CN102974350A - Graphene-supported metallic oxide nanometer material as well as preparation method and application thereof - Google Patents
Graphene-supported metallic oxide nanometer material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of the material science, and relates to a preparation method of a novel graphene-supported metallic oxide nanometer material and a catalytic application of the novel grapheme-supported metallic oxide nanometer material in a Fischer-Tropsch synthesis reaction. The novel graphene-supported metallic oxide nanometer material is prepared by a one-step reaction of a graphite oxide and an acetylacetone metallic compound under a hydrothermal condition, and has a microstructure characteristic that small-sized nanometer oxides are uniformly dispersed on the surface of grapheme to the maximum extent. When a catalyst prepared by the novel graphene-supported metallic oxide nanometer material is used in the Fischer-Tropsch synthesis reaction, the catalyst has the advantages of higher selectivity in gasoline hydrocarbons (C5-11), high stability and the like compared with an unmodified iron catalyst reported by a current document.
Description
Technical field
The invention belongs to material science, be specifically related to a kind of graphene-supported metal oxide nano-material and its preparation method and application.
Background technology
Fischer-Tropsch is synthetic to be a kind of method that the carbon monoxide that coal, natural gas, living beings made by catalysis and hydrogen are converted into liquefied hydrocarbon, the liquid fuel that is synthesized is comprised of straight-chain hydrocarbons, alkene basically, having without sulphur, without nitrogen, without metal, without advantages such as aromatic hydrocarbons, is fuel oil and the chemicals of cleaning, environmental protection.One of key factor that Fischer-Tropsch is synthetic is to develop the catalyst of stability, active good, cheap, wide material sources.For this reason, domestic and international many R﹠D institutions and oil company have all dropped into huge financial resources and manpower is researched and developed, such as (petrochemical technology economy such as Peking University, Xiamen University, Fudan University, Shanxi coalification institute of the Chinese Academy of Sciences, the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, Shenhua Group, Sasol company, Shell company, Exxon companies, 2004,19:8; The chemical industry progress, 2003,22:441).Wherein, the material with carbon element of employing inertia has received the concern of researcher as the catalyst carrier of Fischer-Tropsch synthesis, show when adopting CNT as the carrier of iron preferably the synthetic performance of Fischer-Tropsch (J. Am. Chem. Soc., 2008,130:9414).But CNT is expensive, and the catalyst cupport method is also comparatively complicated.Thereby a kind of preparation method is simple, raw material sources widely the iron Pd/carbon catalyst can in Fischer-Tropsch is synthetic, have a good application prospect.The reserves of iron are abundant, and are cheap, and in Fischer-Tropsch synthesis to the selective height of low-carbon alkene, tend to generate low catenanes, be conducive to the synthetic important raw material of industry such as ethene, propylene, butylene and the high-octane gasoline of preparation etc.Ferrum-based catalyst has higher activity to water gas shift reaction, also is conducive to low H
2The application of the synthesis gas of/CO ratio in Fischer-Tropsch is synthetic.
