CN105771973A - Preparation method for nanocrystalline palladium-carbon catalyst with high activity - Google Patents
Preparation method for nanocrystalline palladium-carbon catalyst with high activity Download PDFInfo
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- CN105771973A CN105771973A CN201410813566.6A CN201410813566A CN105771973A CN 105771973 A CN105771973 A CN 105771973A CN 201410813566 A CN201410813566 A CN 201410813566A CN 105771973 A CN105771973 A CN 105771973A
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Abstract
The invention discloses a preparation method for a nanocrystalline palladium-carbon catalyst with high activity. The preparation method comprises the following steps: preparation of a palladium complex; adsorption and adhesion of the palladium complex; preparation of a reducing agent; ultrasonic-assisted reduction and drying; etc. The nanocrystalline palladium-carbon catalyst with high activity prepared in the invention mainly overcomes the problems of difficulty in effective control of granularity and dispersity of palladium in palladium-carbon catalysts produced by traditional precipitation methods and impregnation methods, poor repeatability of batch production of the catalysts, large particle sizes, wide distribution range, low dispersity and poor stability of prepared active palladium particles, contamination of products caused by shedding of nanometer palladium particles, low repeated usage frequencies, etc. The nanocrystalline palladium-carbon catalyst with high activity prepared in the invention has the advantages of small sizes and smaller dispersity of active palladium particles, and better catalytic activity, better selectivity and higher repeated usage frequencies in catalytic reactions, etc.
Description
Technical field
The present invention relates to loaded noble metal catalyst field, the preparation method being specifically related to a kind of high-activity nano palladium carbon catalyst.
Background technology
It is known that palladium charcoal is a kind of traditional loaded noble metal catalyst, have a wide range of applications in medicine, chemical industry, especially in p-phthalic acid hydrofinishing, rosin-disproportionating manufacture disproportionated rosin and meropenem synthesis etc..Traditional sedimentation method and infusion process prepare the technology stability of palladium carbon catalyst and repeatability is not good enough, and production process is loaded down with trivial details, consuming big, the operation factors affecting properties of product is complicated, wayward, it is big to there is active palladium grain diameter in the palladium carbon catalyst prepared, distribution width, skewness, dispersion is low, the shortcomings such as poor stability and nanoparticle palladium come off polluted product, repeat to apply mechanically number of times few, and hydrogenated products yield is low and by-product is high.
Traditional sedimentation method and infusion process are prepared palladium carbon catalyst and are mainly included the pretreatment of activated carbon, the absorption-deposition of palladium salt, reduction, and washing is dry.In preparation process carrier batch and many complicated factors such as pretreatment, reaction temperature, mixing speed, the concentration of reaction system, the kind of reducing agent and concentration all can affect the particle diameter of active palladium granule, distribution of particles and dispersion.At active palladium granule in the forming process on high-area carbon surface, in general first have to be formed the nucleus of Technique of Nano Pd at carrier surface, the presoma of palladium wants preferential continued growth on the nucleus of Technique of Nano Pd by reducing, and reunites, and therefore the granularity of palladium and dispersion are difficult to control really.Current research all concentrates on the granularity and decentralised control that realize palladium in the surface modification of high-area carbon, but the production cost that the thing followed is greatly improved really, and therefore there is bigger problem in its practicality.
Summary of the invention
The shortcomings such as it is poor to it is an object of the invention to for there is active palladium particle dispersion in traditional palladium carbon catalyst production technology, repeats to apply mechanically number of times few, and hydrogenated products yield is low and by-product is high, it is provided that the preparation method of a kind of high-activity nano crystallite palladium carbon catalyst.The method has energy-conservation, economical, environmental protection, and technique is simple, it is easy to controlling, batch reproducibility is good, and the palladium particle size of activity is little, and dispersion is less, have in catalytic reaction better catalysis selectivity active, better and Geng Gao repeat apply mechanically the advantages such as number of times.The present invention is achieved by the following scheme:
The preparation method of high-activity nano crystallite palladium carbon catalyst, it is characterised in that comprise the following steps:
(1) preparation of palladium complex；
Palladous chloride. (PdCl is dissolved with alcohol water mixed solvent2) after powder, at normal temperatures, stir 30-90min, then add appropriate a certain proportion of choline chloride, carbamide, ethylene glycol mixture, use ultrasonic Treatment 30-90min.
