CN106925324A - A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method - Google Patents

A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method Download PDF

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CN106925324A
CN106925324A CN201511032252.3A CN201511032252A CN106925324A CN 106925324 A CN106925324 A CN 106925324A CN 201511032252 A CN201511032252 A CN 201511032252A CN 106925324 A CN106925324 A CN 106925324A
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nano
range
carbon material
weight
metallic atom
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CN106925324B (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a kind of nano-carbon material containing metallic atom and preparation method and application, the nano-carbon material contains the O elements of 1-15 weight %, the N element of 0.2-2 weight % and the metallic element of 0.2-15 weight %, the amount of the O elements that the content of the O elements determined by the peak of 529.5-530.8eV in XPS is determined for 0.02-0.2 with the ratio of the total amount of the O elements determined by XPS by the peak of 531.0-532.5eV is 0.4-2.5 with the ratio of the amount of the O elements determined by the peak of 532.6-533.5eV, the amount of the N element determined by the peak of 398.5-400.1eV is 0.5-1 with the ratio of the total amount of the N element determined by XPS.Feed stock conversion and selectivity of product higher can be obtained present invention also offers hydrocarbon dehydrogenation reaction method of the nano-carbon material containing metallic atom as catalyst, the method is used.

Description

A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
Technical field
The present invention relates to a kind of nano-carbon material containing metallic atom, the invention further relates to a kind of preparation method containing metallic atom nano-carbon material And by the nano-carbon material containing metallic atom of the method preparation, the present invention further relates to a kind of passing through above-mentioned nano-carbon material containing metallic atom The nano-carbon material containing metallic atom for being calcined and being prepared, the invention further relates to nano-carbon material containing metallic atom of the invention Application and a kind of hydrocarbon dehydrogenation reaction method as the catalyst of hydrocarbon dehydrogenation reaction.
Background technology
The dehydrogenation reaction of hydrocarbons is the important reaction type of a class, such as most of low-carbon (LC) olefine is by the dehydrogenation of low-carbon paraffin React and obtain.Whether dehydrogenation reaction according to oxygen participates in that direct dehydrogenation reaction (that is, oxygen is not involved in) can be divided into and oxidation is de- Hydrogen reaction (that is, oxygen is participated in) two classes.
Polytype nano-carbon material has been demonstrated to be respectively provided with catalytic effect to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation, Oxygen atom and/or nitrogen-atoms are introduced in nano-carbon material can then improve its catalysis activity.
Oxygen atom is introduced in nano-carbon material, hydroxyl, carbonyl, carboxyl, ester group and acid anhydrides etc. can be formed on nano-carbon material surface and contained Oxygen functional group.
Can realize introducing oxygen atom in nano-carbon material by carrying out oxidation processes to nano-carbon material, so that in increasing nano-carbon material The content of oxygen-containing functional group.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or strong oxidizing solution is (such as H2O2、KMnO4) in carry out back flow reaction, can also aid in carrying out heating using microwave or sonic oscillation while back flow reaction, with strengthen The effect of oxidation reaction.But, back flow reaction is carried out in strong acid and/or strong oxidizing solution may be to the skeleton structure of nano-carbon material Have a negative impact, or even destroy the skeleton structure of nano-carbon material.For example：Nano-carbon material is carried out into back flow reaction in nitric acid, though So a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, but easily cause nano-carbon material to be cut off and/or substantially increase graphite Defective bit in network structure, so as to reduce the performance of nano-carbon material, such as heat endurance.In addition, by strong acid and/or strong oxidizing property Back flow reaction is carried out in solution, to introduce during oxygen atom, the introduction volume of oxygen atom is high to the dependence of operation condition, fluctuation range compared with It is wide.
It is generally that nitrogen is former according to the difference of nitrogen-atoms residing chemical environment in nano-carbon material when introducing nitrogen-atoms in nano-carbon material Son is divided into chemical nitrogen and structure nitrogen.Chemical nitrogen is mainly in the form of surface functional group the surface for appearing in material, such as amino or nitrosyl The surface such as base nitrogen-containing functional group.Structure nitrogen refers to the nitrogen-atoms of the skeleton structure into nano-carbon material and carbon atom bonding.Structure nitrogen is main Including graphite mould nitrogen (i.e.,), pyridine type nitrogen (i.e.,) and pyrroles's type nitrogen is (i.e.,).Graphite mould nitrogen is direct Carbon atom in substitution graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen and pyrroles's type nitrogen are unsaturated nitrogen atom, in substitution carbon atom While, can often cause to close on the missing of carbon atom, form defective bit.
Can by introducing nitrogenous feature atmosphere (such as ammonia, nitrogen, urea, melamine) in nano-carbon material building-up process, Nitrogen is incorporated into the skeleton structure and/or table of nano-carbon material simultaneously using high temperature and/or high pressure in the building-up process of nano-carbon material In face；Can also be placed in nitrogenous feature atmosphere (such as ammonia, nitrogen, urea, melamine) by by nano-carbon material, profit Nitrogen is incorporated into the surface of nano-carbon material with high temperature and/or high pressure.High temperature and/or high pressure are although knot can be formed in nano-carbon material Structure nitrogen, but the type of nitrogen containing species depends on reaction condition, is difficult to control；Also, the different types of nitrogen containing species for so producing exist The surface distributed of nano-carbon material is uneven, causes the unstable properties of nitrogenous nano-carbon material.Can also be carried out by by nano-carbon material Oxidation processes, then react with amine, and so as to introduce nitrogen-atoms on nano-carbon material surface, the nitrogen-atoms for so introducing is essentially chemical nitrogen.
Although the research about the doping vario-property and its catalytic performance of nano-carbon material achieves many progress, for some of which base This problem is not built consensus yet, still needs to further investigate doping vario-property nano-carbon material and preparation method thereof and catalytic performance.
The content of the invention
It is an object of the present invention to provide a kind of preparation method containing metallic atom nano-carbon material, can not only be in nanometer using the method Carbon material surface introduces metallic atom, and can stably improve heteroatomic content in nano-carbon material, while to nano-carbon material in itself Structure influence it is little.
It is another object of the present invention to provide a kind of nano-carbon material containing metallic atom, this contains metallic atom nano-carbon material for hydro carbons During the dehydrogenation reaction of material, feed stock conversion and selectivity of product higher can be obtained.
A further object of the present invention is to provide a kind of hydrocarbon dehydrogenation reaction method, and the method can obtain feed stock conversion and product selection higher Property.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metallic atom nano carbon material Material contains C element, O elements, N element and at least one metallic element, on the basis of the total amount containing metallic atom nano-carbon material simultaneously In terms of element, the content of O elements is 1-15 weight %, and the content of N element is 0.2-2 weight %, and the total amount of the metallic element is 0.2-15 Weight %, the content of C element is 68-98.6 weight %,
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron power spectrum is IO t, by X-ray light The content of the O elements that the peak in electron spectrum in the range of 529.5-530.8eV determines is IO m, IO m/IO tIn the range of 0.02-0.2；Should In nano-carbon material containing metallic atom, the amount of the O elements determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum is IO c, the amount of the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum is IO e, IO c/IO e0.4-2.5's In the range of；This contains in metallic atom nano-carbon material, and the N units in the nano-carbon material containing metallic atom are determined by x-ray photoelectron power spectrum The total amount of element is IN t, the amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is IN c, IN c/IN t In the range of 0.5-1.
According to the second aspect of the invention, the invention provides a kind of preparation method containing metallic atom nano-carbon material, the method includes By a kind of aqueous dispersions for being dispersed with raw material nano carbon material, at least one organic base and at least one metallic compound in closed container Reacted, in course of reaction, the temperature of the aqueous dispersions is maintained in the range of 80-300 DEG C.
According to the third aspect of the present invention, the invention provides a kind of by being prepared according to the method for second aspect of the present invention containing metal raw Sub- nano-carbon material.
According to the fourth aspect of the present invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metallic atom nano carbon material Prepared by material is by being calcined according to the nano-carbon material containing metallic atom of present invention one side or the 3rd aspect.
According to the fifth aspect of the present invention, the invention provides nano-carbon material containing metallic atom, the root according to one side of the invention According to the nano-carbon material containing metallic atom of third aspect of the present invention or according to the 4th nano carbon material containing metallic atom of aspect of the invention Expect the application as the catalyst of hydrocarbon dehydrogenation reaction.
According to the sixth aspect of the invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, the method is included in presence or absence of oxygen Under conditions of gas, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon and nano-carbon material containing metallic atom, the basis according to one side of the invention The nano-carbon material containing metallic atom of third aspect of the present invention or according to 4th nano-carbon material containing metallic atom of aspect of the invention Contact.
Preparation method containing metallic atom nano-carbon material of the invention, can not only stably regulate and control and/or improve gold in nano-carbon material Category atom and heteroatomic content, while the structure influence to nano-carbon material in itself is small, the nano-carbon material containing metallic atom of preparation has The performance of stabilization.
Nano-carbon material containing metallic atom of the invention shows good catalytic performance in the dehydrogenation reaction of hydrocarbons, can be substantially Improve feed stock conversion and selectivity of product.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo containing metallic atom nano-carbon material prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of the raw material nano carbon material that embodiment 1 is used.
Specific embodiment
In the present invention, nano-carbon material refers at least one-dimensional carbon material less than 100nm of dispersed phase yardstick.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metallic atom nano carbon material Material contains C element, O elements, N element and at least one metallic element.In the present invention, " at least one " represent one or two with On.
Carbon material containing metal nano of the invention, the metallic element is selected from the metallic element to hydrocarbon dehydrogenation reaction with catalysis activity, Transition metal is preferably selected from, such as selected from Group IIIB metallic element, group ivb metallic element, Group VB gold in the periodic table of elements Category element, vib metals element, VIIB races metallic element, group VIII metallic element, I B-group metal element and ii B Race's metallic element.The instantiation of the metallic element can include but is not limited to scandium, yttrium, thulium (such as lanthanum, cerium, praseodymium), Titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, Jin Hexin.Preferably, institute State metallic element and be selected from group VIII metallic element, when the carbon material containing metal nano now being used as into the catalyst of hydrocarbon dehydrogenation reaction, can obtain The catalysis activity of get Geng Gao.It is highly preferred that the metallic element is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum, this is now contained into metal When nano-carbon material is used as the catalyst of hydrocarbon dehydrogenation reaction, the catalysis activity of further raising can be obtained.
