CN109806903A - A kind of monatomic palladium catalyst and its preparation method and application - Google Patents
A kind of monatomic palladium catalyst and its preparation method and application Download PDFInfo
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- CN109806903A CN109806903A CN201910166823.4A CN201910166823A CN109806903A CN 109806903 A CN109806903 A CN 109806903A CN 201910166823 A CN201910166823 A CN 201910166823A CN 109806903 A CN109806903 A CN 109806903A
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- Y—GENERAL 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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of monatomic palladium catalyst, the structure of the catalyst includes substrate and the active component Pd that is carried in the substrate；The substrate is the graphene of N doping, and the Pd disperses on the graphene of N doping in atom level.The catalyst is for can be realized high conversion of alkyne, high ethylene selectivity and excellent stability in the reaction of catalyzing acetylene preparing ethylene by selective hydrogenation.The invention also discloses the preparation method and application of the catalyst.
Description
Technical field
The present invention relates to catalyst fields.More particularly, to a kind of monatomic palladium catalyst and preparation method thereof and answer
With.
Background technique
Polyethylene is a kind of industrial widely used high molecular material.Industrially, polyethylene mainly passes through vinyl polymerization
Reaction obtains, and the Pintsch process that unstripped gas ethylene then passes through petroleum hydrocarbon is prepared, in cracking process, the product that is enriched with
Inevitably containing the acetylene gas of 0.1-0.5% in ethylene gas.The presence of a small amount of acetylene gas can make in ethylene raw material gas
Vinyl polymerization produces the Ziegler-Natta catalyst poisoning and deactivation of polyethylene process, and then influences the quality of product polyethylene,
Can also catalyst life be made to shorten simultaneously, increase process costs.So a small amount of acetylene effectively removed in ethylene raw material gas is anti-
Only in subsequent polyethylene production process catalyst poisoning effective way.
Catalyzing acetylene selective hydrogenation is to remove the effective way of a small amount of acetylene in material ethylene gas.It is selected by catalyzing acetylene
Selecting property adds hydrogen, not only can effectively remove the acetylene in ethylene raw material gas, can also convert the acetylene to ethylene raw.Pd base is urged
Agent is since its high catalytic activity is industrially to lead acetylene hydrogenation catalyst to be used at present, but just because of Pd base catalyst
High activity, cause inevitable catalyzing acetylene excessive hydrogenation to ethane.Pd base catalyst how is improved to select in catalyzing acetylene
The selectivity of ethylene is thus received significant attention and studied in selecting property hydrogenation reaction.
Accordingly, it is desirable to provide a kind of new catalysis high to the selectivity of ethylene in catalyzing acetylene selective hydrogenation
Agent.
Summary of the invention
The first purpose of this invention is to provide a kind of monatomic palladium catalyst, which selects catalyzing acetylene
Property, which adds in the reaction of hydrogen ethylene, can be realized high conversion of alkyne, high ethylene selectivity and excellent stability.
Second object of the present invention is to provide a kind of preparation method of monatomic palladium catalyst.
Third object of the present invention is to provide a kind of application of monatomic palladium catalyst.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of monatomic palladium catalyst, the structure of the catalyst include substrate and the active group that is carried in the substrate
Divide Pd；The substrate is the graphene of N doping, and the Pd disperses on the graphene of N doping in atom level.
Preferably, by mass percentage, in the catalyst, the load capacity of Pd is 1-3%.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of monatomic palladium catalyst, this method comprises the following steps:
Pd presoma is mixed with carbon source, nitrogen source, high-temperature process restores to obtain the nitrogen-atoms palladium catalyst.
Preferably, the mixing includes the following steps: for Pd presoma, carbon source, nitrogen source to be dissolved in solvent, is heated to thoroughly
Bright solution, then it is freeze-dried removing solvent, obtain dry solid mixture.
It is highly preferred that the solvent is deionized water.
It is highly preferred that the heating, which refers to, is heated to 60-80 DEG C.