(2) by step (1) gained palladium complex under an inert atmosphere by stirring, dripping, impregnate, be adsorbed onto on high-area carbon.
(3) reducing agent prepared in advance is added in the high-area carbon of load palladium, after having reacted, adds deionized water dilution, dispersion, filter, wash and the dry loaded nano crystallite palladium carbon catalyst preparing high dispersive.
In described method, step (1) mixing speed is between 200-1300rpm, and ultrasonic energy controls at 1-15W/cm2Between.
In described method, step (1) alcohol water mixed solvent is alcoholic solvent, and wherein alcoholic solvent is the solvent that one or more components in methanol, ethanol, ethylene glycol, n-butyl alcohol, isopropanol are formulated in any proportion；In described method, choline chloride, carbamide, ethylene glycol mixture can the formulated in any proportion mixture of three components.
In described method, step (2) rate of addition is 1-30ml/min, and mixing speed is at 200-1300rpm, adsorption temp 18-55 DEG C, and adsorption time is 1-5h.
In described method, step (3) reducing agent is one or more formulated mixture of formaldehyde, sodium formate, hydrazine hydrate, glucose, sodium borohydride, and concentration is 0.05-4mol/L；Reducing agent can also be the gaseous mixture of hydrogen and nitrogen, its volume ratio and hydrogen: nitrogen=2:1.
In described method, step (3) reaction temperature 20-80 DEG C, the response time is 30-90min.
The inventive method prepares high-activity nano palladium carbon catalyst, emphasis solves traditional sedimentation method and infusion process produces palladium granularity and dispersion in palladium carbon catalyst and is difficult to control, catalyst batch produces poor repeatability, prepared active palladium grain diameter is big, distribution width, skewness, dispersion is low, poor stability and nanoparticle palladium come off polluted product, repeat to apply mechanically the problems such as number of times is few.High-activity nano palladium carbon catalyst prepared by the inventive method, the palladium particle size of activity is little, and dispersion is less, have in catalytic reaction better catalysis selectivity active, better and Geng Gao repeat apply mechanically the advantages such as number of times.
The choline chloride type ionic liquid of use first of the present invention is applied to prepare palladium carbon catalyst, the method has energy-conservation, economical, environmental protection, technique is simple, it is easy to control, batch reproducibility is good, the palladium particle size of activity is little, and dispersion is less, repeat to apply mechanically number of times can up to 30-150 time, hydrogenated products yield is high, by-product is low and the advantage such as saving resource.
Detailed description of the invention
Below in conjunction with some detailed description of the invention, the invention will be further described.
Embodiment 1:
(1) preparation of palladium complex: by 8.4gPdCl2Join in 100ml ethanol water (volume ratio 2:1) mixed solvent, at 20 DEG C of temperature, stir 45min, then add 20ml choline chloride, carbamide, ethylene glycol mixture (mass ratio of ethylene glycol is 2:1:1 for choline chloride, carbamide), sonic oscillation 35min.
(2) absorption of palladium complex: above-mentioned gained palladium complex is passed through agitation and dropping in a nitrogen atmosphere, dipping is adsorbed onto 95g on pretreated high-area carbon, and rate of addition is 2ml/min, and mixing speed is at 800rpm, adsorption temp 40 DEG C, adsorption time is 2h.
(3) reduction: add concentration for 1mol/L mixing reducing agent (formaldehyde and hydrazine hydrate mol ratio are for 2:1) 60ml with the speed of 1ml/min, controls the pH=6-9 of reactant liquor by adding the NaOH aqueous solution of 5%, after reaction 100min, and cooling, filter；
(4) wash, dry: with deionized water wash to existing without chloride ion with silver nitrate detection, be placed in 80 DEG C of vacuum dryings extremely required moisture.
Embodiment 2:
(1) preparation of palladium complex: by 1.68gPdCl2Join in 25ml ethanol water (volume ratio 1:1) mixed solvent, at 25 DEG C of temperature, stir 30min, then add 5ml choline chloride, carbamide, ethylene glycol mixture (mass ratio of ethylene glycol is 1:1:1 for choline chloride, carbamide), sonic oscillation 25min.
(2) absorption of palladium complex: above-mentioned gained palladium complex is passed through agitation and dropping in a nitrogen atmosphere, dipping is adsorbed onto 99g on pretreated high-area carbon, and rate of addition is 5ml/min, and mixing speed is at 600rpm, adsorption temp 30 DEG C, adsorption time is 4h.