Nano-carbon material containing metallic atom of the invention, on the basis of the total amount containing metallic atom nano-carbon material and in terms of element, The content of O elements is 1-15 weight %, more preferably preferably 2-10 weight %, 4.5-7.5 weight %；The content of N element is 0.2-2 Weight %, preferably 0.4-1.8 weight %, more preferably 0.6-1.7 weight %；The total amount of metallic element is 0.2-15 weight %, preferably 0.5-8 weight %, more preferably 1-7 weight %；The content of C element be 68-98.6 weight %, preferably 80.2-97.1 weight %, it is more excellent Elect 83.8-93.9 weight % as.Wherein, the content of each element is determined using X-ray photoelectron spectroscopy.Sample is before testing at 150 DEG C At a temperature of in helium atmosphere dry 3 hours.
In the present invention, X-ray photoelectron spectroscopic analysis are in Thermo Scientific companies equipped with Thermo Avantage V5.926 Tested on the ESCALab250 type x-ray photoelectron spectroscopies of software, excitaton source is monochromatization Al K α X-rays, energy is 1486.6eV, power is 150W, and penetrating energy used by narrow scan is 30eV, and base vacuum during analysis test is 6.5 × 10-10Mbar, electricity Sub- combination can be corrected with the C1s peaks (284.0eV) of simple substance carbon, and data processing is carried out on Thermo Avantage softwares, in analysis mould Quantitative analysis is carried out using sensitivity factor method in block.
Nano-carbon material containing metallic atom of the invention, this contains in metallic atom nano-carbon material, is determined by x-ray photoelectron power spectrum Oxygen element total content be IO t, determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum O elements (that is, with Metallic atom bonding oxygen atom) content be IO m, IO m/IO tIn the range of 0.02-0.2, preferably in the range of 0.04-0.15, more It is preferred that in the range of 0.06-0.1.Nano-carbon material containing metallic atom of the invention, by x-ray photoelectron power spectrum The content of the O elements that the peak in the range of 531.0-533.5eV determines is IO nm, IO nm/IO tIn the range of 0.8-0.98, preferably in 0.85-0.96 In the range of, more preferably in the range of 0.9-0.94.In the present invention, when number range is represented, " ×-× in the range of " include two Individual binary values.
In the present invention, the area of the O1s spectral peaks in x-ray photoelectron power spectrum is designated as AO 1, O1s spectral peaks are divided into two groups of peaks, will be The area of the spectral peak (corresponding to the oxygen species being connected with metallic atom) in the range of 529.5-530.8eV is designated as AO 2, will be in 531.0-533.5eV In the range of the area of spectral peak (correspond to be not connected with metallic atom oxygen species) be designated as AO 3, wherein, IO m/IO t=AO 2/AO 1, IO nm/IO t =AO 3/AO 1。
Nano-carbon material containing metallic atom of the invention, is determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum O elements (that is, C=O) amount be IO c, the O units determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum The amount of plain (that is, C-O) is IO e, IO c/IO eIn the range of 0.4-2.5, preferably in the range of 0.5-1.5, more preferably in 0.6-1.4 In the range of.In the present invention, by x-ray photoelectron power spectrum in the range of 531.0-533.5eV spectral peak (correspond to not with metallic atom Connected oxygen species) be further separated into two groups of peaks, i.e., spectral peak in the range of 531.0-532.5eV (corresponding to C=O species) and Spectral peak (corresponding to C-O species) in the range of 532.6-533.5eV, A is designated as by the area of the spectral peak in the range of 531.0-532.5eVO 4, The area of the spectral peak in the range of 532.6-533.5eV is designated as AO 5, IO c/IO e=AO 4/AO 5。
Nano-carbon material containing metallic atom of the invention, to be determined by x-ray photoelectron power spectrum in the nano-carbon material containing metallic atom C element total amount on the basis of, C element (that is, the stone determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum Black type carbon) content can be 60-95 weight %, more preferably preferably 70-94 weight %, 80-92 weight %；By X-ray photoelectricity The total content of the C element that peak in the range of 286.0-288.8eV determines can be 5-40 weight %, preferably 6-30 weight % in sub- power spectrum, More preferably 8-20 weight %.In the present invention, by the area A of the C1s spectral peaks in x-ray photoelectron power spectrumC 1Determine the total amount of C element, C1s spectral peaks in x-ray photoelectron power spectrum are divided into two groups of peaks, i.e., the spectral peak in the range of 284.7-284.9eV (corresponds to graphite mould Carbon species) and spectral peak (correspond to non-graphite type carbon species) in the range of 286.0-288.8eV, will be in the range of 284.7-284.9eV The area of spectral peak be designated as AC 2, the area of the spectral peak in the range of 286.0-288.8eV is designated as AC 3, by x-ray photoelectron power spectrum Content=the A of the C element that the peak in the range of 284.7-284.9eV determinesC 2/AC 1, by 286.0-288.8eV models in x-ray photoelectron power spectrum Total content=the A of the C element that the peak in enclosing determinesC 3/AC 1。
Nano-carbon material containing metallic atom of the invention, this contains in metallic atom nano-carbon material, by x-ray photoelectron power spectrum The amount of the C element that the peak in the range of 288.6-288.8eV determines is IC c, in the range of 286.0-286.2eV in x-ray photoelectron power spectrum The amount of the C element that peak determines is IC e, IC c/IC eIn the range of 0.5-5, preferably in the range of 0.6-3.5, more preferably in the model of 0.7-2 In enclosing.In the present invention, the spectral peak (corresponding to agraphitic carbon species) in x-ray photoelectron power spectrum in the range of 286.0-288.8eV is entered One step is divided into two groups of peaks, i.e., spectral peak in the range of 286.0-286.2eV (corresponding to hydroxyl and ether type carbon species) and Spectral peak (corresponding to carboxyl, acid anhydride and ester type carbon species) in the range of 288.6-288.8eV, by the spectral peak in the range of 286.0-286.2eV Area is designated as AC 4, the area of the spectral peak in the range of 288.6-288.8eV is designated as AC 5, IC c/IC e=AC 5/AC 4。
Nano-carbon material containing metallic atom of the invention, in determining the nano-carbon material containing metallic atom by x-ray photoelectron power spectrum The total amount of N element is IN t, the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is (that is, except graphite Type nitrogen and-NO2Nitrogen species outside type nitrogen) amount be IN c, IN c/IN tIn the range of 0.5-1, preferably in the range of 0.6-0.95, more It is preferred that in the range of 0.7-0.92.
Nano-carbon material containing metallic atom of the invention, in determining the nano-carbon material containing metallic atom by x-ray photoelectron power spectrum The total amount of N element is IN t, N element (that is ,-NO determined by the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum2Thing Kind) content be IN n, IN n/IN tIn the range of 0-0.25, preferably in the range of 0.01-0.2, more preferably in the scope of 0.01-0.08 It is interior.
Nano-carbon material containing metallic atom of the invention, is determined by the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum N element (that is, graphite mould nitrogen) content is relatively low does not contain even.Usually, in nano-carbon material containing metallic atom of the invention, The amount of the N element determined by the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum is IN g, IN g/IN tTo be not higher than 0.25, Typically in the range of 0.02-0.2, preferably in the range of 0.02-0.15.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peaks in x-ray photoelectron power spectrumN 1, by X-ray photoelectricity N1s spectral peaks in sub- power spectrum are divided into three groups of peaks, i.e., the spectral peak in the range of 403.5-406.5eV (corresponds to-NO2Species), The spectral peak in the range of spectral peak (corresponding to graphite mould nitrogen species) and 398.5-400.1eV in the range of 400.6-401.5eV (removes graphite mould Nitrogen and-NO2Nitrogen species outside type nitrogen), the area of the spectral peak in the range of 400.6-401.5eV is designated as AN 2, will be in 398.5-400.1eV In the range of the area of spectral peak be designated as AN 3, the area of the spectral peak in the range of 403.5-406.5eV is designated as AN 4, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, IN n/IN t=AN 4/AN 1, when the ratio for obtaining is less than 0.01, it is believed that without such species, and by such species Content be designated as 0.
In the present invention, the combination of the position at each peak as corresponding to the summit at the peak can determine that, the peak that scope determines by mentioned earlier refers to summit Corresponding combination can be in such range peak, a peak can be included within the range, it is also possible to including more than two peaks.For example： Peak in the range of 398.5-400.1eV refers to whole peaks that combination corresponding to summit can be in the range of 398.5-400.1eV.
Nano-carbon material containing metallic atom of the invention can exist with common various forms, be specifically as follows but be not limited to containing metal Atom CNT, Graphene containing metallic atom, thin layer graphite containing metallic atom, nano carbon particle containing metallic atom, received containing metallic atom One or more combination in rice carbon fiber, Nano diamond containing metallic atom and fullerene containing metallic atom.It is described containing metal raw The CNT of son can be SWCN containing metallic atom, double-walled carbon nano-tube containing metallic atom and multi-wall carbon nano-tube containing metallic atom One or more combination in pipe.Nano-carbon material containing metallic atom of the invention, preferably many wall carbon containing metallic atom are received Mitron.
Nano-carbon material containing metallic atom of the invention, it is preferable that the specific surface area containing metallic atom multi-walled carbon nano-tubes is 50-500m2/ g, so can further improve the catalytic performance containing metallic atom nano-carbon material, especially as hydrocarbons dehydrogenation reaction Catalyst catalytic performance.It is highly preferred that this contains the specific surface area of metallic atom multi-walled carbon nano-tubes in 80-300m2In the range of/g. It is further preferred that this contains the specific surface area of metallic atom multi-walled carbon nano-tubes in 100-250m2In the range of/g.It is further preferred that The specific surface area containing metallic atom multi-walled carbon nano-tubes is in 130-180m2In the range of/g.In the present invention, the specific surface area is inhaled by nitrogen Attached BET method is determined.