Preferably, the condition of the high-temperature process includes: and handles at a temperature of 600-1000 DEG C in atmosphere of inert gases
1-4 hours.
It is highly preferred that the inert gas is selected from Ar.Since treatment temperature at this time is higher, compare using N2 etc. other
The inert gas that may be doped into catalyst at these elevated temperatures, Ar more can guarantee not to reaction generate interference.
Preferably, the Pd presoma is selected from one or more of sodium tetrachloropallate, potassium chloropalladate, palladium nitrate.
Preferably, the carbon source is selected from one or more of glucose, sucrose, chitosan.
Preferably, the nitrogen source is selected from one or more of dicyandiamide, urea.
Preferably, Pd presoma, carbon source, the mass ratio of the material of nitrogen source are 1-4:435:3739.
To reach above-mentioned third purpose, the present invention provides above-mentioned monatomic palladium catalyst in catalyzing acetylene selective hydrogenation
Prepare the application in the reaction of ethylene.
Preferably, contain ethylene gas in the reaction gas of the reaction.
It is highly preferred that pressing volume percentage, include in the reaction gas of the reaction: C2H2: 0.5-2.5%, C2H4:
20%-40%, H2: the inert gas of 5%-20% and surplus.
Preferably, during reaction, the reaction is heated by way of illumination.Illumination is utilized for the first time
It heats up to react selective hydrogenation of acetylene, passes through and adjust the adjustable reaction temperature of luminous intensity.
Preferably, the light source of the illumination is xenon lamp.
Preferably, the temperature after the heating is 50-200 DEG C.
Preferably, the pressure of reaction written by is 0-1.0MPa.
Preferably, in the reaction, the dosage of monatomic palladium catalyst is 30-70mg, air speed 1200mL/g.h.
Preferably, in the application, catalyst before use, first using in-situ reducing method handle catalyst, specifically,
By catalyst in 5-30%H20.5-2h is restored at 100-400 DEG C in/Ar atmosphere, is cooled to room temperature to catalyst temperature and carries out again
Selective hydrogenation of acetylene reaction.
Under these experimental conditions, it under Xenon light shining heating, compared to industrial traditional heating method, is expected to using too
Positive energy, is more in line with environmental-friendly and sustainable development.The catalyst amount and reaction temperature, pressure of selected catalysis reaction
By force, air speed is more advantageous to monatomic palladium catalyst catalyzing acetylene selective hydrogenation, obtains preferably conversion of alkyne and second
Alkene selectivity.
Beneficial effects of the present invention are as follows:
A purpose according to the present invention, monatomic palladium catalyst provided in the present invention are applied to selective acetylene and add
When in hydrogen reaction, excellent catalytic performance is shown, can be realized high conversion of alkyne, high ethylene selectivity and excellent
Stability.Another purpose according to the present invention, preparation method provided in the present invention is simple, and by adjusting Pd presoma
The monatomic palladium catalyst of different Pd load capacity can be prepared in additive amount.Another purpose according to the present invention, the present invention
The monatomic palladium catalyst of middle offer can be realized height in the application in the reaction that catalyzing acetylene selective hydrogenation prepares ethylene
Conversion of alkyne, high ethylene selectivity and excellent stability.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the transmission electron microscopy of the monatomic palladium catalyst for the nitrogen-doped graphene load that embodiment 1 obtains
Mirror figure (a), spherical aberration electron microscope (b) and distribution diagram of element (c and d).
Fig. 2 shows the transmission electron microscope figures for the catalyst morphology that embodiment 2 is prepared.
Fig. 3 shows the transmission electron microscope figure for the catalyst morphology that embodiment 3 is prepared.
Fig. 4 is shown in embodiment 4-8, the influence for the performance that different reaction temperatures reacts the photo-thermal acetylene hydrogenation,
Wherein, a is variation of the conversion of alkyne with reaction temperature, and b is that ethylene selectivity changes with reaction temperature.