(3) reduction: add concentration for 0.5mol/L mixing reducing agent (formaldehyde and sodium formate mol ratio are for 1:1) 10ml with the speed of 2ml/min, controls the pH=4-9 of reactant liquor by adding the NaOH aqueous solution of 5%, after reaction 60min, and cooling, filter；
(4) wash, dry: with deionized water wash to existing without chloride ion with silver nitrate detection, be placed in 80 DEG C of vacuum dryings extremely required moisture.
Claims (6)
1. the preparation method of a high-activity nano crystallite palladium carbon catalyst, it is characterised in that comprise the following steps:
(1) preparation of palladium complex: dissolve Palladous chloride. (PdCl with alcohol water mixed solvent2) after powder, at normal temperatures, stir 30-90min, then add appropriate a certain proportion of choline chloride, carbamide, ethylene glycol mixture, use ultrasonic Treatment 30-90min；
(2) by step (1) gained palladium complex under an inert atmosphere by stirring, dripping, impregnate, be adsorbed onto on high-area carbon；
(3) reducing agent prepared in advance is added in the high-area carbon of load palladium, after having reacted, adds deionized water dilution, dispersion, filter, wash and the dry loaded nano crystallite palladium carbon catalyst preparing high dispersive.
2. the preparation method of a kind of high-activity nano crystallite palladium carbon catalyst according to claim 1, it is characterised in that step (1) mixing speed is between 200-1300rpm, and ultrasonic energy controls at 1-15W/cm2Between.
3. the preparation method of a kind of high-activity nano crystallite palladium carbon catalyst according to claim 1, it is characterized in that step (1) alcohol water mixed solvent is alcoholic solvent, wherein alcoholic solvent is the solvent that one or more components in methanol, ethanol, ethylene glycol, n-butyl alcohol, isopropanol are formulated in any proportion；Choline chloride, carbamide, ethylene glycol mixture can the formulated in any proportion mixture of three components.
4. the preparation method of a kind of high-activity nano crystallite palladium carbon catalyst according to claim 1, it is characterised in that step (2) rate of addition is 1-30ml/min, and mixing speed is at 200-1300rpm, adsorption temp 18-55 DEG C, and adsorption time is 1-5h.
5. the preparation method of a kind of high-activity nano crystallite palladium carbon catalyst according to claim 1, it is characterized in that one or more formulated mixture that step (3) reducing agent is formaldehyde, sodium formate, hydrazine hydrate, glucose, sodium borohydride, concentration is 0.05-4mol/L；Reducing agent can also be the gaseous mixture of hydrogen and nitrogen, its volume ratio and hydrogen: nitrogen=2:1.
6. the preparation method of a kind of high-activity nano crystallite palladium carbon catalyst according to claim 1, it is characterised in that step (3) reaction temperature 20-80 DEG C, the response time is 30-90min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142024A (en) * | 2017-07-20 | 2017-09-08 | 广西容县宏旺树脂有限公司 | A kind of disproportionated rosin production technology of high dehydrogenation abietic acid |
| CN115555014A (en) * | 2021-07-01 | 2023-01-03 | 谷育英 | High-activity palladium-carbon catalyst and preparation method and application thereof |
| CN117732465A (en) * | 2024-02-20 | 2024-03-22 | 山西安仑化工有限公司 | Continuous preparation method and preparation device of palladium/carbon black catalyst |
-
2014
- 2014-12-24 CN CN201410813566.6A patent/CN105771973A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142024A (en) * | 2017-07-20 | 2017-09-08 | 广西容县宏旺树脂有限公司 | A kind of disproportionated rosin production technology of high dehydrogenation abietic acid |
| CN115555014A (en) * | 2021-07-01 | 2023-01-03 | 谷育英 | High-activity palladium-carbon catalyst and preparation method and application thereof |
| CN117732465A (en) * | 2024-02-20 | 2024-03-22 | 山西安仑化工有限公司 | Continuous preparation method and preparation device of palladium/carbon black catalyst |
| CN117732465B (en) * | 2024-02-20 | 2024-05-03 | 山西安仑化工有限公司 | Continuous preparation method and preparation device of palladium/carbon black catalyst |
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