Nano-carbon material containing metallic atom of the invention, temperature range of the multi-walled carbon nano-tubes containing metallic atom at 400-800 DEG C Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that in the range of 0.01-0.5, More preferable catalytic effect is so obtained in that, during catalyst particularly as hydrocarbons dehydrogenation reaction, more preferable catalytic reaction can be obtained Effect.It is highly preferred that w500/w800In the range of 0.02-0.4.It is further preferred that w500/w800In the range of 0.05-0.15. In the present invention, w800=W800- W400, w500=W500- W400, W400It is the mass loss determined at a temperature of 400 DEG C Rate, W800It is the mass loss rate determined at a temperature of 800 DEG C, W500It is the mass loss rate determined at a temperature of 500 DEG C；It is described Weight-loss ratio is determined using thermogravimetric analyzer in air atmosphere, and test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample is being surveyed Depressed in 150 DEG C of temperature and 1 normal atmosphere before examination and dried 3 hours in helium atmosphere.
It is of the invention it is a kind of preferred embodiment in, the nano-carbon material containing metallic atom is preferably multi-wall carbon nano-tube containing metallic atom Pipe, this contains the specific surface area of metallic atom multi-walled carbon nano-tubes in 50-500m2In the range of/g, preferably in 80-300m2In the range of/g, More preferably in 100-250m2In the range of/g, further preferably in 130-180m2In the range of/g；Also, w500/w800In 0.01-0.5 In the range of, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.15.
Nano-carbon material containing metallic atom of the invention, for other nonmetallic heteroatoms outside oxygen atom and nitrogen-atoms, such as sulphur is former Son and phosphorus atoms, its content can be customary amount.Usually, in nano-carbon material containing metallic atom of the invention, oxygen atom Can be below 0.5 weight %, preferably 0.2 weight with the total amount of other nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) outside nitrogen-atoms Amount below %, more preferably more preferably below 0.1 weight %, below 0.05 weight %.It is of the invention containing metallic atom nanometer Carbon material, in addition to aforesaid metal elements, can also contain other metallic atoms, and described other metallic atoms for example can be from preparation The catalyst used during nano-carbon material.The content of other metallic atoms is generally below 2.5 weight %, preferably below 2 weight %, More preferably below 1 weight %, is still more preferably below 0.5 weight %, particularly preferably below 0.2 weight %.
According to the second aspect of the invention, the invention provides a kind of preparation method containing metallic atom nano-carbon material, the method includes By a kind of aqueous dispersions for being dispersed with raw material nano carbon material, at least one organic base and at least one metallic compound in closed container Reacted.In the present invention, " at least one " represents one or more.
The organic base is selected from amine and quaternary ammonium base.
The quaternary ammonium base is specifically as follows the compound shown in Formulas I：
(Formulas I)
In Formulas I, R1、R2、R3And R4Can be each C1-C20Alkyl (including C1-C20Straight chained alkyl and C3-C20Side chain Alkyl) or C6-C12Aryl.The C1-C20Alkyl instantiation can include but is not limited to：Methyl, ethyl, n-propyl, It is isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl, n-hexyl, just pungent Base, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, positive ten One or more in six alkyl, n-octadecane base and n-eicosane base.The C6-C12Aryl instantiation can include but not It is limited to phenyl, naphthyl, aminomethyl phenyl and ethylphenyl.Preferably, R1、R2、R3And R4Respectively C1-C10Alkyl (including C1-C10 Straight chained alkyl and C3-C10Branched alkyl).It is further preferred that R1、R2、R3And R4Respectively C1-C6Alkyl (including C1-C6 Straight chained alkyl and C3-C6Branched alkyl).
The amine refers to the material that one, two or three hydrogen in amino molecule is replaced and formed by organic group, and the organic group can be with Cyclic structure is formed with nitrogen atom bonding.The organic group can for substitution (such as hydroxyl substitution) or unsubstituted aliphatic alkyl and/or Substitution (such as hydroxyl substitution) or unsubstituted aromatic hydrocarbyl, the aliphatic alkyl can be (such as hydroxyl substitution) or unsubstituted for substitution Representative examples of saturated aliphatic chain alkylene, substitution (such as hydroxyl substitution) or unsubstituted unsaturated aliphatic chain alkylene, substitution (such as hydroxyl substitution) Or unsubstituted saturated alicyclic hydrocarbon base and substitution (such as hydroxyl substitution) or unsubstituted unsaturated lipid cyclic hydrocarbon radical in one or two with On.Specifically, the amine can for substitution (such as hydroxyl substitution) or unsubstituted representative examples of saturated aliphatic amine, substitution (such as hydroxyl substitution) or Unsubstituted unsaturated aliphatic amine, substitution (such as hydroxyl substitution) or unsubstituted saturation aliphatic cyclic amine, substitution (such as hydroxyl substitution) or not Substituted unsaturated lipid cyclammonium, substitution (such as hydroxyl substitution) or unsubstituted heterocyclic amine and replace (such as hydroxyl substitution) or unsubstituted One or more in aromatic amine.
The unsaturated aliphatic amine refers to the aliphatic streptamine containing unsaturated group in molecular structure, and the unsaturated group is preferably alkene Base (that is ,-C=C-).The quantity of the unsaturated group and amino can be each one or more, be not particularly limited.
The method according to the invention, the instantiation of the organic base can include but is not limited to methylamine, dimethylamine, trimethylamine, ethamine, Diethylamine, triethylamine, n-propylamine, di-n-propylamine, Tri-n-Propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, Tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, Neopentyl amine, iso-amylamine, di-iso-amylamine, triisoamylamine, tertiary amylamine, n-hexylamine, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane Base amine, dodecyl amine, dodecyl-dimethyl amine, n-tridecane base amine, n-tetradecane base amine, n-pentadecane base amine, positive ten Six alkylamines, triethanolamine, triisopropanolamine, diethanol amine, two normal propyl alcohol amine, three normal propyl alcohol amine, two n-butanol amine, three n-butanols Amine, dodecyl-dimethyl amine, tetradecyldimethylamine, hexadecyldimethyl benzyl ammonium amine, ethylenediamine, propane diamine, butanediamine, penta 2 Amine, hexamethylene diamine, substituted or unsubstituted pyrroles, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, substitution do not take The hexahydropyridine in generation, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substitution or unsubstituted EEDQ, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinolin, substitution Or unsubstituted pyrimidine, aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, a methyl Aniline, open-chain crown ether, 23 dimethyl aniline, 2,4- dimethylanilines, 2,5- dimethylanilines, 2,6- dimethylanilines, 3,4- diformazans Base aniline, 3,5- dimethylanilines, 2,4,6- trimethylanilines, o ethyl aniline, N- butylanilines, 2,6- diethylanilines, cyclohexylamine, Cyclopentamine, hexamethylenetetramine, diethylenetriamine, triethylene tetramine, TMAH, tetraethyl ammonium hydroxide, tetrapropyl hydrogen Amine-oxides (including its various isomers, such as four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH (including its Various isomers, such as 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide) With one or more in four pentyl ammonium hydroxide (including its various isomers).
The method according to the invention, the amine is preferably the compound shown in Formula II, the compound shown in formula III and general formula R12(NH2)2 One or more in the material of expression,
(Formula II),
(formula III).
In Formula II, R5、R6And R7Respectively H, C1-C6Alkyl or C6-C12Aryl, and R5、R6And R7It is asynchronously H. In the present invention, C1-C6Alkyl instantiation can include but is not limited to：It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, secondary Butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl and n-hexyl.In the present invention, C6-C12Aryl Instantiation includes but is not limited to phenyl, naphthyl, aminomethyl phenyl and ethylphenyl.
In formula III, R8、R9And R10Respectively-R11OH or hydrogen, and R8、R9And R10At least one of be-R11OH, R11 It is C1-C4Alkylidene.In the present invention, C1-C4Alkylidene include C1-C4Straight-chain alkyl-sub and C3-C4Branched alkylidene, its Instantiation can be included but is not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, isobutylidene and sub- uncle Butyl.
General formula R12(NH2)2In, R12Can be C1-C6Alkylidene or C6-C12Arlydene.In the present invention, C1-C6Alkylidene Including C1-C6Straight-chain alkyl-sub and C3-C6Branched alkylidene, its instantiation can include but is not limited to：Methylene, ethylidene, Sub- n-propyl, isopropylidene, sub- normal-butyl, isobutylidene, the sub- tert-butyl group, sub- n-pentyl and sub- n-hexyl.In the present invention, C6-C12 The instantiation of arlydene include but is not limited to phenylene and naphthylene.
The method according to the invention, the metallic element in the metallic compound is selected from the metal unit can to hydrocarbon dehydrogenation reaction with catalysis activity Element, is preferably selected from transition metal.Metallic element in the metallic compound specifically can be selected from Group IIIB gold in the periodic table of elements Category element, group ivb metallic element, Group VB metallic element, vib metals element, VIIB races metallic element, VIII Race's metallic element, I B-group metal element and group iib metallic element.The instantiation of the metallic element in the metallic compound can be with Including but not limited to scandium, yttrium, thulium (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, Cobalt, rhodium, nickel, palladium, platinum, copper, silver, Jin Hexin.Preferably, the metallic element in the metallic compound is selected from group VIII metal Element, the carbon material containing metal nano for thus preparing can obtain catalysis activity higher in the catalyst as hydrocarbon dehydrogenation reaction.It is more excellent Selection of land, the metallic element in the metallic compound is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum, the carbon containing metal nano for thus preparing When material is used as the catalyst of hydrocarbon dehydrogenation reaction, the catalysis activity of further raising can be obtained.
The metallic compound can be selected from metal nitrate, metal acetate, metal carbonate, metal sulfate, basic metal carbonic acid Salt, metal hydroxides, metal chloride and metal complex, more preferably metal acetate, metal carbonate, metal base Formula carbonate, metal hydroxides and metal complex.
