CN109806867A - Nano-sized carbon loads atom level dispersion copper-based catalysts and its preparation method and application - Google Patents
Nano-sized carbon loads atom level dispersion copper-based catalysts and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of nano-sized carbon load atom level dispersion copper-based catalysts and its preparation method and application, belong to selective hydrogenation of acetylene reactive applications catalyst technical field.Acetylene hydrogenation is generated ethylene in mixed raw material gas by the atom level dispersion copper-based catalysts, and the use temperature of catalyst is 100 DEG C -200 DEG C；By the way that copper is dispersed on nano-carbon material with atom level, compared with traditional palladium base carbon material and business palladium catalyst, nano-sized carbon of the present invention load atom level dispersion copper-based catalysts can effectively catalyzing acetylene be converted into ethylene, acetylene hydrogenation selectively significantly improves.And the catalyst is cheap, and stability is good, during the reaction not easy in inactivation.
Description
Technical field
The present invention relates to acetylene hydrogenation catalysts technical fields, and in particular to a kind of nano-sized carbon load atom level dispersion
Copper-based catalysts and its preparation method and application.
Background technique
Ethylene (C2H2) a kind of basic chemical industry raw material as synthetic plastic, fiber, rubber etc., there is highly important work
Industry application value.However, usually containing a small amount of acetylene in the ethylene product obtained by petroleum cracking, the presence of acetylene is reduced
The quality of downstream polymerisation object production, while can also poison the catalyst of downstream polymerisation reaction.It therefore, will be few in ethylene raw
Amount selective hydrogenation of acetylene prepares ethylene and has a very important significance in fine chemistry industry and polymer industry production process.
Most widely used tradition selective hydrocatalyst of acetylene is noble metal palladium base Lindlar catalysis in industrial reaction
Agent.It is active metal component that Lindlar catalyst, which selects precious metal palladium, expensive.Simultaneously in Lindlar containing sulphur and lead at
Point, it can be lost in environment, pollute the environment with product.
Therefore, the present invention attempts using nano-carbon material to be carrier, researches and develops the new selective hydrogenation of acetylene that is suitable for and reacts
Nonhazardous, non-precious metal catalyst.
Summary of the invention
The purpose of the present invention is to provide a kind of nano-sized carbon load atom level dispersion copper-based catalysts and preparation method thereof and
Using prepared nano-sized carbon load atom level dispersion copper-based catalysts have preferable selection in acetylene hydrogenation reaction process
Property and stability.
To achieve the above object, technical solution of the present invention is as follows:
A kind of nano-sized carbon load atom level dispersion copper-based nano-catalyst, the catalyst is using copper as active material, nano-sized carbon
For carrier, copper is dispersed on nano-carbon material carrier in the form of atom level.
The nano-carbon material carrier is core-shell structure, and Nano diamond is core, and grapheme material is shell；Copper is with atom
Form is dispersed in graphene shell layer surface, and with the carbon atom bonding in graphene defect.
In the catalyst, the load capacity of copper is 0.25~0.5wt.%.
The nano-carbon material carrier is obtained after high-temperature process using Nano diamond as raw material；At the high temperature
Manage detailed process are as follows: Nano diamond is placed in tubular heater, is roasted under the conditions of inert atmosphere and 900~1100 DEG C
4h-6h, i.e. acquisition nano-carbon material carrier.Nanometer carbon carrier surface defect abundant, be conducive to active metal copper dispersion and
Stablize.
The preparation method of the nano-sized carbon load atom level dispersion copper-based catalysts, includes the following steps:
(1) prepare nano-carbon material carrier；
(2) deposition-precipitation method is used, is deposited copper on nano-carbon material carrier, nano-sized carbon load copper-based catalysts are obtained
Predecessor；
(3) nano-sized carbon is loaded copper-based catalyst precursors to be placed in quartz ampoule, in the gaseous mixture of hydrogen and helium
Disperse copper-based catalysts after middle carry out reduction treatment to get to nano-sized carbon load atom level.
In above-mentioned steps (2), the process of the deposition-precipitation method are as follows: 20-40mL water is added in 100mL round-bottomed flask,
200mg nanometers of carbon carriers are put into, ultrasonic disperse is uniform, then adjusts pH value to 11-12 with sodium carbonate liquor, obtains nano-sized carbon load
Dispersion liquid；Then copper nitrate solution is prepared, and calculates the dosage of copper nitrate solution according to the load capacity of copper in catalyst, by nitre
Sour copper solution is added in nano-sized carbon support dispersion；Finally in oil bath pan insulated and stirred 1-2 hours under the conditions of 80-100 DEG C,
Then it is cooled to room temperature, nano-sized carbon is obtained after suction filtration and washing and loads copper-based catalyst precursors.