Graphene owing to have unique physics and chemistry character, receives increasing concern in fields such as electricity, magnetics, optics, catalysis and drug deliveries as a kind of new carbon.But the at present preparation of Graphene is generally comparatively being carried out under the exacting terms, such as needs high temperature, high pressure, high-energy, prices of raw and semifnished materials costliness and complicated process of preparation etc.Simultaneously, be subjected to its blemish position, impact that functional group is few, the particle diameter of the nano particle of its area load is difficult to controlled, and is difficult to accomplish Uniform Dispersion, and particle diameter is large.And large particle diameter means little catalyst activity surface area, so that the utilization ratio of catalyst activity component reduces, catalytic activity is low in Fischer-Tropsch synthesis.Take Graphene, iron chloride, vitamin C, Macrogol 6000, urea as raw material, adopt hydro-thermal method to prepare iron oxide/graphene composite material such as Wang etc., the iron oxide particle diameter reaches 2-5 μ m(J. Alloys Compd., and 2011,509:L216).Wang etc. are take Graphene, ferric nitrate, sodium acetate, PEG 20000 as raw material, adopt the ethylene glycol solvent by the use of thermal means to prepare iron oxide/graphene nanocomposite material, the gathering of ferric oxide nanometer particle height (Mater. Chem. Phys., 2011,128:336).Zhou etc. adopt graphene-supported iron hydroxide, under Ar atmosphere 600
oThe C reduction has prepared the iron oxide material of Graphene parcel, and not only preparation temperature is high, and the iron oxide particle diameter that obtains is also very large, reaches 196 nm(Chem. Mater., and 2010,22:5306).The employing ferric acetates such as Wu, polypyrrole, graphite oxide are raw material, and in the aerogel material by the hydro-thermal method preparation, the particle diameter of iron oxide reaches 20 –, 80 nm(J. Am. Chem. Soc., 2012,134:9082).Zhu etc. adopt in the Graphene/ferric oxide composite material of precipitation from homogeneous solution-hydrazine reduction two-step method preparation, and the particle diameter of iron oxide reaches 60 nm(ACS Nano, and 2011,5:3333).The employing one-step method such as Su have prepared iron oxide-graphene nanocomposite material, about 7.1 nm of iron oxide particle diameter, its source of iron is iron chloride, and in water-heat process, added hydrazine reducing agent (J. Phys. Chem. C, 2011,115:14469).From the above results as can be known, the common more complicated of method for preparing graphene-supported oxide material in the document, generally need first graphite oxide to be reduced to Graphene, or at comparatively complicated chemical environment or load oxide under the exacting terms comparatively, and the oxide particle particle diameter is larger, and more the material preparation method of small particle diameter has to be developed.Thereby, develop a kind of simple and easy, energy consumption is low, the preparation method of environmental protection, efficient graphene-supported metal oxide nano-material, and the metal oxide nano-material of institute's load has, and size is little, the characteristics of high dispersive, has undoubtedly very important using value in the fields such as catalysis.
Summary of the invention
The object of the invention is to propose that a kind of utilization of materials is high, the preparation method is simple, catalytic efficiency is high, the graphene-supported metal oxide nano-material of good stability and its preparation method and application.
The preparation method of the graphene-supported metal oxide nano-material that the present invention proposes, its concrete steps are as follows:
1) 30
oC ~ 50
oIn the temperature range of C, ultrasonic being dispersed in of graphite oxide made suspension in the distilled water;
2) 60
oC ~ 80
oIn the temperature range of C, acetylacetone metallic compound is added in the above-mentioned suspension; After stirring 1 ~ 4h under this temperature, be transferred in the band teflon-lined water heating kettle;
3) water heating kettle is placed 140
oC ~ 180
oHydrothermal treatment consists 12 ~ 48 h in the baking oven of C; Then take out water heating kettle, naturally cooling, filtration, washing, oven dry make required nano material.
Wherein, graphite oxide quality optimization 0.5 ~ 2 g, preferred 100 ~ 400 mL of distilled water volume, hydrothermal temperature preferred 160 ~ 180
oC, preferred 12 ~ 24 h of hydro-thermal time.
The mass ratio of described graphite oxide and acetylacetone metallic compound is 1:1 ~ 1:5.
Described acetylacetone metallic compound is soluble metallic salt, a kind of in ferric acetyl acetonade, acetylacetone cobalt, the nickel acetylacetonate.
Among the present invention, employing graphite oxide and acetylacetone metallic compound together further hydrothermal reduction are Graphene, be formed on simultaneously the metal oxide nanoparticles that the Graphene surface uniform disperses, the metal oxide particle diameter that obtains can be less than 3 nm, high dispersive not only, and can in high temperature reduction and macrocyclic Fischer-Tropsch synthesis, keep stable.
Among the present invention, the raw material of employing only is graphite oxide and acetylacetone metallic compound, and without the adding of other reducing agents, dispersant or precipitating reagent, raw material is single.Utilize the abundant oxy radical in graphite oxide surface and the coordination of acetylacetone,2,4-pentanedione, namely realized easily the high dispersive of metal oxide nanoparticles and firmly grappling.