The metallic compound can specifically be selected from, but not limited to, nickel nitrate, nickel acetate, nickel sulfate, basic nickel carbonate, nickel chloride, hydrogen-oxygen Change nickel, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, ferrous acetate, ferric sulfate, Basic carbonate iron, iron chloride, iron hydroxide, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, zinc chloride, zinc hydroxide, nitre Sour copper, copper acetate, copper sulphate, basic copper carbonate, copper chloride, Kocide SD, lanthanum nitrate, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, Cerous nitrate, cerous carbonate, cerium chloride, cerium hydroxide, nitric acid ruthenium, ruthenic chloride, hydroxide ruthenium, palladium nitrate, palladium bichloride, palladium dydroxide, Acid chloride, platinum nitrate, platinum chloride, acetylacetone,2,4-pentanedione platinum, rhodium nitrate, rhodium acetate, four ammino bicarbonate palladiums, nitric acid ammonia palladium (such as nitric acid four Ammino palladium), radium chloride and palladium acetylacetonate.
The consumption of the method according to the invention, the organic base and the metallic compound can be according to it is contemplated that draw in raw material nano carbon material The content and species of the nitrogen, oxygen element and the metallic element that enter are selected.In the final nano-carbon material containing metallic atom for preparing In the catalyst as hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material：Organic base：The weight ratio of metallic compound is 1：0.01-15： In the range of 0.01-5, the nano-carbon material containing metallic atom for thus preparing can be carried further in the catalyst as hydrocarbon dehydrogenation reaction Catalytic reaction effect high.It is highly preferred that raw material nano carbon material：Organic base：The weight ratio of metallic compound is 1：0.01-8：0.05-3 In the range of.It is further preferred that raw material nano carbon material：Organic base：The weight ratio of metallic compound is 1：0.5-4：The model of 0.07-2 In enclosing.
The method according to the invention, the method according to the invention, the mol ratio of the organic base and the metallic compound is preferably 1： In the range of 0.001-50, oxygen atom, nitrogen-atoms and metallic atom are in nano carbon material in the nano-carbon material containing metallic atom for thus preparing More uniformly spreading for material surface, also has more excellent catalysis activity in the catalyst as hydrocarbon dehydrogenation reaction.It is highly preferred that institute Organic base is stated with the mol ratio of the metallic compound 1：In the range of 0.005-10.It is further preferred that the organic base and the gold Belong to the mol ratio of compound 1：In the range of 0.01-3.
Method according to the invention it is possible to the amount according to raw material nano carbon material is selected the consumption of water.Preferably, raw material nano carbon Material：H2The weight ratio of O is 1：In the range of 2-500, when the consumption of water is within the scope of being somebody's turn to do, nano-carbon material is in processing procedure In structural form retentivity more preferably, for example：For CNT, will not be cut off substantially in processing procedure.It is highly preferred that Raw material nano carbon material：H2The weight ratio of O is 1：In the range of 50-200.It is further preferred that raw material nano carbon material：H2O's Weight ratio is 1：In the range of 60-100.
The method according to the invention, in a preferred embodiment, the organic base is quaternary ammonium base, the quaternary ammonium preferably shown in Formulas I Alkali, the metallic element of the metallic compound is selected from iron, cobalt, nickel, and the nano-carbon material containing metallic atom for thus preparing is as hydrocarbon dehydrogenation More preferable catalytic reaction effect can be obtained during the catalyst of reaction.Raw material nano carbon material：Organic base：The weight of metallic compound is than preferred 1：0.02-0.8：In the range of 0.05-8, more preferably 1：0.4-0.6：In the range of 0.08-0.15.This preferred embodiment in, Organic base：The mol ratio of metallic compound is preferably 1：In the range of 0.1-15, more preferably 1：In the range of 0.1-0.2.It is preferred at this Implementation method in, raw material nano carbon material：H2The weight ratio of O is preferably 1：In the range of 20-100, more preferably 1：50-80's In the range of.
The method according to the invention, in another preferred embodiment, the organic base is amine, the metal unit of the metallic compound Element is selected from ruthenium, rhodium, palladium and platinum, and the nano-carbon material containing metallic atom for thus preparing can be obtained more in the catalyst as hydrocarbon dehydrogenation reaction Good catalytic reaction effect.Raw material nano carbon material：Organic base：The weight ratio of metallic compound is preferably 1：0.01-4：The model of 0.05-4 In enclosing, more preferably 1：1-4：In the range of 0.07-2.This preferred embodiment in, organic base：The mol ratio of metallic compound It is preferred that 1：In the range of 0.005-50, more preferably 1：In the range of 0.01-0.3.This preferred embodiment in, raw material nano Carbon material：H2The weight ratio of O is preferably 1：In the range of 40-150, more preferably 1：In the range of 80-100.
The method according to the invention, oxygen atom, nitrogen-atoms and the metal raw of the condition of the reaction to be enough to improve in raw material nano carbon material The content of son is defined.Preferably, in course of reaction, the temperature of the aqueous dispersions in the range of 80-300 DEG C, such as 80-260 DEG C of model In enclosing.When the temperature of the aqueous dispersions is within above range, can not only effectively improve oxygen atom in raw material nano carbon material, Nitrogen-atoms and metal atom content, and the generation of the structural form of raw material nano carbon material will not be significantly affected.It is highly preferred that reacting Cheng Zhong, the temperature of the aqueous dispersions is in the range of 110-220 DEG C.
The method according to the invention, duration of the reaction can be selected according to the temperature of reaction, with can be in raw material nano carbon Enough oxygen atoms, nitrogen-atoms and metallic atom is introduced in material to be defined.Usually, the duration of the reaction can be small in 0.5-96 When in the range of, preferably in the range of 2-72 hours, more preferably in the range of 12-48 hours.
Method according to the invention it is possible to the aqueous dispersions are formed using conventional various methods, for example can be by raw material nano carbon materials Material is dispersed in water (preferably deionized water), is subsequently adding the organic base and the metallic compound, is dissipated so as to obtain the moisture Liquid.In order to further improve the dispersion effect of raw material nano carbon material, while shorten the scattered time, can be using the method for sonic oscillation Raw material nano carbon material is dispersed in water.The condition of the sonic oscillation can be conventional selection, and the condition of the sonic oscillation can be Conventional selection, usually, the frequency of the sonic oscillation can be 10-200kHz, preferably 80-150kHz；The sonic oscillation is held The continuous time can be 0.1-6 hours, preferably 1-4 hours.The method according to the invention, the nitrogen-containing compound and the metal compound Thing can be provided according to specific species in the form of solution (the preferably aqueous solution), it is also possible to be provided in the form of pure material, without spy Do not limit.
The method according to the invention, the content of oxygen element and nitrogen is not particularly limited in the raw material nano carbon material, can be conventional Selection.Usually, in the raw material nano carbon material oxygen element content be not higher than 1.5 weight %, preferably not higher than 1.2 weight %, More preferably not above 0.5 weight %, more preferably not higher than 0.3 weight %；The content of nitrogen is not higher than 0.5 weight %, Preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, more preferably not higher than 0.05 weight %, further Preferably not higher than 0.02 weight %.The method according to the invention, remaining in the raw material nano carbon material outside oxygen atom and nitrogen-atoms The total amount (in terms of element) of nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) can be as customary amount.Usually, the raw material nano The total amount (in terms of element) of remaining nonmetallic heteroatoms in carbon material in addition to oxygen element and nitrogen is not higher than 0.5 weight %, preferably Not higher than 0.2 weight %, more preferably not above 0.1 weight %, more preferably not higher than 0.05 weight %.Side of the invention Method, the raw material nano carbon material may contain some metallic elements, such as from preparing raw material nano carbon material according to the difference in source Metallic atom in the catalyst used during material.The content (in terms of element) of metallic atom is generally 2.5 in the raw material nano carbon material Below weight %, preferably below 1.8 weight %, more preferably below 0.5 weight %, are still more preferably below 0.1 weight %.
The method according to the invention, raw material nano carbon material (is such as washed using preceding can pretreatment using method commonly used in the art Wash), to remove some impurity of raw material nano carbon material surface；Can not also be pre-processed, directly be used.Implementation disclosed by the invention In example, raw material nano carbon material is pre-processed using preceding.
Method according to the invention it is possible to the nano-carbon material of various existing forms is processed, so that in improving the nano-carbon material Oxygen atom, nitrogen-atoms and metal element content.The raw material nano carbon material can be but be not limited to CNT, Graphene, nm of gold One or more combination in hard rock, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene.The CNT can Think one or more the combination in SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes.Preferably, the raw material Nano-carbon material is CNT, more preferably multi-walled carbon nano-tubes.
The method according to the invention, in a preferred embodiment, the raw material nano carbon material is multi-walled carbon nano-tubes, described many The specific surface area of wall carbon nano tube can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, further preferably It is 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nano-tubes, mistake of the multi-walled carbon nano-tubes in 400-800 DEG C of temperature range Rate is w again800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800Can be in the range of 0.01-0.5, preferably In the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably in the range of 0.05-0.15.
In a kind of implementation method being more highly preferred to of the invention, the raw material nano carbon material is multi-walled carbon nano-tubes, and many wall carbon are received The specific surface area of mitron is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, more preferably 120-190m2/g；Weight-loss ratio of the multi-walled carbon nano-tubes in 400-800 DEG C of temperature range is w800, 400-500 DEG C of humidity province Interior weight-loss ratio is w500, w500/w800In the range of 0.01-0.5, preferably in the range of 0.02-0.4, more preferably in 0.05-0.35 In the range of, further preferably in the range of 0.05-0.15.
The method according to the invention, the reaction is carried out in closed container.The reaction (that is, can additionally not apply in self-generated pressure Pressure) under carry out, it is also possible to carry out under pressure.Preferably, the reaction is carried out at autogenous pressures.The closed container Can be the common reactor that can realize sealing and heating, such as autoclave.
The method according to the invention, can also include isolating solid matter, and the solids that will be isolated in the mixture obtained from reaction Matter is dried, so as to obtain the nano-carbon material containing metallic atom.