During above-mentioned steps (3) reduction treatment, in the gaseous mixture of the hydrogen and helium, hydrogen volume score is
10%, the flow velocity 50mL/min of gaseous mixture；Reduction treatment temperature is 200~300 DEG C, and the recovery time is 1 hour；After reduction treatment
Room temperature is dropped in 50mL/min helium atmosphere.
The catalyst that nano-sized carbon load atom level dispersion copper-based catalysts are reacted as acetylene hydrogenation, it is former in mixing
Catalyzing acetylene is hydrogenated to ethylene in material gas.
In the acetylene hydrogenation reaction process, the use temperature of catalyst is 100~200 DEG C；In mixed raw material gas: acetylene
For 1vol.%, hydrogen 10vol.%, ethylene 20vol.%, helium is Balance Air；Air speed 6000mL/gh.
The catalyst in acetylene hydrogenation reaction process, conversion of alkyne to be 2~95%, ethylene selectivity is 98~
100%；Catalyst can be stablized under 200 DEG C of reaction temperatures using 60 hours.
Advantage of the present invention is as follows:
1, the present invention is for the first time using nano-sized carbon load atom level dispersion copper-based catalysts as acetylene hydrogenation catalysts.
It is active material that the catalyst, which selects base metal copper, and nano-sized carbon is carrier, extensive, the low in cost, environment with material source
Friendly, the advantages that manufacturing process is mature, there is outstanding catalytic selectivity and good stability in acetylene hydrogenation reaction, be
The base metal metallic catalyst of great industrial applications prospect.
2, the present invention is using nano-sized carbon load atom level dispersion copper-based catalysts as acetylene hydrogenation catalysts.This is urged
Agent high stability, shown in acetylene hydrogenation reaction process the conversion ratio of excellent hydrogenation selectivity energy and acetylene compared with
Height improves the yield of product ethylene.At 200 DEG C, conversion of alkyne 95%, ethylene selectivity 98%.
3, the present invention is using nano-sized carbon load atom level dispersion copper-based catalysts as acetylene hydrogenation catalysts.This is urged
Agent has good stable circulation performance, sustainable to use 60 hours under 200 DEG C of reaction temperatures in acetylene hydrogenation reaction
Do not occur performance decline.
4, used catalyst mature production technology of the present invention, preparation method is easy, low in cost to be produced on a large scale.
5, carrier of the nano-carbon material as catalyst can recycle gold by way of burning from waste and old catalyst
Belong to.
Detailed description of the invention
Fig. 1 is the HAADF-TEM figure that nanocarbons grade prepared by embodiment 1 disperses copper-based catalysts；
Fig. 2 is that nano-sized carbon prepared by comparative example 1 loads nanocluster dispersion copper-based catalysts HAADF-TEM figure.
Specific embodiment
The present invention is described in detail with reference to embodiments.
In following example 1 and comparative example 1, the preparation process of nanometer carbon carrier is as follows:
Nano diamond is placed in tubular heater, 4h is roasted under the conditions of inert atmosphere and 1100 DEG C, obtains nanometer
Diamond/graphene composite material, as nanometer carbon carrier.