Fig. 5 shows stability diagram of monatomic palladium catalyst at a temperature of temperature is 125 DEG C in embodiment 15.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
A kind of preparation method of monatomic palladium catalyst, includes the following steps:
1) 2mL tetrachloro-palladium acid sodium solution, 0.5g glucose and 2g dicyandiamide are add to deionized water, sodium tetrachloropallate
The concentration of solution is 6.250mmol/L, by gained mixture oil bath heating to 80 DEG C to complete clear；
2) solution of step 1) is removed into solvent deionized water, the solid mixture being completely dried by freeze-drying
Sample；
3) the solid mixture sample for obtaining step 2) is in the processing of tube furnace high temperature, and Ar atmosphere is enclosed, at 800 DEG C of temperature
Reason obtains the monatomic palladium catalyst of nitrogen-doped graphene load for 2 hours.
The transmission electron microscope figure of the monatomic palladium catalyst of the nitrogen-doped graphene load shown in Fig. 1
(a), spherical aberration electron microscope (b) and distribution diagram of element (c and d) show: Pd is dispersed in nitrogen-doped graphene base with monatomic form
On bottom.Inductively coupled plasma atomic emission as the result is shown monatomic palladium catalyst Pd content be 2.30wt.%.
Embodiment 2
Embodiment 1 is repeated, difference is: the concentration of Pd presoma sodium tetrachloropallate is become from 6.250mmol/L
3.125mmol/L, Pd content is as shown in table 1 in catalyst, and the transmission electron microscope characterization result of catalyst morphology is shown in Fig. 2.
Embodiment 3
Embodiment 1 is repeated, difference is: the concentration of Pd presoma sodium tetrachloropallate is become from 6.250mmol/L
12.50mmol/L, Pd content is as shown in table 1 in catalyst, and the transmission electron microscope characterization result of catalyst morphology is shown in Fig. 3.
Pd content in Pd precursor concentration and catalyst in 1 embodiment 1-3 of table
| Pd precursor concentration (mmol/L) | Pd content (wt.%) in catalyst |
| 3.125 | 1.04 |
| 6.250 | 2.30 |
| 12.50 | 2.91 |
As it can be seen that the content of Pd in catalyst can be regulated and controled by the additional amount for changing Pd presoma sodium tetrachloropallate.
Embodiment 4
The catalyst obtained with embodiment 1 carries out acetylene hydrogenation reaction under 0.02MPa (relative to standard atmospheric pressure):
50mg catalyst is laid in reactor, volume content 10%H2150 DEG C of reduction 0.5h in/Ar atmosphere, after being down to room temperature
125 DEG C of progress selective hydrogenation of acetylene reactions are warming up to by Xenon light shining, by volume percentage, reaction gas composition are as follows:
C2H2Account for 1%, C2H4Account for 20%, H220% is accounted for, remaining is Ar gas Balance Air, and air speed 1200mL/g.h, product analysis is using island
Saliva gas-chromatography, hydrogen flame ionization detector.Reaction time 1h, reaction result are as shown in table 2.
Embodiment 5
Embodiment 4 is repeated, difference is: reaction temperature becomes 75 DEG C from 125 DEG C, and reaction result is as shown in table 2.
Embodiment 6
Embodiment 4 is repeated, difference is: reaction temperature becomes 100 DEG C from 125 DEG C, and reaction result is as shown in table 2.
Embodiment 7
Embodiment 4 is repeated, difference is: reaction temperature becomes 150 DEG C from 125 DEG C, and reaction result is as shown in table 2.
Embodiment 8
Embodiment 4 is repeated, difference is: reaction temperature becomes 175 DEG C from 125 DEG C, and reaction result is listed in table 2.
Fig. 4 is shown in embodiment 4-8, the influence for the performance that different reaction temperatures reacts the photo-thermal acetylene hydrogenation,
Wherein, a is variation of the conversion of alkyne with reaction temperature, and b is that selective acetylene changes with reaction temperature.