Solid matter is isolated in the mixture that can be obtained from reaction using conventional solid-liquid separating method, such as in centrifugation, filtering and decantation One or more combination.
The dry condition can be conventional selection, be defined by that can remove the volatile materials in the solid matter isolated.Usually, The drying can be carried out at a temperature of 50-200 DEG C, be carried out preferably at a temperature of 80-180 DEG C, more preferably in 120-150 DEG C of temperature Carried out under degree.The dry duration can be selected according to dry temperature.Usually, the dry duration can be with It is 0.5-48 hours, preferably 6-24 hours, more preferably 10-12 hours.The drying can be at normal pressure (that is, 1 standard atmospheric pressure) Under carry out, it is also possible to carry out at reduced pressure.From the angle for further improving dry efficiency, the drying is preferably in decompression Under conditions of carry out.
The method according to the invention, can effectively improve oxygen atom in raw material nano carbon material, nitrogen-atoms and metal atom content, while The structural form of raw material nano carbon material will not be produced and significantly affected.
According to the third aspect of the present invention, the invention provides a kind of method preparation as according to second aspect of the invention containing gold Category atom nano-carbon material.
According to the fourth aspect of the present invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metallic atom nano carbon material Material is will to be received containing metallic atom according to the nano-carbon material containing metallic atom of one side of the invention or according to third aspect of the present invention Prepared by rice carbon material is calcined.
The roasting can be carried out under normal conditions.Preferably, the roasting is carried out at a temperature of 250-500 DEG C.It is highly preferred that The roasting is carried out at a temperature of 300-450 DEG C, is carried out such as at a temperature of 350-450 DEG C.The duration of the roasting can basis The temperature of roasting is selected.Usually, the duration of the roasting can be 1-24 hours, preferably 2-12 hours, more preferably 2-4 hours.The roasting can be carried out in oxygen-containing atmosphere, it is also possible to be carried out in the atmosphere formed by inert gas.The oxygen-containing atmosphere It can be air atmosphere；Can also be mixed atmosphere that oxygen and inert gas are mixed to form, in the mixed atmosphere, the content of oxygen can Think 0.1-22 volumes %.The inert gas can include but is not limited to nitrogen and/or rare gas, and the rare gas can be argon gas And/or helium.Angularly consider from convenience and cost, it is preferable that the roasting is carried out in oxygen-containing atmosphere (such as air atmosphere).
Nano-carbon material containing metallic atom of the invention is had by nano-carbon material containing metallic atom prepared by the method for the present invention Good catalytic performance, particularly shows catalysis activity higher in hydrocarbons dehydrogenation reaction.
Nano-carbon material containing metallic atom of the invention can be with by nano-carbon material containing metallic atom prepared by the method for the present invention It is directly used as catalyst, it is also possible to used in the form of preformed catalyst.The preformed catalyst can contain of the invention containing metal Atom nano-carbon material or the nano-carbon material containing metallic atom and binding agent that are prepared by the method for the present invention.The binding agent can be with root Selected according to the specifically used occasion of the preformed catalyst, disclosure satisfy that use requirement is defined, for example can for organic binder bond and/or Inorganic binder.The organic binder bond can be common various polymer-type binding agents, and the inorganic binder can be common each Plant heat-resistant inorganic oxide, such as aluminum oxide and/or silica.The preformed catalyst be to hydrocarbon dehydrogenation reaction (such as direct dehydrogenation reaction and Oxidative dehydrogenation), particularly when there is the preformed catalyst of catalytic action to oxidative dehydrogenation, the binding agent is preferably inorganic bond Agent.In the preformed catalyst, the content containing metallic atom nano-carbon material can be selected according to specifically used requirement, without special Limit, usually, on the basis of the total amount of the preformed catalyst, the content containing metallic atom nano-carbon material can be 5-95 weights Amount %.
According to the fifth aspect of the present invention, the invention provides nano-carbon material containing metallic atom, the root according to one side of the invention According to the nano-carbon material containing metallic atom of third aspect of the present invention or according to the 4th nano carbon material containing metallic atom of aspect of the invention Expect the application as the catalyst of hydrocarbon dehydrogenation reaction.
Application according to the present invention, the nano-carbon material containing metallic atom is used directly for hydrocarbon dehydrogenation reaction, it is also possible to be used for after shaping Hydrocarbon dehydrogenation reaction.The dehydrogenation reaction can be carried out in the presence of oxygen, it is also possible to not carried out in the presence of oxygen.Preferably, it is described de- Hydrogen reaction is carried out in the presence of oxygen, can so obtain more preferable catalytic effect.
According to the sixth aspect of the invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, the method is included in presence or absence of oxygen Under conditions of gas, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon and nano-carbon material containing metallic atom, the basis according to one side of the invention The nano-carbon material containing metallic atom of third aspect of the present invention or according to 4th nano-carbon material containing metallic atom of aspect of the invention Contact.
Hydrocarbon dehydrogenation reaction method of the invention, the nano-carbon material containing metallic atom is used directly for being contacted with hydrocarbon, it is also possible to will For being contacted with hydrocarbon after the shaping of nano-carbon material containing metallic atom.
Hydrocarbon dehydrogenation reaction method of the invention can carry out dehydrogenation to polytype hydrocarbon, so as to obtain unsaturated hydrocarbons, such as alkene.Root According to process of this invention is particularly practical for carrying out dehydrogenation to alkane, so as to obtain unsaturated hydrocarbons, such as alkene.
The method according to the invention, the hydrocarbon is preferably alkane, such as C2-C12Alkane.Specifically, the hydrocarbon can be but be not limited to second Alkane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethyls penta Alkane, 2,3- dimethyl pentanes, 2,4- dimethyl pentanes, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethyl Hexane, 2,4- dimethylhexanes, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- Trimethylpentane, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4- dimethyl heptanes, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- trimethyl cyclohexanes, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyl cyclohexanes, 2,4,4- trimethyl cyclohexanes, 2- Methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- methyl -4- ethyl hexanes, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- ethyl cyclohexanes, n-propyl hexamethylene, isopropyl cyclohexane, Trimethyl-cyclohexane (including the various isomers of trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- trimethyl-cyclohexanes, 1,2,5- Trimethyl-cyclohexane, 1,3,5- trimethyl-cyclohexanes), n-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyls octane, 4- ethyls octane, 2,3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethylheptanes, 2,4,5- trimethylheptanes, 2,4,6- trimethylheptanes, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- Trimethylheptane, 2,2,6- trimethylheptanes, 2,3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 2- methyl -4- Ethyl heptane, 2- methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyl heptanes, 4- first Base -4- ethyl heptanes, 4- propyl group heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- diethylpentanes, vinylbenzene, In 1- phenyl-propanes, 2- phenyl-propanes, 1- phenyl butanes, 2- phenyl butanes, 1- phenyl pentanes, 2- phenyl pentanes and 3- phenyl pentanes one Plant or two or more combinations.It is highly preferred that the hydrocarbon be propane, normal butane, iso-butane and vinylbenzene in one or more. It is further preferred that the hydrocarbon is normal butane.
Hydrocarbon dehydrogenation reaction method of the invention, the reaction can be carried out under conditions of it there is oxygen, it is also possible in the absence of oxygen Under conditions of.Preferably, hydrocarbon dehydrogenation reaction method of the invention, is carried out under conditions of it there is oxygen.The method of the present invention is being deposited When being carried out under conditions of oxygen, the consumption of oxygen can be conventional selection.Usually, hydrocarbon and the mol ratio of oxygen can be 0.01-100： 1, preferably 0.1-10：1, more preferably 0.2-5：1, most preferably 0.5-2：1.
Hydrocarbon dehydrogenation reaction method of the invention, receives in hydrocarbon and optional oxygen being sent into reactor by carrier gas with containing metallic atom Rice carbon material haptoreaction.The carrier gas can will not occur chemistry mutually with reactant and reaction product at reaction conditions for conventional The gas that act on and will not decompose, such as one or more the combination in nitrogen, carbon dioxide, rare gas and vapor. The consumption of the carrier gas can be conventional selection.Usually, the content of carrier gas can be 30-99.5 volume %, preferably 50-99 volumes %, More preferably 70-98 volumes %.
Hydrocarbon dehydrogenation reaction method of the invention, the temperature of the contact can be conventional selection, to be enough to make hydrocarbon that dehydrogenation reaction to occur be It is accurate.Usually, the contact can be carried out at a temperature of 200-650 DEG C, be carried out preferably at a temperature of 300-600 DEG C, more preferably be existed Carried out at a temperature of 350-550 DEG C, carried out further preferably at a temperature of 400-450 DEG C.
Hydrocarbon dehydrogenation reaction method of the invention, the contact can be carried out in fixed bed reactors, it is also possible in fluidized-bed reactor In carry out, be not particularly limited.Preferably, the contact is carried out in fixed bed reactors.
Hydrocarbon dehydrogenation reaction method of the invention, the duration of the contact can be selected according to the temperature of contact, be connect as described Touch when being carried out in fixed bed reactors, the duration of contact can be represented with the volume space velocity of the gas of charging.Usually, feed The volume space velocity of gas can be 0.1-10000h-1, preferably 1-6000h-1, more preferably 5-5000h-1, more preferably 10-4000h-1, such as 500-800h-1。
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, X-ray photoelectron spectroscopic analysis are in Thermo Scientific companies equipped with Thermo Tested on the ESCALab250 type x-ray photoelectron spectroscopies of Avantage V5.926 softwares, excitaton source is monochromatization Al K α X Ray, energy is 1486.6eV, and power is 150W, and penetrating energy used by narrow scan is 30eV, and base vacuum during analysis test is 6.5×10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, in the Thermo enterprising line numbers of Avantage softwares According to treatment, quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is big in 150 DEG C of temperature and 1 standard before testing Dried 3 hours in helium atmosphere under air pressure.