Comparative example 1
200mg Nano diamond/graphene carrier, ultrasonic disperse are put into the 100mL round-bottomed flask equipped with 30mL water
PH value is adjusted to 11 with 0.25mol/L sodium carbonate liquor after uniformly, obtains nano-sized carbon support dispersion.It is by copper load capacity
0.5wt% calculates copper nitrate solution dosage, and then 0.016mol/L copper nitrate solution is added in nano-sized carbon support dispersion,
100 DEG C insulated and stirred 1 hour, is then cooled to room temperature in oil bath pan, is filtered, washs acquisition Nano diamond/graphene
The copper-based catalysts predecessor of composite material load.Then 200mg nano-sized carbon is loaded into copper-based catalyst precursors and is placed in quartz
Guan Zhong handles 1 hour at 600 DEG C with the hydrogen and helium mix gas of 50mL/min flow velocity (hydrogen volume score is 10%), so
Room temperature is dropped in 50mL/min helium atmosphere afterwards and disperses copper-based catalysts to get to nano-sized carbon load nanocluster.It is denoted as
Cun/ND@G。
Embodiment 1
200mg Nano diamond/graphene carrier, ultrasonic disperse are put into the 100mL round-bottomed flask equipped with 30mL water
PH value is adjusted to 11 with 0.25mol/L sodium carbonate liquor after uniformly, obtains nano-sized carbon support dispersion.It is by load capacity
0.25wt% calculates copper nitrate solution dosage, and then 0.016mol/L copper nitrate solution is added in nano-sized carbon carrier solution,
100 DEG C insulated and stirred 1 hour, is then cooled to room temperature in oil bath pan, is filtered, washs acquisition nickel base nanometer diamond/stone
Black alkene composite catalyst predecessor.Then 200mg nano-sized carbon is loaded copper-based catalyst precursors to be placed in quartz ampoule, is used
The hydrogen and helium mix gas (hydrogen volume score is 10%) of 50mL/min flow velocity are handled 1 hour at 200 DEG C, are then existed
Room temperature is dropped in 50mL/min helium atmosphere disperses copper-based catalysts to get to nano-sized carbon load atom level.It is denoted as Cu1/ND@G。
Embodiment 2
Catalyst obtained in embodiment 1 and comparative example 1 is added in fixed bed reactors.It is passed through mixed raw material gas
Are as follows: 1% acetylene, 10% hydrogen, 20% ethylene, helium are Balance Air, and air speed 6000mL/gh, wherein percentage composition is volume
Percentage, catalyzing acetylene are hydrogenated to ethylene, and the use temperature of catalyst is 100 DEG C -200 DEG C；Reaction product is by gas-chromatography
Analysis detection.Wherein Cun/ ND@G ethylene selectivity is lower than 60%, and atom level disperses Cu1/ ND@G is in 200 DEG C of conversion of alkyne
95%, ethylene selectivity 98%.In lasting use 60, as a child catalyst performance is not decreased obviously, and illustrates present invention side
The nano-sized carbon load atom level dispersion copper-based catalysts of method preparation can obviously obtain higher acetylene catalytic reaction activity and second
Alkene selectivity.
With spherical aberration correction angle of elevation annular dark field-scanning transmission electron microscope (HAADF-STEM) observation embodiment 1 and right
The transmission electron microscope picture (Fig. 1-2) of 1 gained catalyst of ratio, it can be found that CunCopper on/ND@G is mainly in the form of nanocluster
It is dispersed on carrier.And Cu1Copper on/ND@G is mainly dispersed on carrier in the form of single atom.
By acetylene reaction as a result, 1 gained Cu of comparative examplen/ ND@G catalyzing acetylene hydrogenation conversion is lower, and selectivity is poor.
1 gained Cu of embodiment1The selectivity and conversion ratio of/ND@G catalyst acetylene hydrogenation are higher, illustrate nanometer of the present invention
Carbon, which loads atom level dispersion copper-based catalysts, has higher acetylene hydrogenation catalytic activity and ethylene selectivity.
In summary experimental result can be seen that nano-sized carbon load atom level dispersion copper-based catalysts proposed by the present invention,
This catalyst catalytic performance is good, and in catalyzing acetylene hydrogenation reaction, the selectivity of ethylene is significantly improved, can be at 200 DEG C
Obtain 95% conversion of alkyne and 98% ethylene selectivity.And the process for synthetic catalyst is mature, and modifying process is convenient easily real
It applies, is easily recycled environmentally friendly.
The above are preferred embodiments of the present invention, but protection content of the invention is not limited to the above embodiment, and are not carrying on the back
From under the spirit and scope of inventive concept, various changes and advantages that will be apparent to those skilled in the art are also included in the present invention.
Claims (10)
1. a kind of nano-sized carbon load atom level disperses copper-based catalysts, it is characterised in that: the catalyst is received using copper as active material
Rice carbon material is carrier, and copper is dispersed on nano-carbon material carrier in the form of atom level.
2. nano-sized carbon load atom level according to claim 1 disperses copper-based catalysts, it is characterised in that: the nano-sized carbon
Material support is core-shell structure, and Nano diamond is core, and grapheme material is shell；Copper is dispersed in graphite with atomic form
Alkene shell layer surface, and with the carbon atom bonding in graphene defect.
3. nano-sized carbon load atom level according to claim 1 disperses copper-based catalysts, it is characterised in that: the catalyst
In, the load capacity of copper is 0.25~0.5wt.%.
