CN103933973A - Preparation method of supported nano palladium/carbon catalyst - Google Patents
Preparation method of supported nano palladium/carbon catalyst Download PDFInfo
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- CN103933973A CN103933973A CN201410173418.2A CN201410173418A CN103933973A CN 103933973 A CN103933973 A CN 103933973A CN 201410173418 A CN201410173418 A CN 201410173418A CN 103933973 A CN103933973 A CN 103933973A
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Abstract
The invention discloses a preparation method of a supported nano palladium/carbon catalyst. According to the technical scheme, the preparation method of the supported nano palladium/carbon catalyst is characterized by comprising the following steps: first, dissolving an organic small molecule containing amino and carboxyl functional groups into ethylene glycol, adding palladium chloride aqueous solution with the mass concentration of 2mg/ml, and adjusting the pH value of a reaction system to be 9 to 12 by using an ethylene glycol solution of potassium hydroxide under the condition of stirring; then, adding activated carbon, uniformly dispersing a mixed system by ultrasound, stirring 5 to 12 hours under normal pressure in a water bath at the temperature of 50 to 100 DEG C, carrying out suction filtration, respectively washing a filter cake by using secondary distilled water and absolute ethyl alcohol, collecting a sample, and drying the sample at the temperature of 40 DEG C to obtain the supported nano palladium/carbon catalyst. The preparation method of the supported nano palladium/carbon catalyst is low in production cost, convenient to operate and is environment-friendly; the conditions are not harsh; the prepared supported nano palladium/carbon catalyst has stable properties; palladium nanoparticles can be uniformly dispersed on a carrier.
Description
Technical field
The invention belongs to loaded noble metal catalyst synthesis technical field, be specifically related to a kind of preparation method of loaded nano palladium/carbon catalyst.
Background technology
Supported palladium/carbon catalyst is a kind of conventional hydrogenation catalyst, is widely used in the fields such as carbonyl hydrogen, hydrogenation of olefins, nitro and nitroso hydrogenation.The method of preparing palladium nano-particles has two kinds of Physical and chemical methods, with chemical method research at most.Physical mainly contains sonochemical method, comprises ultrasonic and microwave method, and palladium nanometer purity prepared by Physical is higher, but the size of nano particle and uniformly dispersed be that physical method is restive; And chemical method is mainly chemical reduction method and electrochemical process, prepared nano particle need to be stablized by macromolecule, surfactant or special ligand conventionally.
At present, chemical reduction method, according to the difference of reducing agent reducing power, can be divided into strong reductant and weak reductant.Strong reductant mainly contains: hydrazine hydrate, boron hydride and hydrogen, they have very strong reducing power, reaction speed is fast, the palladium nano-particles particle diameter generating is larger, and reducing agent self is unstable, be difficult for long-time control, and weak reductant has alcohol/aldehyde compound, formic acid and N, dinethylformamide etc., the rate of reduction of these reducing agents is slower, and easily controls in course of reaction, but conventionally need to heat reaction system.Hydrazine hydrate is strong basicity, has very strong reducing power under alkali condition, if prepared metallic particles need to complete under acid condition, the reproducibility of hydrazine hydrate can not be brought into play; Boron hydride (sodium borohydride, potassium borohydride, hydroboration TBuA) is as a kind of more conventional strong reductant, in metal nanoparticle synthetic, be more and more concerned, sodium borohydride chemical property is very active, easily decomposes, very unstable when reduction; Hydrogen is by a kind of reducibility gas of people's extensive use; although hydrogen is clean type reducing agent; but generally need nitrogen atmosphere protection as reducing agent with hydrogen; prevent being again oxidized of palladium particle after reduction; simultaneously as inflammable and explosive hydrogen; aspect processing safety, also there is certain hidden danger; and in reduction process; if hydrogen is scattering and permeating in made palladium film; hydrogen is dissolved in palladium and forms Pd-H solid solution with palladium in mutually; cause Hydrogen Brittleness Phenomena, the saturating Hydrogen Energy power of palladium is had to certain impact.