In following examples and comparative example, thermogravimetric analysis is carried out on TA5000 thermal analyzers, and test condition is air atmosphere, and heat up speed It is 10 DEG C/min to spend, and temperature range is room temperature (25 DEG C) to 1000 DEG C.Sample temperature and 1 standard atmospheric pressure before testing at 150 DEG C Under in helium atmosphere dry 3 hours.Using the ASAP2000 types N of Micromertrics companies of the U.S.2Physical adsorption appearance is determined and compares table Area.The high-resolution-ration transmission electric-lens produced using FEI Co. of the U.S. analyze raw material nano carbon material and containing metallic atom nano-carbon material Microscopic appearance.
In following examples and comparative example, organic base is provided in the form of the aqueous solution of 20 weight %, and metallic compound is with the shape of solid matter Formula is provided.
Embodiment 1-30 is used to illustrate nano-carbon material containing metallic atom of the invention and preparation method thereof.
Embodiment 1
(1) using 20g, used as the multi-walled carbon nano-tubes of raw material nano carbon material, (specific surface area is 136m2/ g, oxygen atom content is 0.3 weight Amount %, nitrogen atom content is 0.02 weight %, remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) in addition to nitrogen-atoms and oxygen atom Total content is 0.01 weight %, and metallic atom total content is 0.1 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w800, Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) In deionized water, being dispersed under the conditions of sonic oscillation is carried out, and sonic oscillation condition includes for dispersion：Frequency is 140kHz, and the time is 1 small When.Then, the tetraethyl ammonium hydroxide as organic base and the ferrous acetate as metallic compound are added, so as to obtain aqueous dispersions, Wherein, by raw material nano carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：0.5：0.1：60 ratio feeds intake.
(2) aqueous dispersions that will be obtained are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 120 DEG C, in spontaneous pressure Reacted 36 hours under power.After reaction terminates, after the temperature in autoclave is down to room temperature, reactor is opened, reactant mixture is entered Row filtering and washing, and collect solid matter.The solid matter that will be collected into is in normal pressure (1 standard atmospheric pressure, similarly hereinafter), 120 DEG C of temperature Degree is lower dry 12 hours after, obtain nano-carbon material containing metallic atom, composition that this contains metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Fig. 1 is the transmission electron microscope photo containing metallic atom nano-carbon material for preparing, and Fig. 2 is as the multi-walled carbon nano-tubes of raw material Transmission electron microscope photo.The microscopic pattern containing metallic atom nano-carbon material is can be seen that from Fig. 1 and Fig. 2 well, show anti- Answer process little to the structure influence of nano-carbon material.
Comparative example 1
Aqueous dispersions same as Example 1 are placed in and are equipped with the there-necked flask of condenser pipe, the there-necked flask is placed in temperature for 120 DEG C Oil bath in, in back flow reaction under normal pressure 36 hours.After the temperature in there-necked flask is down to room temperature, by reactant mixture carry out filtering and Washing, and collect solid matter.After the solid matter that will be collected into is dried 12 hours at a temperature of normal pressure, 120 DEG C, obtain containing metal Atom nano-carbon material.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1, table The breadth coefficient of the breadth coefficient of face oxygen atom, the breadth coefficient of surface nitrogen atom and surface metal atoms is listed in table 2.
Comparative example 2
Nano-carbon material is prepared using method same as Example 1, unlike, the aqueous dispersions that step (1) is prepared are free of metal Compound, it is, by the dispersion of raw material nano carbon material in deionized water, be subsequently adding as the tetraethyl ammonium hydroxide of organic base, So as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：0.5：0： 60 ratio feeds intake.The composition of the nano-carbon material of preparation, specific surface area and w500/w800Listed in table 1.
Comparative example 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, the moisture that step (1) is prepared dissipates Liquid is free of organic base, it is, by the dispersion of raw material nano carbon material in deionized water, being subsequently adding sub- as the acetic acid of metallic compound Iron, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：0： 0.1：60 ratio feeds intake.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Comparative example 4
In deionized water, will be dispersed under the conditions of sonic oscillation to enter using the nano-carbon material dispersion prepared with the identical method of comparative example 2 OK, sonic oscillation condition includes：Frequency is 140kHz, and the time is 1 hour.Then, add as the ferrous acetate of metallic compound, So as to obtain aqueous dispersions, wherein, (used using when preparing nano-carbon material with the identical method of comparative example 2 by raw material nano carbon material Raw material nano carbon material)：Metallic compound：H2The weight ratio of O is 1：0.1：60 ratio feeds intake.The aqueous dispersions that will be obtained exist In autoclave with polytetrafluoroethyllining lining, at a temperature of 120 DEG C, react 36 hours at autogenous pressures.After reaction terminates, After the temperature in autoclave is down to room temperature, reactor is opened, reactant mixture is filtered and washed, and collects solid matter. After the solid matter that will be collected into is dried 12 hours at a temperature of normal pressure, 120 DEG C, nano-carbon material containing metallic atom is obtained, this contains gold Belong to composition, specific surface area and the w of atom nano-carbon material500/w800Listed in table 1.
Comparative example 5
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), organic base is used The NaOH of equimolar amounts replaces.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Comparative example 6
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, the moisture that step (1) is prepared dissipates Liquid is free of organic base, it is, by the dispersion of raw material nano carbon material in deionized water, being subsequently adding sub- as the acetic acid of metallic compound Iron, so as to obtain aqueous dispersions, wherein, mole and organic base in embodiment 1 and the integral molar quantity phase of metallic compound of ferrous acetate Together, the consumption of raw material nano carbon material and deionized water is same as Example 1.The composition containing metallic atom nano-carbon material, the ratio for preparing Surface area and w500/w800Listed in table 1.
Embodiment 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), as raw material The specific surface area of the multi-walled carbon nano-tubes (being purchased from Shandong great Zhan nano materials Co., Ltd) of nano-carbon material is 251m2/ g, in 400-800 DEG C temperature range in weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.33, oxygen Atom content is 0.62 weight %, and nitrogen atom content is 0.01 weight %, remaining the nonmetallic heteroatoms (phosphorus in addition to nitrogen-atoms and oxygen atom Atom and sulphur atom) total content be 0.01 weight %, metallic atom total content be 0.08 weight %.The nano-sized carbon containing metallic atom for preparing The composition of material, specific surface area and w500/w800Listed in table 1.
Embodiment 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (2), by what is obtained Aqueous dispersions at a temperature of 90 DEG C, react 36 hours at autogenous pressures in the autoclave with polytetrafluoroethyllining lining. The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), received by raw material Rice carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：0.02：0.1：60 ratio feeds intake.Prepare containing metal raw The composition of sub- nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 5
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), received by raw material Rice carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：0.5：8：60 ratio feeds intake.Prepare containing metallic atom The composition of nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 6
Using 20g, used as the multi-walled carbon nano-tubes of raw material nano carbon material, (specific surface area is 183m2/ g, oxygen atom content is 0.2 weight %, Nitrogen atom content is 0.01 weight %, the total content of remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) in addition to nitrogen-atoms and oxygen atom It is 0.04 weight %, metallic atom total content is 0.03 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w800, in 400-500 DEG C temperature range in weight-loss ratio be w500, w500/w800It is 0.07, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) dispersion In deionized water, being dispersed under the conditions of sonic oscillation is carried out, and sonic oscillation condition includes：Frequency is 90kHz, and the time is 4 hours. Then, the aniline as organic base and the acid chloride as metallic compound are added, so as to obtain aqueous dispersions, wherein, by raw material nano Carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：4：0.1：80 ratio feeds intake.
(2) aqueous dispersions that will be obtained are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 220 DEG C, in spontaneous pressure Reacted 12 hours under power.After reaction terminates, after the temperature in autoclave is down to room temperature, reactor is opened, reactant mixture is entered Row filtering and washing, and collect solid matter.After the solid matter that will be collected into is dried 10 hours at a temperature of normal pressure, 150 DEG C, obtain To nano-carbon material containing metallic atom, composition, specific surface area and w that this contains metallic atom nano-carbon material500/w800Listed in table 1.
Comparative example 7
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, the moisture that step (1) is prepared dissipates Liquid is free of organic base, it is, by the dispersion of raw material nano carbon material in deionized water, be subsequently adding as the acid chloride of metallic compound, So as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：0：0.1： 80 ratio feeds intake.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Comparative example 8
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, the moisture that step (1) is prepared dissipates Liquid is free of organic base, it is, by the dispersion of raw material nano carbon material in deionized water, be subsequently adding as the acid chloride of metallic compound, So as to obtain aqueous dispersions, wherein, the mole of acid chloride is identical with the integral molar quantity of organic base and metallic compound in embodiment 6, former The consumption of material nano-carbon material and deionized water is same as Example 6.The composition containing metallic atom nano-carbon material, the specific surface area for preparing And w500/w800Listed in table 1.
Embodiment 7
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), as raw material The specific surface area of the multi-walled carbon nano-tubes (being purchased from Shandong great Zhan nano materials Co., Ltd) of nano-carbon material is 103m2/ g, w500/w800 It is 0.23, oxygen atom content is 1.1 weight %, nitrogen atom content is 0.03 weight %, is denitrogenated and remaining the nonmetallic heteroatoms (phosphorus outside oxygen And sulphur) total content be 0.01 weight %, metallic atom total content be 1.6 weight %.The composition containing metallic atom nano-carbon material of preparation, Specific surface area and w500/w800Listed in table 1.
Embodiment 8
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (2), by what is obtained Aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 260 DEG C, are reacted 12 hours at autogenous pressures. The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 9
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), organic base with Under conditions of the gross weight of metallic compound keeps constant, make organic base：The mol ratio of metallic compound is 1：10.Prepare containing metal The composition of atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 10
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), acid chloride is used The palladium acetylacetonate of equimolar amounts replaces.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 1 In list.
Embodiment 11
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), acid chloride is used The ferrous acetate of equimolar amounts replaces.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 1 List.
Embodiment 12
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), acid chloride is used The acetylacetone,2,4-pentanedione platinum of equimolar amounts replaces.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 1 In list.
Embodiment 13
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), aniline is used etc. The TMAH of mole replaces.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table Listed in 1.