4. nano-sized carbon load atom level according to claim 1 or 2 disperses copper-based catalysts, it is characterised in that: described to receive
Rice carbon material carrier is obtained after high-temperature process using Nano diamond as raw material；The high-temperature process detailed process are as follows: will
Nano diamond is placed in tubular heater, roasts 4h-6h under the conditions of inert atmosphere and 900~1100 DEG C, i.e. acquisition nanometer
Carbon material carrier.
5. the preparation method of nano-sized carbon load atom level dispersion copper-based catalysts according to claim 1, it is characterised in that:
The preparation method includes the following steps:
(1) prepare nano-carbon material carrier；
(2) deposition-precipitation method is used, is deposited copper on nano-carbon material carrier, nano-sized carbon is obtained and loads copper-based complex catalyst precursor
Object；
(3) nano-sized carbon copper-based catalyst precursors are loaded to be placed in quartz ampoule, in the gaseous mixture of hydrogen and helium into
Disperse copper-based catalysts after row reduction treatment to get to nano-sized carbon load atom level.
6. the preparation method of nano-sized carbon load atom level dispersion copper-based catalysts according to claim 4, it is characterised in that:
In step (2), the process of the deposition-precipitation method are as follows: 20-40mL water is added in 100mL round-bottomed flask, is put into 200mg nanometers
Carbon carrier, ultrasonic disperse is uniform, then adjusts pH value to 11-12 with sodium carbonate liquor, obtains nano-sized carbon support dispersion；Then
Copper nitrate solution is prepared, and calculates the dosage of copper nitrate solution according to the load capacity of copper in catalyst, then copper nitrate solution is added
Enter into nano-sized carbon support dispersion；Finally then it is cooled to insulated and stirred 1-2 hours under the conditions of 80-100 DEG C in oil bath pan
Room temperature obtains nano-sized carbon after suction filtration and washing and loads copper-based catalyst precursors.
7. the preparation method of nano-sized carbon load atom level dispersion copper-based catalysts according to claim 4, it is characterised in that:
During step (3) reduction treatment, in the gaseous mixture of the hydrogen and helium, hydrogen volume score is 10%, gaseous mixture
Flow velocity 50mL/min；Reduction treatment temperature is 200~300 DEG C, and the recovery time is 1 hour；In 50mL/min helium after reduction treatment
Room temperature is dropped in gas atmosphere.
8. the application of nano-sized carbon load atom level dispersion copper-based catalysts according to claim 1, it is characterised in that: by institute
The catalyst that nano-sized carbon load atom level dispersion copper-based catalysts are reacted as acetylene hydrogenation is stated, is catalyzed second in mixed raw material gas
Alkynes is hydrogenated to ethylene.
9. the application of nano-sized carbon load atom level dispersion copper-based catalysts according to claim 8, it is characterised in that: described
In acetylene hydrogenation reaction process, the use temperature of catalyst is 100~200 DEG C；In mixed raw material gas: acetylene 1vol.%, hydrogen
Gas is 10vol.%, and ethylene 20vol.%, helium is Balance Air；Air speed 6000mL/gh.
10. the application of nano-sized carbon load atom level dispersion copper-based catalysts according to claim 9, it is characterised in that:
In acetylene hydrogenation reaction process, conversion of alkyne is 2%~95%, and ethylene selectivity is 98~100%；Catalyst is at 200 DEG C
It can stablize under reaction temperature using 60 hours.
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| CN111203219A (en) * | 2020-03-05 | 2020-05-29 | 南昌大学 | Copper-based catalyst for preparing formic acid from carbon dioxide, preparation method and application |
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| CN112337466A (en) * | 2020-11-27 | 2021-02-09 | 辽宁大学 | Nano-carbon-loaded cluster-state copper nanoenzyme and preparation method and application thereof |
| CN113786843A (en) * | 2021-10-09 | 2021-12-14 | 辽宁大学 | Nano-carbon-supported palladium-iron bimetallic cluster nanoenzyme as well as preparation method and application thereof |
| CN115672322A (en) * | 2022-10-12 | 2023-02-03 | 中国石油大学(华东) | Cu-series eggshell catalyst, preparation method and oxalic acid diester hydrogenation method |
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| CN113786843B (en) * | 2021-10-09 | 2024-03-22 | 辽宁大学 | Nanometer carbon-loaded palladium-iron bimetallic cluster nano-enzyme and preparation method and application thereof |
| CN115672322A (en) * | 2022-10-12 | 2023-02-03 | 中国石油大学(华东) | Cu-series eggshell catalyst, preparation method and oxalic acid diester hydrogenation method |
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