At present, alcohol compound is that reducing agent mainly comprises ethanol, ethylene glycol and tetraethylene-glycol, because many alcohol reducing process is preparing unique advantage in elemental metals nano material, the pattern of its metal nano material obtaining is abundanter, but also can be widely used in different metals, therefore cause numerous researchers' very big interest.The use 4-methyl-2 pentanones such as Tano T are solvent, prepare palladium nano-particles by palladium thermal decomposition, but the particle obtaining larger (about 250nm).What Po Lam etc. improves the method, has obtained the palladium nano-particles of the about 35nm of particle diameter by microwave heating method.Recently, the spent glycols such as Wang Yuan have synthesized platinum, rhodium, ruthenium nano-particle as solvent, the colloidal solid particle diameter of gained is little, narrowly distributing, concentration are high, good stability, but be both the palladium of platinum metal, in ethylene glycol, but can not get stable palladium nanoparticle, above reducing condition is harsher, cannot be in industrial large-scale production, so be necessary to seek a kind of simple method for synthesizing of novel stable nanometer palladium/carbon catalyst, so that the application of suitability for industrialized production.
Summary of the invention
The present invention provides a kind of preparation method of loaded nano palladium/carbon catalyst for overcoming the deficiencies in the prior art, this preparation method is taking the organic molecule containing amino and carboxyl functional group as additive, taking ethylene glycol as solvent with reducing agent, taking active carbon as carrier, first after the amino containing on additive and carboxyl and palladium coordination, low temperature stirs lower reduction palladium, obtains particle diameter and be the palladium nano-particles of 7nm and be dispersed in activated carbon surface forming loaded nano palladium/carbon catalyst.
Technical scheme of the present invention is: a kind of preparation method of loaded nano palladium/carbon catalyst, it is characterized in that: first will be dissolved in ethylene glycol containing the organic molecule of amino and carboxyl functional group, adding mass concentration is the palladium chloride aqueous solution of 2mg/ml, and under the condition stirring, regulating the pH value of reaction system with the ethylene glycol solution of potassium hydroxide is 9-12; Then add active carbon, be uniformly dispersed by the ultrasonic mixed system that makes, in the water-bath of 50-100 DEG C, normal pressure stirs 5-12h, and suction filtration, uses respectively redistilled water and absolute ethanol washing filter cake, collects 40 DEG C of dry loaded nano palladium/carbon catalysts that make of sample.Organic molecule containing amino and carboxyl functional group of the present invention comprises p-aminobenzoic acid, 6-aminocaprolc acid, threonine, lysine, tryptophan or phenylalanine.The molar concentration of the ethylene glycol solution of potassium hydroxide of the present invention is 1mol/L.
The present invention has following beneficial effect: (1) production cost is low, easy and simple to handle, and condition is not harsh, environmental friendliness, and without dangerous, reaction system is to complete in the water-bath of 50-100 DEG C, without harsh high temperature high pressure device; (2) prepared nanometer palladium/carbon catalyst stable in properties, palladium nano-particles can be scattered on carrier equably.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the loaded nano palladium/carbon catalyst prepared of the embodiment of the present invention 1, and Fig. 2 is the transmission electron microscope picture of the loaded nano palladium/carbon catalyst prepared of the embodiment of the present invention 1.