Embodiment 14
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), aniline uses oneself Diamines replaces, and the mole of hexamethylene diamine is 0.5 times of the mole of aniline in embodiment 6.Prepare containing metallic atom nano-carbon material Composition, specific surface area and w500/w800Listed in table 1.
Embodiment 15
Nano-carbon material containing metallic atom is prepared using method same as Example 1, difference is as follows：In step (1), by original The dispersion of material nano-carbon material in deionized water, is subsequently adding the triethanolamine as organic base and the rhodium acetate as metallic compound, from And aqueous dispersions are obtained, wherein, by raw material nano carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：1：0.5：100 Ratio feed intake；In step (2), the aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, in 150 DEG C At a temperature of, react 36 hours at autogenous pressures.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800 Listed in table 2.
Comparative example 9
It is equipped with being placed in the identical aqueous dispersions of embodiment 15 in the there-necked flask of condenser pipe, it is 150 that the there-necked flask is placed in into temperature DEG C oil bath in, in back flow reaction under normal pressure 36 hours.It is after the temperature in there-necked flask is down to room temperature, reaction is mixed after reaction terminates Compound is filtered and washed, and collects solid matter.The solid matter that will be collected into is dried 12 hours at a temperature of normal pressure, 120 DEG C Afterwards, nano-carbon material containing metallic atom is obtained.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800 Listed in table 2.
Comparative example 10
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, the moisture that step (1) is prepared dissipates Liquid is free of organic base, it is, by the dispersion of raw material nano carbon material in deionized water, be subsequently adding as the rhodium acetate of metallic compound, So as to obtain aqueous dispersions, wherein, the mole of rhodium acetate is identical with the integral molar quantity of organic base and metallic compound in embodiment 15, former The consumption of material nano-carbon material and deionized water is identical with embodiment 15.The composition containing metallic atom nano-carbon material, the specific surface area for preparing And w500/w800Listed in table 2.
Comparative example 11
Nano-carbon material is prepared using with the identical method of embodiment 15, unlike, the aqueous dispersions that step (1) is prepared are free of metal Compound, it is, by the dispersion of raw material nano carbon material in deionized water, be subsequently adding as the triethanolamine of organic base, so that To aqueous dispersions, wherein, by raw material nano carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：1：0：100 ratio Example feeds intake.The composition of the nano-carbon material of preparation, specific surface area and w500/w800Listed in table 2.
Embodiment 16
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, in step (2), by what is obtained Aqueous dispersions at a temperature of 90 DEG C, react 36 hours at autogenous pressures in the autoclave with polytetrafluoroethyllining lining. The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 2.
Embodiment 17
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, as raw material nano carbon material Multi-walled carbon nano-tubes is with embodiment 2.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 2 List.
Embodiment 18
Using with the identical method of embodiment 15 prepare nano-carbon material containing metallic atom, unlike, in step (1), organic base with Under conditions of the integral molar quantity of metallic compound keeps constant, make organic base：The mol ratio of metallic compound is 10：1.Prepare containing gold Belong to composition, specific surface area and the w of atom nano-carbon material500/w800Listed in table 2.
Embodiment 19
Nano-carbon material containing metallic atom is prepared using method same as Example 6, difference is as follows：In step (1), by original The dispersion of material nano-carbon material in deionized water, is subsequently adding the n-butylamine as organic base and the four ammino bicarbonates as metallic compound Palladium, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：2： 2：90 ratio feeds intake；In step (2), the aqueous dispersions that will be obtained in the autoclave with polytetrafluoroethyllining lining, in 110 At a temperature of DEG C, react 48 hours at autogenous pressures.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 2.
Embodiment 20
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (1), as raw material The multi-walled carbon nano-tubes of nano-carbon material is same as Example 7.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 2.
Embodiment 21
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (1), received by raw material Rice carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：0.01：2：90 ratio feeds intake.Prepare containing metallic atom The composition of nano-carbon material, specific surface area and w500/w800Listed in table 2.
Embodiment 22
Nano-carbon material containing metallic atom is prepared with the identical method of embodiment 19, unlike, in step (1), by raw material nano Carbon material：Organic base：Metallic compound：H2The weight ratio of O is 1：2：0.01：90 ratio feeds intake.What is prepared receives containing metallic atom The rice composition of carbon material, specific surface area and w500/w800Listed in table 2.
Embodiment 23
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (2), by what is obtained Aqueous dispersions at a temperature of 80 DEG C, react 48 hours at autogenous pressures in the autoclave with polytetrafluoroethyllining lining. The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 2.
Embodiment 24
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (1), n-butylamine is used The TBAH of equimolar amounts replaces.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800 Listed in table 2.
Embodiment 25
Nano-carbon material containing metallic atom prepared by embodiment 1 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 12
Nano-carbon material containing metallic atom prepared by comparative example 1 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 13
Nano-carbon material containing metallic atom prepared by comparative example 2 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 14
Nano-carbon material containing metallic atom prepared by comparative example 3 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 15
Nano-carbon material containing metallic atom prepared by comparative example 4 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 16
Nano-carbon material containing metallic atom prepared by comparative example 5 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 17
Nano-carbon material containing metallic atom prepared by comparative example 6 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 26
Nano-carbon material containing metallic atom prepared by embodiment 2 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 27
Nano-carbon material containing metallic atom prepared by embodiment 3 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 28
Nano-carbon material containing metallic atom prepared by embodiment 4 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 29
Nano-carbon material containing metallic atom prepared by embodiment 5 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 30
Nano-carbon material containing metallic atom prepared by embodiment 19 is calcined 2 hours in air atmosphere at a temperature of 450 DEG C.
Embodiment 31-60 is used to illustrate the application containing metallic atom nano-carbon material of the invention and hydrocarbon dehydrogenation reaction method.
Embodiment 31-54
Nano-carbon material containing metallic atom prepared by 0.2g (admission space is 1.9mL) embodiment 1-24 is existed as Catalyst packing respectively In universal fixed bed miniature quartz pipe reactor, the end seal of miniature quartz pipe reactor two has quartz sand, under the conditions of 0.1MPa and 450 DEG C, By the gas containing hydrocarbon and oxygen, (concentration of normal butane is 1.98 volume %, normal butane and oxygen molar ratio 0.5：1, it is balance of as load The nitrogen of gas) with cumulative volume air speed as 700h-1It is passed through in reactor and is reacted, the reactant mixture that continuous monitoring is exported from reactor Composition, and calculate n-butane conversion, total olefin selectivity and butadiene selective, the result of reaction 3 hours and 24 hours is listed in table In 3.
Comparative example 18-28
Reacted using with embodiment 31-54 identical methods, unlike, respectively using comparative example 1-11 prepare containing metallic atom Nano-carbon material is used as catalyst.Reaction result is listed in table 3.
Comparative example 29
Reacted using with embodiment 31-54 identical methods, unlike, use raw material nano carbon material same as Example 1 As catalyst.Reaction result is listed in table 3.
Comparative example 30
Reacted using with embodiment 31-54 identical methods, unlike, use raw material nano carbon material same as Example 6 As catalyst.Reaction result is listed in table 3.
Embodiment 55-60
Reacted using with embodiment 31-54 identical methods, unlike, the carbon containing metallic atom prepared using embodiment 25-30 Nanotube is used as catalyst.Reaction result is listed in table 4.
Comparative example 31-36
Reacted using with embodiment 31-54 identical methods, unlike, the carbon containing metallic atom prepared using comparative example 12-17 Nanotube is used as catalyst.Reaction result is listed in table 4.
Comparative example 37
Reacted using with embodiment 31-54 identical methods, unlike, catalyst is by raw material nano same as Example 1 Obtained from carbon material is calcined 4 hours in 350 DEG C of air atmospheres.Reaction result is listed in table 4.
Comparative example 38
Reacted using with embodiment 31-54 identical methods, unlike, catalyst is by raw material nano same as Example 6 Obtained from carbon material is calcined 12 hours in 300 DEG C of air atmospheres.Reaction result is listed in table 4.
Table 3
Table 4
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to the detail in above-mentioned implementation method, In range of the technology design of the invention, various simple variants can be carried out to technical scheme, these simple variants belong to this The protection domain of invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in the case of reconcilable, Can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is no longer another to various possible combinations Row explanation.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to thought of the invention, It should equally be considered as content disclosed in this invention.

Claims (32)

1. a kind of nano-carbon material containing metallic atom, this contains metallic atom nano-carbon material and contains C element, O elements, N element and extremely A kind of few metallic element, on the basis of the total amount containing metallic atom nano-carbon material and in terms of element, the content of O elements is 1-15 weight %, the content of N element is 0.2-2 weight %, and the total amount of the metallic element is 0.2-15 weight %, and the content of C element is 68-98.6 Weight %,
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron power spectrum is IO t, by X-ray light The content of the O elements that the peak in electron spectrum in the range of 529.5-530.8eV determines is IO m, IO m/IO tIn the range of 0.02-0.2；
This contains in metallic atom nano-carbon material, the O elements determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum Amount be IO c, the amount of the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum is IO e, IO c/IO eIn 0.4-2.5 In the range of；
This contains in metallic atom nano-carbon material, and the N element in the nano-carbon material containing metallic atom is determined by x-ray photoelectron power spectrum Total amount be IN t, the amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is IN c, IN c/IN t In the range of 0.5-1.
2. nano-carbon material containing metallic atom according to claim 1, wherein, IO m/IO tIn the range of 0.04-0.15, preferably In the range of 0.06-0.1；IO c/IO eIn the range of 1-2；IN c/IN tIn the range of 0.6-0.95, preferably in the range of 0.7-0.92.
3. nano-carbon material containing metallic atom according to claim 1 and 2, wherein, this contains in metallic atom nano-carbon material, The amount of the C element determined by the peak in the range of 288.6-288.8eV in x-ray photoelectron power spectrum is IC c, by x-ray photoelectron power spectrum The amount of the C element that the peak in the range of 286.0-286.2eV determines is IC e, IC c/IC eIn the range of 0.5-5, preferably in the scope of 0.6-3.5 It is interior, more preferably in the range of 0.7-2.