Among the present invention, it adopts the aqueous solution that contains graphite oxide and cetylacetone metallic to prepare target material through a step Hydrothermal Synthesis, utilize graphite oxide under hydrothermal condition, can be reduced to Graphene, acetylacetone metallic compound can be hydrolyzed to oxide under hydrothermal condition, next step has realized the reduction of graphene oxide and the load of metal oxide nanoparticles at the preparation condition of gentleness.
According to the graphene-supported metal oxide nano-material of the inventive method preparation, the active component nano particle is dispersed on the Graphene.Transmission electron microscope photo shows that to be carried on the lip-deep nanoparticulate dispersed degree of Graphene very high, and uniform particle diameter can be used as the presoma of catalyst in the Fischer-Tropsch synthesis.Be applied to the front reduction activation of Fischer-Tropsch synthesis and carry out in tube furnace, reducing condition is as follows: H
2/ Ar flow velocity is 20 ~ 60 ml/min, preferred 30 ~ 50 ml/min; Reduction temperature is 300 ~ 600
oC, preferred 400 ~ 500
oC; Recovery time is 180 ~ 2880 min, preferred 300 ~ 1440 min.
The active available following method evaluation of catalyst provided by the invention:
Fischer-Tropsch synthesis carries out in the high-pressure flow fixed-bed micro-reactor.The stainless steel reaction bore is 10 mm, and length is 470 mm, and beds is positioned at the electric tube furnace flat-temperature zone, and thermocouple places the beds middle part by sleeve pipe.Reacting gas or pretreatment gas are by the accurate adjust flux of mass flowmenter, and Fischer-Tropsch synthetic adopts gas-chromatography to analyze.
Description of drawings
Fig. 1 is the microscopic appearance of the embodiment of the invention 1 gained nano particle.
Fig. 2 is the microscopic appearance of the embodiment of the invention 2 gained nano particles.
Fig. 3 is the microscopic appearance of the embodiment of the invention 3 gained nano particles.
Fig. 4 is the microscopic appearance of the embodiment of the invention 4 gained nano particles.
The specific embodiment
The invention is further illustrated by the following examples, but therefore do not limit the present invention.
Embodiment 1: the preparation of novel graphite alkene load iron nano particle catalysis material
1 g graphite oxide is added in the 200 mL distilled water, and suspension was made in ultrasonic dispersion in 2 hours.2 g ferric acetyl acetonades are added in the above-mentioned suspension under magnetic agitation.Mixed solution is 80
oStirred 2 hours under the C, change over to afterwards in the band teflon-lined water heating kettle.Water heating kettle is placed 160
oThen Hydrothermal Synthesis certain hour in the C baking oven takes out nature cooling, filters, washing, in air atmosphere 50
oDrying is 10 hours under the C.The TEM photo of the microscopic appearance of graphene-supported iron nano-particle is seen Fig. 1 in this example, and the average grain diameter of iron nano-particle is 2.4 nm only, and particle diameter is evenly distributed.
Embodiment 2: the preparation of novel graphite alkene Supported Co nano particle catalysis material
1 g graphite oxide is added in the 200 mL distilled water, and suspension was made in ultrasonic dispersion in 2 hours.5 g acetylacetone cobalts are added in the above-mentioned suspension under magnetic agitation.Mixed solution is 80
oStirred 2 hours under the C, change over to afterwards in the band teflon-lined water heating kettle.Water heating kettle is placed 160
oThen Hydrothermal Synthesis certain hour in the C baking oven takes out nature cooling, filters, washing, in air atmosphere 50
oDrying is 10 hours under the C.The TEM photo of the microscopic appearance of graphene-supported cobalt nano-particle is seen Fig. 2 in this example, and the average grain diameter of cobalt nano-particle is 8.1 nm only, and particle diameter is evenly distributed.
