CN106925319A - 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 PDFInfo
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- CN106925319A CN106925319A CN201511031571.2A CN201511031571A CN106925319A CN 106925319 A CN106925319 A CN 106925319A CN 201511031571 A CN201511031571 A CN 201511031571A CN 106925319 A CN106925319 A CN 106925319A
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- carbon material
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- metallic atom
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 380
- 238000000034 method Methods 0.000 title claims abstract description 142
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 62
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 62
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 56
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000001228 spectrum Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 30
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- -1 nitrogen-containing compound Chemical class 0.000 claims description 47
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- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 39
- 239000001301 oxygen Substances 0.000 claims description 39
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- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
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- 125000005842 heteroatom Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical class CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 6
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- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 6
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- 239000001307 helium Substances 0.000 description 5
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
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- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
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- 229910052746 lanthanum Inorganic materials 0.000 description 3
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- LTHAIAJHDPJXLG-UHFFFAOYSA-N pentan-2-ylbenzene Chemical class CCCC(C)C1=CC=CC=C1 LTHAIAJHDPJXLG-UHFFFAOYSA-N 0.000 description 1
- GJYLBGHKIMDUIH-UHFFFAOYSA-N pentane-2,4-dione;rhodium Chemical compound [Rh].CC(=O)CC(C)=O GJYLBGHKIMDUIH-UHFFFAOYSA-N 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- BGXXXYLRPIRDHJ-UHFFFAOYSA-N tetraethylmethane Chemical class CCC(CC)(CC)CC BGXXXYLRPIRDHJ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- JXPOLSKBTUYKJB-UHFFFAOYSA-N xi-2,3-Dimethylhexane Chemical class CCCC(C)C(C)C JXPOLSKBTUYKJB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- 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
-
- B01J35/613—
-
- B01J35/615—
-
- 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
Abstract
The invention discloses a kind of nano-carbon material containing metallic atom and its preparation method and application, the nano-carbon material containing metallic atom contains the O elements of 2-15 weight %, the N element of 0.8-10 weight %, the metallic element of 1-10 weight % and the C element of 65-96.2 weight %, in x-ray photoelectron power spectrum, the content of the O elements that the peak in the range of 529.5-530.8eV determines is 0.02-0.2 weight %, the amount of the O elements determined by the peak in the range of 531.0-532.5eV is 0.2-1 with the ratio of the amount of the O elements determined by the peak in the range of 532.6-533.5eV, the amount of the N element determined by the peak in the range of 398.5-400.1eV is 0.7-1 with the ratio of the total amount of N element.Present invention also offers a kind of hydrocarbon dehydrogenation reaction method for using the nano-carbon material containing metallic atom as catalyst.The nano-carbon material containing metallic atom shows good catalytic performance in the dehydrogenation reaction of hydrocarbons, can significantly improve feed stock conversion and selectivity of product.
Description
Technical field
The present invention relates to a kind of nano-carbon material containing metallic atom, the invention further relates to a kind of nano carbon material containing metallic atom
The preparation method of material and the nano-carbon material containing metallic atom prepared by the method, the present invention further relate to a kind of by will be above-mentioned
The nano-carbon material containing metallic atom that nano-carbon material containing metallic atom is calcined and is prepared, the invention further relates to basis
Application and a kind of hydrocarbon dehydrogenation reaction side of the nano-carbon material containing metallic atom of the invention as the catalyst of hydrocarbon dehydrogenation reaction
Method.
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 low-carbon (LC)
The dehydrogenation reaction of alkane and obtain.Whether dehydrogenation reaction participates in that direct dehydrogenation reaction (that is, oxygen can be divided into according to oxygen
Gas is not involved in) and oxidative dehydrogenation (that is, oxygen is participated in) two classes.
Polytype nano-carbon material has been demonstrated equal to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation
With catalytic effect, introducing oxygen atom and/or nitrogen-atoms can then improve its catalysis activity in nano-carbon material.