4. the nano-carbon material containing metallic atom according to any one in claim 1-3, wherein, with the nano-sized carbon containing metallic atom On the basis of the total amount of the C element determined by x-ray photoelectron power spectrum in material, by 284.7-284.9eV models in x-ray photoelectron power spectrum The content of the C element that the peak in enclosing determines is 60-95 weight %, preferably 70-94 weight %, more preferably 80-92 weight %, by X The content of the C element that the peak in X-ray photoelectron spectroscopy X in the range of 286.0-288.8eV determines is 5-40 weight %, preferably 6-30 weight %, more preferably 8-20 weight %.
5. the nano-carbon material containing metallic atom according to any one in claim 1-4, wherein, by x-ray photoelectron power spectrum The total amount for determining the N element in the nano-carbon material containing metallic atom is IN t, by 400.6-401.5eV scopes in x-ray photoelectron power spectrum The amount of the N element that interior peak determines is IN g, IN g/IN tTo be not higher than 0.25, preferably in the range of 0.02-0.2, more preferably in 0.02-0.15 In the range of；
Determine that the total amount of the N element in the nano-carbon material containing metallic atom is I by x-ray photoelectron power spectrumN t, by x-ray photoelectron The content of the N element that the peak in power spectrum in the range of 403.5-406.5eV determines is IN n, IN n/IN tIn the range of 0-0.25, preferably exist In the range of 0.01-0.2, more preferably in the range of 0.01-0.08.
6. the nano-carbon material containing metallic atom according to any one in claim 1-5, wherein, with the nano-sized carbon containing metallic atom On the basis of the total amount of material and in terms of element, the content of O elements is 2-10 weight %, preferably 4.5-7.5 weight %, the content of C element It is 80.2-97.1 weight %, preferably 83.8-93.9 weight %, the content of N element is 0.4-1.8 weight %, preferably 0.6-1.7 weight %, The total amount of the metallic element is 0.5-8 weight %, preferably 1-7 weight %.
7. the nano-carbon material containing metallic atom according to any one in claim 1-6, wherein, the metallic element is selected from transition Metallic element, is preferably selected from group VIII metallic element, is more preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
8. the nano-carbon material containing metallic atom according to any one in claim 1-7, wherein, this contains metallic atom nano carbon material Material is CNT containing metallic atom；Preferably, it is multi-walled carbon nano-tubes containing metallic atom that this contains metallic atom nano-carbon material.
9. nano-carbon material containing metallic atom according to claim 8, wherein, the ratio containing metallic atom multi-walled carbon nano-tubes Surface area is in 50-500m2In the range of/g, preferably in 80-300m2In the range of/g, more preferably in 100-250m2In the range of/g, enter One step is preferably in 130-180m2In the range of/g.
10. nano-carbon material containing metallic atom according to claim 8 or claim 9, wherein, the multi-walled carbon nano-tubes containing metallic atom Weight-loss ratio in 400-800 DEG C of temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800 In the range of 0.01-0.5, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.15, the weight-loss ratio is in air Determined in atmosphere.
A kind of 11. preparation methods containing metallic atom nano-carbon material, the method includes for one kind being dispersed with raw material nano carbon material, at least The aqueous dispersions of a kind of organic base and at least one metallic compound are reacted in closed container, and in course of reaction, the moisture dissipates The temperature of liquid is maintained in the range of 80-300 DEG C.
12. methods according to claim 11, wherein, raw material nano carbon material：Organic base：The weight ratio of metallic compound is 1： 0.01-15：In the range of 0.01-5, preferably 1：0.01-8：In the range of 0.05-3, more preferably 1：0.5-4：The scope of 0.07-2 It is interior；
Raw material nano carbon material：H2The weight ratio of O is 1：In the range of 2-500, preferably 1：In the range of 50-200, more preferably exist 1：In the range of 60-100.
13. method according to claim 11 or 12, wherein, organic base：The mol ratio of metallic compound is 1：0.001-50 In the range of, preferably 1：In the range of 0.005-10, more preferably 1：In the range of 0.01-3.
14. method according to any one in claim 11-13, wherein, the metallic element in the metallic compound was selected from Metallic element is crossed, group VIII metallic element is preferably selected from, iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum is more preferably selected from；
The metallic compound is preferably selected from metal acetate, metal carbonate, basic metal carbonates, metal hydroxides and metal Complex compound.
15. method according to any one in claim 11-14, wherein, the organic base is selected from amine and quaternary ammonium base；
The organic base is preferably selected from compound and formula shown in the compound shown in Formulas I, the compound shown in Formula II, formula III R12(NH2)2The material of expression, R12It is C1-C6Alkylidene or C6-C12Arlydene,
In Formulas I, R1、R2、R3And R4Respectively C1-C20Alkyl or C6-C12Aryl；
In Formula II, R5、R6And R7Respectively H, C1-C6Alkyl or C6-C12Aryl, and R5、R6And R7It is asynchronously H；
In formula III, R8、R9And R10Respectively-R11OH, hydrogen or C1-C6Alkyl, and R8、R9And R10At least one of For-R11OH, R11It is C1-C4Alkylidene.
16. method according to any one in claim 11-15, wherein, the organic base is quaternary ammonium base, the metal The metallic element of compound is selected from iron, cobalt, nickel, raw material nano carbon material：Organic base：The weight ratio of metallic compound is 1：0.02-0.8： In the range of 0.05-8, preferably 1：0.4-0.6：In the range of 0.08-0.15, organic base：The mol ratio of metallic compound is 1：0.1-15 In the range of, preferably 1：In the range of 0.1-0.2, raw material nano carbon material：H2The weight ratio of O is 1：It is excellent in the range of 20-100 It is selected in 1：In the range of 50-80；Or
The organic base is amine, and the metallic element of the metallic compound is selected from ruthenium, rhodium, palladium and platinum, raw material nano carbon material：Organic base： The weight ratio of metallic compound is 1：0.01-4：In the range of 0.05-4, preferably 1：1-4：In the range of 0.07-2, organic base：Gold Belong to the mol ratio of compound 1：In the range of 0.005-50, preferably 1：In the range of 0.01-0.3, raw material nano carbon material：H2O Weight ratio 1：In the range of 40-150, preferably 1：In the range of 80-100.
17. method according to any one in claim 11-16, wherein, in course of reaction, the temperature of the aqueous dispersions is protected Hold in the range of 80-260 DEG C, preferably remain in the range of 110-220 DEG C.
18. method according to any one in claim 11-17, wherein, the duration of the reaction was at 0.5-96 hours In the range of, preferably in the range of 2-72 hours, more preferably in the range of 12-48 hours.
19. method according to any one in claim 11-18, wherein, in the raw material nano carbon material, N element contains It is not higher than 0.5 weight % to measure, and preferably not higher than 0.2 weight %, more preferably not above 0.1 weight % be not more preferably high It is not higher than 1.5 weight % still more preferably to be not higher than the content of 0.02 weight %, O element in 0.05 weight %, it is preferably not high In 1.2 weight %, more preferably not above 0.5 weight %, more preferably not higher than 0.3 weight %, the total amount of metallic element is 2.5 Below weight %, preferably below 1.8 weight %, more preferably below 0.5 weight %, are still more preferably below 0.1 weight %.
20. method according to any one in claim 11-19, wherein, the raw material nano carbon material is CNT；It is excellent Selection of land, the raw material nano carbon material is multi-walled carbon nano-tubes.
21. methods according to claim 20, wherein, the specific surface area of the multi-walled carbon nano-tubes is 50-500m2/ g, preferably It is 80-300m2/ g, more preferably 100-260m2/ g, more preferably 120-190m2/g。
22. method according to claim 20 or 21, wherein, the multi-walled carbon nano-tubes is in 400-800 DEG C of temperature range Weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, preferably In the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably in the range of 0.05-0.15, the weight-loss ratio Determined in air atmosphere.
23. method according to any one in claim 11-22, wherein, the method is also included in the mixture obtained from reaction Solid matter is isolated, and the solid matter that will be isolated is dried.
24. methods according to claim 23, wherein, the drying is carried out at a temperature of 50-200 DEG C, preferably in 80-180 Carried out at a temperature of DEG C, carried out more preferably at a temperature of 120-150 DEG C, the dry duration is 0.5-48 hours, preferably 6-24 hours, more preferably 10-12 hours.
Nano-carbon material containing metallic atom prepared by the method in a kind of 25. 11-24 as claim described in any one.
A kind of 26. nano-carbon materials containing metallic atom, it is by described in any one in claim 1-10 that this contains metallic atom nano-carbon material Nano-carbon material containing metallic atom or claim 25 described in nano-carbon material containing metallic atom prepared by be calcined.
27. nano-carbon materials containing metallic atom according to claim 26, wherein, the roasting is entered at a temperature of 250-500 DEG C OK, carried out preferably at a temperature of 300-450 DEG C, duration of the roasting is 1-24 hours, preferably 2-12 hours, more preferably It is 2-4 hours.
Appoint in nano-carbon material containing metallic atom or claim 26-27 in 28. claim 1-10 and 25 described in any one Meaning one described in nano-carbon material containing metallic atom as the catalyst of hydrocarbon dehydrogenation reaction application.
29. applications according to claim 28, wherein, the dehydrogenation reaction is carried out in the presence of oxygen.
30. application according to claim 28 or 29, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably It is normal butane.
A kind of 31. hydrocarbon dehydrogenation reaction methods, the method is included in presence or absence of under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, Hydrocarbon is any one with the nano-carbon material containing metallic atom or claim 26-27 described in any one in claim 1-10 and 25 The contact of nano-carbon material containing metallic atom described in.
32. methods according to claim 31, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably just Butane.
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US20110123409A1 (en) * 2007-11-30 2011-05-26 Cuong Phamhuu Chemical reactor with nanometric superstructure
CN101718011A (en) * 2009-11-16 2010-06-02 天津工业大学 Method for preparing carbon nanofibers
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CN105148837A (en) * 2015-07-29 2015-12-16 桂林电子科技大学 Composite material by using carbon nano-tube as core and ferriferrous oxide as shell and preparation method thereof

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