CN104383963B - A kind of ligand modified support type acetylene hydrogenation Pd catalyst and preparation method thereof - Google Patents
A kind of ligand modified support type acetylene hydrogenation Pd catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of ligand modified support type acetylene hydrogenation Pd catalyst and preparation method thereof, relates to a kind of catalyst and preparation method thereof, and described Pd is active component, and its weight/mass percentage composition is 1% 3%；Its surface grafting of carrier silicas contains the organic group of N, S；Its alkyl hydrosulfide is as part, and tetrabutyl ammonium borohydride is as reducing agent；The palladium salt used is PdCl2Or Palladous nitrate., solvent is toluene solution, palladium salt is dissolved in toluene solution, adds alkyl hydrosulfide part, and ultrasonic wave concussion, in clarification colored solutions, is subsequently adding tetrabutyl ammonium borohydride, is eventually adding organically-modified SiO 2 powder, obtains catalyst.This catalyst can be with Effective Regulation Pt-supported catalyst performance by introducing alkyl hydrosulfide part, and under the conditions of lower temperature reaction temperature and high hydrogen alkynes ratio, conversion of alkyne is 100%, ethylene selectivity more than 90%, and stable performance.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, particularly relate to a kind of ligand modified support type acetylene hydrogenation Pd catalyst and preparation method thereof.
Background technology
In catalytic reaction process, the committed step that catalytic action is relevant, desorption etc. such as absorption, diffusion and the product of reactant all refers to the electron transmission between catalyst surface and reaction species, and distribution and the structure of the valency electron of catalyst surface have highly important impact to the catalytic performance of catalyst.Therefore, the most effectively characteristic of regulating catalyst surface electronic, particularly valency electron, is the key core problem realizing catalyst initiative.Loaded catalyst generally improves the performance of catalyst by changing character and the addition auxiliary agent etc. of carrier.Park etc. add alkali metal potassium on palladium/aluminium oxide catalyst or alkaline earth metals calcium, magnesium etc. modify alumina support, improve ethylene selectivity, decrease green oil generating amount, extend cycle of operation.Chinayon introduces Zn in alumina support by sol-gel process and reduces the acidity of carrier, makes the selectivity of ethylene improve.The comparative studies such as Huang Na+The palladium catalyst of exchange beta-zeolite molecular sieve load and traditional Pd/ γ-Al2O3The acetylene hydrogenation performance of catalyst.Ihm etc. have studied Pd/TiO2The C of catalyst2Fraction selects hydrogenation catalyst performance, finds that titania support under certain condition can be by hydrogen reduction and strongly can interact with metal, Pd/TiO2Catalyst reduces at 250 DEG C, and ethylene selectivity is the highest, about reaches 91 %, and its catalytic performance is substantially better than Pd/Al2O3Catalyst.Chu etc. find that introducing MgO in titania support significantly improves the ethylene selectivity of Pd catalyst and the stability of catalyst.Panpranot etc. have studied the acetylene hydrogenation performance of the palladium catalyst of micron and nano-crystalline titanium dioxide load.The present invention uses part to regulate and control Pt-supported catalyst acetylene hydrogenation performance first, it is achieved 100% conversion of alkyne and the result of more than 90% ethylene selectivity.
Summary of the invention
It is an object of the invention to provide a kind of ligand modified support type acetylene hydrogenation Pd catalyst and preparation method thereof, the method can be with Effective Regulation Pt-supported catalyst performance by introducing alkyl hydrosulfide part, under the conditions of lower temperature reaction temperature and high hydrogen alkynes ratio, conversion of alkyne is 100%, ethylene selectivity more than 90%, and stable performance.
It is an object of the invention to be achieved through the following technical solutions:
A kind of ligand modified support type acetylene hydrogenation Pd catalyst, described Pd is active component, and its weight/mass percentage composition is 1%-3%；Its surface grafting of carrier silicas contains the organic group of N, S；Its alkyl hydrosulfide is as part, and tetrabutyl ammonium borohydride is as reducing agent；The palladium salt used is PdCl2 or Palladous nitrate., and solvent is toluene solution, and every 0.01g PdCl2 needs to be dissolved in 5-10
In ml toluene solution；Part and palladium mol ratio are 1:1-3:1；Pd load capacity is 1%-3%.
A kind of ligand modified support type acetylene hydrogenation Pd method for preparing catalyst; described method includes being dissolved in toluene solution palladium salt; add alkyl hydrosulfide part; ultrasonic wave concussion, in clarification colored solutions, is subsequently adding tetrabutyl ammonium borohydride, is eventually adding organically-modified SiO 2 powder; it is stirred continuously to solvent and evaporates; filtration washing, vacuum drying, obtain ligand protection load type palladium nanocatalyst.
Advantages of the present invention with effect is:
This catalyst can be with Effective Regulation Pt-supported catalyst performance by introducing alkyl hydrosulfide part, and under the conditions of lower temperature reaction temperature and high hydrogen alkynes ratio, conversion of alkyne is 100%, ethylene selectivity more than 90%, and stable performance.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Palladous chloride. is dissolved in toluene solution; add the mercaptan of different carbon chain lengths; ultrasonic wave concussion is in clarification colored solutions; it is subsequently adding tetrabutyl ammonium borohydride; being eventually adding SiO 2 powder, 40-60 DEG C of condition is stirred continuously to solvent and evaporates, filtration washing; 60-80 DEG C of vacuum drying, obtains ligand protection load type palladium nanocatalyst；Wherein alkyl hydrosulfide is as part, and tetrabutyl ammonium borohydride is as reducing agent；Wherein Pd load capacity is 1%-3%, and part and palladium mol ratio are 1:1-3:1.