Detailed description of the invention
By the following examples foregoing of the present invention is described in further details, but this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realizing based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Get the p-aminobenzoic acid of 50mg in the ethylene glycol of 50ml (EG), ultrasonic extremely without bulky grain solid, then add 11.16ml, the PdCl of 2mg/ml
2the aqueous solution, under intense agitation, regulate reaction system pH=11 with the EG solution (molar concentration of the EG solution of KOH is 1mol/L) of KOH, afterwards, add the active carbon of 1g, be uniformly dispersed by the ultrasonic mixed system that makes, stir after 1-2h, after 100 DEG C of agitating heating 5-12h of water-bath, suction filtration, use respectively redistilled water and absolute ethanol washing filter cake, collect sample, in vacuum drying chamber, 40 DEG C of temperature are dried to obtain nanometer palladium/carbon catalyst, Fig. 1 is the x-ray diffractogram of powder spectrum of the nanometer palladium/carbon catalyst prepared of the present embodiment, in this collection of illustrative plates, diffraction maximum is corresponding with the diffraction data of palladium, respectively at 39.77 °, 46.30 °, four diffraction maximums of 67.42 ° and 81.90 ° correspond respectively to (111) of the palladium of face-centred cubic structure, (200), and (311) crystal face (220), Fig. 2 is the transmission electron microscope picture of the nanometer palladium/carbon catalyst prepared of the present embodiment, wherein the particle mean size of the palladium of load is 7nm left and right.
Embodiment 2
Get the 6-aminocaprolc acid of 50mg in the ethylene glycol of 50ml (EG), ultrasonic extremely without bulky grain solid, then add 11.16ml, the PdCl of 2mg/ml
2the aqueous solution, under intense agitation, regulate reaction system pH=11 with the EG solution (molar concentration of the EG solution of KOH is 1mol/L) of KOH; Afterwards, add the active carbon of 1g, be uniformly dispersed by the ultrasonic mixed system that makes, stir after 1-2h, after 100 DEG C of agitating heating 5-12h of water-bath, suction filtration, use respectively redistilled water and absolute ethanol washing filter cake, collect sample, in vacuum drying chamber, 40 DEG C of temperature obtain nanometer palladium/carbon catalyst after being dried.
Embodiment 3
Get the threonine of 50mg in the ethylene glycol of 50ml (EG), ultrasonic extremely without bulky grain solid, then add 11.16ml, the PdCl of 2mg/ml
2the aqueous solution, under intense agitation, regulate reaction system pH=11 with the EG solution (molar concentration of the EG solution of KOH is 1mol/L) of KOH; Afterwards, add the active carbon of 1g, be uniformly dispersed by the ultrasonic mixed system that makes, stir after 1-2h, after 100 DEG C of normal heating 5-12h of water-bath, suction filtration, use respectively redistilled water and absolute ethanol washing filter cake, collect sample, in vacuum drying chamber, 40 DEG C of temperature obtain nanometer palladium/carbon catalyst after being dried.
Embodiment 4
Get the lysine of 50mg in the ethylene glycol of 50ml (EG), ultrasonic extremely without bulky grain solid, then add 11.16ml, the PdCl of 2mg/ml
2the aqueous solution, under intense agitation, regulate reaction system pH=11 with the EG solution (molar concentration of the EG solution of KOH is 1mol/L) of KOH; Afterwards, add the active carbon of 1g, be uniformly dispersed by the ultrasonic mixed system that makes, stir after 1-2h, after 100 DEG C of agitating heating 5-12h of water-bath, suction filtration, use respectively redistilled water and absolute ethanol washing filter cake, collect sample, in vacuum drying chamber, 40 DEG C of temperature obtain nanometer palladium/carbon catalyst after being dried.
Embodiment 5
Get the tryptophan of 50mg in the ethylene glycol of 50ml (EG), ultrasonic extremely without bulky grain solid, then add 11.16ml, the PdCl of 2mg/ml
2the aqueous solution, under intense agitation, regulate reaction system pH=11 with the EG solution (molar concentration of the EG solution of KOH is 1mol/L) of KOH; Afterwards, add the active carbon of 1g, be uniformly dispersed by the ultrasonic mixed system that makes, stir after 1-2h, after 50 DEG C of agitating heating 5-12h of water-bath, suction filtration, use respectively redistilled water and absolute ethanol washing filter cake, collect sample, in vacuum drying chamber, 40 DEG C of temperature obtain nanometer palladium/carbon catalyst after being dried.