Embodiment 9
Multiple embodiment 4, difference is: the additive amount of catalyst is 30mg, and reaction result is as shown in table 2 below.
Embodiment 10
Multiple embodiment 4, difference is: the additive amount of catalyst is 70mg, and reaction result is as shown in table 2 below.
Embodiment 11
Repeat embodiment 4, difference is: catalyst is the catalyst that embodiment 2 is prepared, reaction result such as the following table 2
It is shown.
Embodiment 12
Repeat embodiment 4, difference is: catalyst is the catalyst that embodiment 3 is prepared, reaction result such as the following table 2
It is shown.
2 embodiment 4-10 of table is catalyzed reaction result
Embodiment 13
Embodiment 4 is repeated, difference is: by volume percentage, reaction gas composition are as follows: C2H2Account for 0.8%, C2H4It accounts for
25%, H215% is accounted for, surplus is Ar gas Balance Air.Remaining condition is constant, and reaction result is close with embodiment 4.
Embodiment 14
Embodiment 4 is repeated, difference is: by volume percentage, reaction gas composition are as follows: C2H2Account for 1.5%, C2H4It accounts for
30%, H210% is accounted for, surplus is Ar gas Balance Air.Remaining condition is constant, and reaction result is close with embodiment 4.
Embodiment 15
Repeat embodiment 4, difference is: reaction temperature is maintained at 125 DEG C, reacts 12h, and at interval of 1h, sample detection is produced
Object carries out stability test.Catalytic stability result is listed in Fig. 5.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of monatomic palladium catalyst, which is characterized in that the structure of the catalyst includes substrate and is carried on the substrate
On active component Pd；The substrate is the graphene of N doping, and the Pd disperses on the graphene of N doping in atom level.
2. monatomic palladium catalyst according to claim 1, which is characterized in that by mass percentage, the catalyst
In, the load capacity of Pd is 1-3%.
3. such as the preparation method of the described in any item monatomic palladium catalysts of claim 1-2, which is characterized in that the preparation side
Method includes the following steps:
Pd presoma is mixed with carbon source, nitrogen source, high-temperature process restores to obtain the nitrogen-atoms palladium catalyst.
4. preparation method according to claim 3, which is characterized in that it is described mixing include the following steps: by Pd presoma,
Carbon source, nitrogen source are dissolved in solvent, are heated to obtaining clear solution, then are freeze-dried removing solvent, obtain dry solid mixture；It is excellent
Selection of land, the solvent are deionized water；Preferably, the heating, which refers to, is heated to 60-80 DEG C.
5. preparation method according to claim 3, which is characterized in that the condition of the high-temperature process includes: in indifferent gas
In body atmosphere, handled 1-4 hours at a temperature of 600-1000 DEG C；Preferably, the inert gas is selected from Ar.
6. preparation method according to claim 3 or 4, which is characterized in that the Pd presoma is selected from sodium tetrachloropallate, chlorine
One or more of palladium acid potassium, palladium nitrate；The carbon source is selected from one or more of glucose, sucrose, chitosan；It is described
Nitrogen source is selected from one or more of dicyandiamide, urea.
7. preparation method according to claim 3 or 4, which is characterized in that the substance of the Pd presoma, carbon source, nitrogen source
Amount ratio be 1-4:435:3739.
8. as the described in any item monatomic palladium catalysts of claim 1-2 prepare the anti-of ethylene in catalyzing acetylene selective hydrogenation
Application in answering.
9. application according to claim 8, which is characterized in that contain ethylene gas in the reaction gas of the reaction；It is preferred that
Ground includes: C in the reaction gas of the reaction by volume percentage2H2: 0.5-2.5%, C2H4: 20%-40%, H2: 5%-
20% and surplus inert gas.