Embodiment 1: the Palladous chloride. of 0.01g is dissolved in 5ml toluene solution; add 0.023g n-dodecyl mereaptan; ultrasonic wave concussion is to clarification; it is subsequently adding 0.0533g tetrabutyl ammonium borohydride, is eventually adding the modified SiO 2 powder of the organic S of 1g, be stirred continuously under the conditions of 40 DEG C to solvent and evaporate; filtration washing; 60 DEG C of vacuum drying 12h, grind tabletting, obtain ligand protection load type palladium nanocatalyst.
Embodiment 2: the Palladous chloride. of 0.02g is dissolved in 10ml toluene solution; add 0.046g n-dodecyl mereaptan; ultrasonic wave concussion is to clarification; being subsequently adding 0.1066g tetrabutyl ammonium borohydride, being eventually adding 1g has the modified SiO 2 powder of S machine, is stirred continuously to solvent and evaporates under the conditions of 40 DEG C; filtration washing; 60 DEG C of vacuum drying 12h, grind tabletting, obtain ligand protection load type palladium nanocatalyst.
Embodiment 3: the Palladous chloride. of 0.03g is dissolved in 15ml toluene solution; add 0.069g n-dodecyl mereaptan; ultrasonic wave concussion is to clarification; being subsequently adding 0.1599g tetrabutyl ammonium borohydride, being eventually adding 1g has the modified SiO 2 powder of S machine, is stirred continuously to solvent and evaporates under the conditions of 40 DEG C; filtration washing; 60 DEG C of vacuum drying 12h, grind tabletting, obtain ligand protection load type palladium nanocatalyst.
Embodiment 4: the Palladous chloride. of 0.01g is dissolved in 5ml toluene solution; add 0.023g n-dodecyl mereaptan; ultrasonic wave concussion is to clarification; it is subsequently adding 0.533g tetrabutyl ammonium borohydride, is eventually adding the SiO 2 powder that 1g Organic N is modified, be stirred continuously under the conditions of 40 DEG C to solvent and evaporate; filtration washing; 60 DEG C of vacuum drying 12h, grind tabletting, obtain ligand protection load type palladium nanocatalyst.
Embodiment 5: be dissolved in 10ml toluene solution by the Palladous chloride. of 0.02g, adds 0.046g C6H13SH; ultrasonic wave concussion is to clarification; it is subsequently adding 0.1066g tetrabutyl ammonium borohydride; it is eventually adding the SiO 2 powder that 1g Organic N is modified; it is stirred continuously under the conditions of 40 DEG C to solvent and evaporates, filtration washing, 60 DEG C of vacuum drying 12h; grind tabletting, obtain ligand protection load type palladium nanocatalyst.
Embodiment 6: be dissolved in 15ml toluene solution by the Palladous chloride. of 0.03g, adds 0.069g C8H17SH; ultrasonic wave concussion is to clarification; it is subsequently adding 0.1599g tetrabutyl ammonium borohydride; it is eventually adding the SiO 2 powder that 1g Organic N is modified; it is stirred continuously under the conditions of 40 DEG C to solvent and evaporates, filtration washing, 60 DEG C of vacuum drying 12h; grind tabletting, obtain ligand protection load type palladium nanocatalyst.
By the catalyst tabletting of preparation, pulverize the granule preparing 40-60 mesh.Take 0.1g beaded catalyst to load in the glass reaction tube that internal diameter is 4mm.It is passed through the H that flow is 24ml/min2, reduction 90min under the conditions of 120 DEG C.It is passed through the H that flow is 24ml/min the most simultaneously2It is the C of 30ml/min with flow2H2Gaseous mixture, react under condition of different temperatures, product is analyzed by gas chromatogram.
Experimental result is as shown in table 1.
Table 1 reaction result
| Example | Temperature (DEG C) when acetylene converts completely | Conversion of alkyne (%) | Ethylene selectivity (%) |
| 1 | 120 | 100 | 94 |
| 2 | 90 | 100 | 92 |
| 3 | 80 | 100 | 94 |
| 4 | 120 | 100 | 86 |
| 5 | 70 | 100 | 78 |
| 6 | 40 | 100 | 82 |
Claims (2)
1. a ligand modified support type acetylene hydrogenation Pd catalyst, it is characterised in that described Pd is active component, and its weight/mass percentage composition is 1%-3%；Its surface grafting of carrier silicas contains the organic group of N, S；Wherein alkyl hydrosulfide is as part, and tetrabutyl ammonium borohydride is as reducing agent；The palladium salt used is PdCl2Or Palladous nitrate., solvent is toluene solution, every 0.01g PdCl2Need to be dissolved in 5-10 mL toluene solution；Part and palladium mol ratio are 1:1-3:1；Pd load capacity is 1%-3%；Wherein the preparation method of catalyst includes being dissolved in toluene solution palladium salt; add alkyl hydrosulfide part; ultrasonic wave concussion is in clarification colored solutions; it is subsequently adding tetrabutyl ammonium borohydride; it is eventually adding organically-modified SiO 2 powder, is stirred continuously to solvent and evaporates, filtration washing; vacuum drying, obtains ligand protection load type palladium nanocatalyst.
The preparation method of a kind of ligand modified support type acetylene hydrogenation Pd catalyst the most according to claim 1; it is characterized in that; described preparation method includes being dissolved in toluene solution palladium salt, adds alkyl hydrosulfide part, and ultrasonic wave concussion is in clarification colored solutions; it is subsequently adding tetrabutyl ammonium borohydride; it is eventually adding organically-modified SiO 2 powder, is stirred continuously to solvent and evaporates, filtration washing; vacuum drying, obtains ligand protection load type palladium nanocatalyst.
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