solution by ultrasonic treatment.
8. the application with Cabbeen-palladium structure catalyst in selective hydrogenation of acetylene reaction as described in claim 1, Before, first catalyst is restored with hydrogen, reduction temperature is 60-150 DEG C, recovery time 1-3h.
9. application as claimed in claim 8, it is characterised in that: the condition of selective hydrogenation of acetylene reaction is: reaction temperature is 50-160 DEG C, reaction pressure 0.1-1MPa, air speed 4000-15000h-1
10. application as claimed in claim 9, it is characterised in that: reaction temperature is 70-80 DEG C, and reaction pressure is normal pressure.
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