Embodiment 3: the preparation of novel graphite alkene nickel-loaded nano particle catalysis material
1 g graphite oxide is added in the 200 mL distilled water, and suspension was made in ultrasonic dispersion in 2 hours.5 g nickel acetylacetonates are added in the above-mentioned suspension under magnetic agitation.Mixed solution is 80
oStirred 2 hours under the C, change over to afterwards in the band teflon-lined water heating kettle.Water heating kettle is placed 160
oThen Hydrothermal Synthesis certain hour in the C baking oven takes out nature cooling, filters, washing, in air atmosphere 50
oDrying is 10 hours under the C.The TEM photo of the microscopic appearance of graphene-supported nano nickel particles is seen Fig. 3 in this example, and the average grain diameter of nano nickel particles is 7.5 nm only, and particle diameter is evenly distributed.
The comparative example 1: the in advance preparation of the graphene-supported iron nano-particle catalysis material of reduction
1 g graphite oxide is added in the 200 mL distilled water, and suspension was made in ultrasonic dispersion in 2 hours.Then in suspension, add 5 mL concentration and be 85% hydrazine hydrate solution, 50
oThe C lower magnetic force stirs reduction 12 hours.Gained black Graphene solid after filtration, after the distilled water washing, ultrasonic being dispersed in the 200 mL distilled water made the Graphene suspension again.2 g ferric acetyl acetonades are added in the Graphene suspension under magnetic agitation, and mixed solution is 80
oStirred 2 hours under the C, change over to afterwards in the band teflon-lined water heating kettle.Water heating kettle is placed 160
oThen Hydrothermal Synthesis certain hour in the C baking oven takes out nature cooling, filters, washing, then in air atmosphere 50
oDrying is 10 hours under the C.The TEM photo of the microscopic appearance of the graphene-supported iron nano-particle that reduces in advance in this example is seen Fig. 4, and the average grain diameter of iron nano-particle reaches 32.7 nm.
Reactivity worth Evaluation operation example 1: novel graphite alkene load iron nanoparticle catalyst
Catalyst after the oven dry is sieved, get 80 ~ 120 purposes and partly pack in the reaction tube, logical H
2/ Ar(volume ratio 5%) gaseous mixture is 450
oIn-situ reducing 12 h under the C, gas flow is 50 ml/min, heating rate is 2
oC/min.The gained catalyst is designated as Fe-rGO.Fischer-Tropsch synthesis carries out under the following conditions: P=2.0 MPa, T=270
oC, gas flow rate are 33.3 ml/ min, and the unstripped gas mole consists of H
2/ CO=2, catalyst loading amount are 1 g.Reaction result is listed in table 1.
Reactivity worth Evaluation operation example 2: novel graphite alkene Supported Co nanoparticle catalyst
Catalyst after the oven dry is sieved, get 80 ~ 120 purposes and partly pack in the reaction tube, logical H
2/ Ar(volume ratio 5%) gaseous mixture is 450
oIn-situ reducing 12 h under the C, gas flow is 50 mL/min, heating rate is 2
oC/min.The gained catalyst is designated as Co-rGO.Fischer-Tropsch synthesis carries out under the following conditions: P=2.0 MPa, T=250
oC, gas flow rate are 33.3 mL/ min, and the unstripped gas mole consists of H
2/ CO=2, catalyst loading amount are 1 g.Reaction result is listed in table 2.
As seen from Table 1, the graphene-supported iron nano-particle catalyst of the method preparation that this patent proposes has shown good stability in Fischer-Tropsch synthesis, in the product gasoline section hydrocarbon selective be higher than existing bibliographical information without the result on the addition agent modified Fe fischer-tropsch synthetic catalyst, shown good application prospect.As seen from Table 2, graphene-supported cobalt nano-particle catalyst has shown good stability equally in Fischer-Tropsch synthesis, and gasoline section hydrocarbon selective has had and increases substantially on its catalyst of what is more important.