Embodiment 6
Get the phenylalanine of 50mg in the ethylene glycol of 50ml (EG), ultrasonic extremely without bulky grain solid, then add 11.16ml, the PdCl of 2mg/ml
2the aqueous solution, under intense agitation, regulate reaction system pH=11 with the EG solution (molar concentration of the EG solution of KOH is 1mol/L) of KOH; Afterwards, add the active carbon of 1g, be uniformly dispersed by the ultrasonic mixed system that makes, stir after 1-2h, after 70 DEG C of agitating heating 5-12h of water-bath, suction filtration, use respectively redistilled water and absolute ethanol washing filter cake, collect sample, in vacuum drying chamber, 40 DEG C of temperature obtain nanometer palladium/carbon catalyst after being dried.
Embodiment 7
Get the p-aminobenzoic acid of 50mg in the ethylene glycol of 50ml (EG), ultrasonic extremely without bulky grain solid, then add 11.16ml, the PdCl of 2mg/ml
2the aqueous solution, under intense agitation, regulate reaction system pH=9 with the EG solution (molar concentration of the EG solution of KOH is 1mol/L) of KOH; Afterwards, add the active carbon of 1g, be uniformly dispersed by the ultrasonic mixed system that makes, stir after 1-2h, after 80 DEG C of agitating heating 5-12h of water-bath, suction filtration, use respectively redistilled water and absolute ethanol washing filter cake, collect sample, in vacuum drying chamber, 40 DEG C of temperature obtain nanometer palladium/carbon catalyst after being dried.
Embodiment 8
Get the tryptophan of 50mg in the ethylene glycol of 50ml (EG), ultrasonic extremely without bulky grain solid, then add 11.16ml, the PdCl of 2mg/ml
2the aqueous solution, under intense agitation, regulate reaction system pH=12 with the EG solution (the EG solution concentration of KOH is 1mol/L) of KOH; Afterwards, add the active carbon of 1g, be uniformly dispersed by the ultrasonic mixed system that makes, stir after 1-2h, after 50 DEG C of agitating heating 5-12h of water-bath, suction filtration, use respectively redistilled water and absolute ethanol washing filter cake, collect sample, in vacuum drying chamber, 40 DEG C of temperature obtain nanometer palladium/carbon catalyst after being dried.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention, to be apparent for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can be in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments, therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (3)
1. the preparation method of a loaded nano palladium/carbon catalyst, it is characterized in that: first will be dissolved in ethylene glycol containing the organic molecule of amino and carboxyl functional group, adding mass concentration is the palladium chloride aqueous solution of 2mg/ml, and under the condition stirring, regulating the pH value of reaction system with the ethylene glycol solution of potassium hydroxide is 9-12; Then add active carbon, be uniformly dispersed by the ultrasonic mixed system that makes, in the water-bath of 50-100 DEG C, normal pressure stirs 5-12h, and suction filtration, uses respectively redistilled water and absolute ethanol washing filter cake, collects 40 DEG C of dry loaded nano palladium/carbon catalysts that make of sample.
2. the preparation method of loaded nano palladium/carbon catalyst according to claim 1, is characterized in that: the described organic molecule containing amino and carboxyl functional group comprises p-aminobenzoic acid, 6-aminocaprolc acid, threonine, lysine, tryptophan or phenylalanine.
3. the preparation method of loaded nano palladium/carbon catalyst according to claim 1, is characterized in that: the molar concentration of the ethylene glycol solution of described potassium hydroxide is 1mol/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108236953A (en) * | 2016-12-26 | 2018-07-03 | 天津仁智科技发展有限责任公司 | A kind of preparation method of Technique of Nano Pd formaldehyde remover |
| CN109772282A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| CN112675839A (en) * | 2021-01-11 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | High-performance palladium-carbon catalyst and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108236953A (en) * | 2016-12-26 | 2018-07-03 | 天津仁智科技发展有限责任公司 | A kind of preparation method of Technique of Nano Pd formaldehyde remover |
| CN109772282A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| CN112675839A (en) * | 2021-01-11 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | High-performance palladium-carbon catalyst and preparation method thereof |
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Application publication date: 20140723 |