Oxygen atom is introduced in nano-carbon material, hydroxyl, carbonyl, carboxyl, ester group can be formed on nano-carbon material surface
With the oxygen-containing functional group such as acid anhydrides.
Can realize introducing oxygen atom in nano-carbon material by carrying out oxidation processes to nano-carbon material, so as to increase
The content of oxygen-containing functional group in nano-carbon material.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or it is strong
Oxidizing solution (such as H2O2、KMnO4) in carry out back flow reaction, can also aid in carrying out heating using microwave while back flow reaction
Or sonic oscillation, to strengthen the effect of oxidation reaction.But, carrying out back flow reaction in strong acid and/or strong oxidizing solution can
Can have a negative impact to the skeleton structure of nano-carbon material, or even destroy the skeleton structure of nano-carbon material.For example：To receive
Rice carbon material carries out back flow reaction in nitric acid, although can introduce a large amount of oxygen-containing functional groups on nano-carbon material surface, but
Easily cause nano-carbon material to be cut off and/or substantially increase the defective bit in graphite network structure, so as to reduce nano carbon material
The performance of material, such as heat endurance.In addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, it is former to introduce oxygen
The period of the day from 11 p.m. to 1 a.m, the introduction volume of oxygen atom is high to the dependence of operation condition, and fluctuation range is wider.
When introducing nitrogen-atoms in nano-carbon material, according to nitrogen-atoms, residing chemical environment is not in nano-carbon material
Together, nitrogen-atoms is generally divided into chemical nitrogen and structure nitrogen.Chemical nitrogen is mainly material is appeared in the form of surface functional group
Surface, such as amino or nitrosyl radical surface nitrogen-containing functional group.Structure nitrogen refer into nano-carbon material skeleton structure with
The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly includes graphite mould nitrogen (i.e.,), pyridine type nitrogen (i.e.,) and pyrrole
Cough up type nitrogen (i.e.,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen and
Pyrroles's type nitrogen is unsaturated nitrogen atom, while carbon atom is replaced, can often cause to close on the missing of carbon atom, forms defect
Position.
Can by introduce in nano-carbon material building-up process nitrogenous feature atmosphere (such as ammonia, nitrogen, urea,
Melamine), nitrogen is incorporated into nano carbon material simultaneously in the building-up process of nano-carbon material using high temperature and/or high pressure
In the skeleton structure of material and/or surface；Nitrogenous feature atmosphere (such as ammonia, nitrogen can also be placed in by by nano-carbon material
Gas, urea, melamine) in, nitrogen is incorporated into the surface of nano-carbon material using high temperature and/or high pressure.High temperature and/or
Although high pressure can form structure nitrogen in nano-carbon material, the type of nitrogen containing species depends on reaction condition, not easily-controllable
System；Also, the different types of nitrogen containing species for so producing are uneven in the surface distributed of nano-carbon material, cause nitrogenous nanometer
The unstable properties of carbon material.Oxidation processes can also be carried out by by nano-carbon material, then be reacted with amine, so as in nanometer
Carbon material surface introduces nitrogen-atoms, and 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 basic problem is not built consensus yet, is still needed to doping vario-property nano-carbon material and preparation method thereof and catalysis
Performance is furtherd investigate.
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, using the method
Metallic atom can not only be introduced on nano-carbon material surface, and can stably improve heteroatomic content in nano-carbon material,
Structure influence simultaneously to nano-carbon material in itself 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-sized carbon
When material is used for the dehydrogenation reaction of hydrocarbons, 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 raw material conversion higher
Rate and selectivity of product.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material contains C element, O elements, N element and at least one metallic element, with the nano carbon material containing metallic atom
On the basis of the total amount of material and in terms of element, the content of O elements is 2-15 weight %, and the content of N element is 0.8-10 weight %, institute
The total amount of metallic element is stated for 1-10 weight %, the content of C element is 65-96.2 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
The content of the O elements that the peak in x-ray photoelectron power spectrum in the range of 529.5-530.8eV determines is IO m, IO m/IO tIn 0.02-
In the range of 0.2；This contains in metallic atom nano-carbon material, in the range of 531.0-532.5eV in x-ray photoelectron power spectrum
The amount of the O elements that peak determines is IO c, the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum
It is I to measureO e, IO c/IO eIn the range of 0.2-1；This contains in metallic atom nano-carbon material, and this is determined by x-ray photoelectron power spectrum
The total amount of the N element in nano-carbon material containing metallic atom is IN t, by 398.5-400.1eV scopes in x-ray photoelectron power spectrum
The amount of the N element that interior peak determines is IN c, IN c/IN tIn the range of 0.7-1.