Reactivity worth is estimated comparative example 1: the in advance preparation of the graphene-supported iron nano-particle catalysis material of reduction
Catalyst after the oven dry is sieved, get 80 ~ 120 purposes and partly pack in the reaction tube, logical H
2/ Ar(volume ratio 5%) gaseous mixture is 450
oIn-situ reducing 12 h under the C, gas flow is 50 mL/min, heating rate is 2
oC/min.The gained catalyst is designated as Fe/p-rGO.Fischer-Tropsch synthesis carries out under the following conditions: P=2.0 MPa, T=250
oC, gas flow rate are 33.3 mL/ min, and the unstripped gas mole consists of H
2/ CO=2, catalyst loading amount are 1 g.Reaction result is listed in table 3.
As seen from Table 3, the Fe/p-rGO catalyst that the method that employing is reduced graphite oxide in advance with hydrazine hydrate prepares, because the iron nano-particle particle diameter is excessive, reactivity worth is very poor in Fischer-Tropsch synthesis.The catalyst initial activity is low, and in course of reaction obvious inactivation occurs.The long-chain selectivity of product is lower on this catalyst simultaneously, constantly reduces at course of reaction medium chain growing ability.
Table 1,The catalytic performance of graphene-supported iron nano-particle catalyst in Fischer-Tropsch synthesis
Table 2,The catalytic performance of graphene-supported cobalt nano-particle catalyst in Fischer-Tropsch synthesis
Table 3,The catalytic performance of Fe/p-rGO nanoparticle catalyst in Fischer-Tropsch synthesis
Claims (7)
1. the preparation method of a graphene-supported metal oxide nano-material is characterized in that concrete steps are as follows:
1) 30
oC ~ 50
oIn the temperature range of C, ultrasonic being dispersed in of graphite oxide made suspension in the distilled water;
2) 60
oC ~ 80
oIn the temperature range of C, acetylacetone metallic compound is added in the above-mentioned suspension; After stirring 1 ~ 4h under this temperature, be transferred in the band teflon-lined water heating kettle;
3) water heating kettle is placed 140
oC ~ 180
oHydrothermal treatment consists 12 ~ 48 h in the baking oven of C; Then take out water heating kettle, naturally cooling, filtration, washing, oven dry namely make required nano material.
2. the preparation method of a graphene-supported metal oxide nano-material as claimed in claim 1 is characterized in that described graphite oxide quality is 0.5 ~ 2 g, and the distilled water volume is 100 ~ 400 mL, and hydrothermal temperature is 160 ~ 180
oC, the hydro-thermal time is 12 ~ 24 h.
3. the preparation method of a graphene-supported metal oxide nano-material as claimed in claim 1 is characterized in that described acetylacetone metallic compound is ferric acetyl acetonade, acetylacetone cobalt or nickel acetylacetonate.
4. the preparation method of a graphene-supported metal oxide nano-material as claimed in claim 1, the mass ratio that it is characterized in that graphite oxide and acetylacetone metallic compound is 1:1 ~ 1:5.
5. the graphene-supported metal oxide nano-material that is prepared by the described method of one of claim 1-4.
After the graphene-supported metal oxide nano-material reduction activation as claimed in claim 5 in Fischer-Tropsch synthesis as the application of catalyst.
7. application according to claim 6 is characterized in that being applied to the front reduction activation of Fischer-Tropsch synthesis and carries out in tube furnace, and reducing condition is as follows: H
2/ Ar flow velocity is 20 ~ 60 ml/min, and reduction temperature is 300 ~ 600
oC, the recovery time is 180 ~ 2880 min.
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| CN108155020A (en) * | 2016-12-02 | 2018-06-12 | 中国石油化工股份有限公司 | Graphene composite material and its preparation method and application |
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| CN107754793A (en) * | 2017-11-23 | 2018-03-06 | 中科合成油技术有限公司 | Fischer-tropsch synthetic catalyst of porous carbon load and its preparation method and application |
| WO2019100497A1 (en) * | 2017-11-23 | 2019-05-31 | 中科合成油技术有限公司 | Porous carbon-supported fischer-tropsch synthesis catalyst, preparation method therefor, and use thereof |
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