10. application according to claim 8, which is characterized in that during reaction, to described by way of illumination
Reaction is heated；Preferably, the light source of the illumination is xenon lamp；Preferably, the temperature after the heating is 50-200 DEG C；
Preferably, the pressure of the reaction is 0-1.0MPa；Preferably, in the reaction, the dosage of monatomic palladium catalyst is 30-
70mg, air speed 1200mL/g.h.
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| CN110813282A (en) * | 2019-09-27 | 2020-02-21 | 南京宁智高新材料研究院有限公司 | Device and method for coupling application of single-site metal catalyst and electrolytic hydrogen sulfide system |
| CN111545234A (en) * | 2020-04-20 | 2020-08-18 | 西安交通大学 | Zinc-doped graphene catalyst and preparation method and application thereof |
| CN112337462A (en) * | 2020-11-06 | 2021-02-09 | 辽宁大学 | Atomic-level dispersed Pd catalyst prepared by nitric acid steam method and application thereof |
| CN114308107A (en) * | 2021-12-27 | 2022-04-12 | 西北化工研究院有限公司 | Graphene-based nitrogen-doped hierarchical porous carbon supported palladium catalyst and preparation method and application thereof |
| CN114433085A (en) * | 2022-02-24 | 2022-05-06 | 海南大学 | Monoatomic catalyst and its preparing process |
| CN114534768A (en) * | 2022-03-25 | 2022-05-27 | 北京单原子催化科技有限公司 | Monoatomic site catalyst with M-N-C structure, preparation and application thereof |
| CN115739158A (en) * | 2022-11-28 | 2023-03-07 | 东南大学 | N-doped Pd-based catalyst and preparation method and application thereof |
| CN115845840A (en) * | 2022-12-23 | 2023-03-28 | 辽宁大学 | Graphene-loaded atomic-level dispersed palladium-based catalyst and preparation method and application thereof |
| CN116063206A (en) * | 2022-12-28 | 2023-05-05 | 重庆建峰化工股份有限公司 | High-quality urea for vehicles and production process thereof |
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| CN110813282A (en) * | 2019-09-27 | 2020-02-21 | 南京宁智高新材料研究院有限公司 | Device and method for coupling application of single-site metal catalyst and electrolytic hydrogen sulfide system |
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| CN111545234A (en) * | 2020-04-20 | 2020-08-18 | 西安交通大学 | Zinc-doped graphene catalyst and preparation method and application thereof |
| CN112337462A (en) * | 2020-11-06 | 2021-02-09 | 辽宁大学 | Atomic-level dispersed Pd catalyst prepared by nitric acid steam method and application thereof |
| CN112337462B (en) * | 2020-11-06 | 2023-08-11 | 辽宁大学 | Atomic-level dispersed Pd catalyst prepared by nitric acid steam method and application thereof |
| CN114308107A (en) * | 2021-12-27 | 2022-04-12 | 西北化工研究院有限公司 | Graphene-based nitrogen-doped hierarchical porous carbon supported palladium catalyst and preparation method and application thereof |
| CN114308107B (en) * | 2021-12-27 | 2023-12-05 | 西北化工研究院有限公司 | Graphene-based nitrogen-doped hierarchical pore carbon supported palladium catalyst and preparation method and application thereof |
| CN114433085A (en) * | 2022-02-24 | 2022-05-06 | 海南大学 | Monoatomic catalyst and its preparing process |
| CN114534768A (en) * | 2022-03-25 | 2022-05-27 | 北京单原子催化科技有限公司 | Monoatomic site catalyst with M-N-C structure, preparation and application thereof |
| CN115739158A (en) * | 2022-11-28 | 2023-03-07 | 东南大学 | N-doped Pd-based catalyst and preparation method and application thereof |
| CN115845840A (en) * | 2022-12-23 | 2023-03-28 | 辽宁大学 | Graphene-loaded atomic-level dispersed palladium-based catalyst and preparation method and application thereof |
| CN116063206A (en) * | 2022-12-28 | 2023-05-05 | 重庆建峰化工股份有限公司 | High-quality urea for vehicles and production process thereof |
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