According to the second aspect of the invention, the invention provides a kind of preparation side containing metallic atom nano-carbon material
Method, the method includes for one kind being dispersed with raw material nano carbon material, at least one nitrogen-containing compound and at least one metallization
The aqueous dispersions of compound are reacted in closed container, and the nitrogen-containing compound is selected from NH3, hydrazine and urea, in course of reaction,
The temperature of the aqueous dispersions is maintained in the range of 60-300 DEG C.
According to the third aspect of the present invention, the invention provides a kind of by according to second method system of aspect of the invention
Standby nano-carbon material containing metallic atom.
According to the fourth aspect of the present invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material is will to be carried out according to present invention one side or the 3rd nano-carbon material containing metallic atom of aspect
Prepared by roasting.
According to the fifth aspect of the present invention, the invention provides being received containing metallic atom according to one side of the invention
Rice carbon material, according to third aspect of the present invention nano-carbon material containing metallic atom or according to 4th aspect of the invention
Nano-carbon material containing metallic atom as the catalyst of hydrocarbon dehydrogenation reaction application.
According to the sixth aspect of the invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, the method is included in deposits
Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with according to one side of the invention containing metal
Atom nano-carbon material, according to third aspect of the present invention nano-carbon material containing metallic atom or according to the present invention the 4th
The contact of nano-carbon material containing metallic atom of individual aspect.
Preparation method containing metallic atom nano-carbon material of the invention, can not only stably regulate and control and/or improve
Metallic atom and heteroatomic content in nano-carbon material, while the structure influence to nano-carbon material in itself is small.Also, according to
Preparation method containing metallic atom nano-carbon material of the invention, the nano-carbon material containing metallic atom of preparation has the property of stabilization
Energy.
Nano-carbon material containing metallic atom of the invention shows good urging in the dehydrogenation reaction of hydrocarbons
Change performance, feed stock conversion and selectivity of product can be significantly improved.
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 metal
Atom nano-carbon material contains C element, O elements, N element and at least one metallic element.In the present invention, " at least one " table
Show one or more.
Carbon material containing metal nano of the invention, the metallic element is selected from has catalytic action to hydrocarbon dehydrogenation reaction
Metallic element, transition metal is preferably selected from, such as selected from Group IIIB metallic element, group ivb gold in the periodic table of elements
Category element, Group VB metallic element, vib metals element, VIIB races metallic element, group VIII metallic element, IB
Race's metallic element and group iib metallic element.The instantiation of the metallic element can include but is not limited to scandium, yttrium, rare earth
Metallic element (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, Jin He
Zinc.Preferably, the metallic element is selected from group VIII metallic element, and the carbon material containing metal nano now is used as into hydrocarbon dehydrogenation
During the catalyst of reaction, catalysis activity higher can be obtained.It is highly preferred that the metallic element is selected from group VIII metal unit
Element, is more preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum, and the carbon material containing metal nano now is used as into urging for hydrocarbon dehydrogenation reaction
During agent, 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 2-15 weight %, more preferably preferably 3-9 weight %, 4-8 weight %；N element
Content is 0.8-10 weight %, more preferably preferably 1-6 weight %, 1.1-5 weight %；The total amount of metallic element is 1-10 weights
Amount %, more preferably preferably 1.2-6 weight %, 1.5-4.5 weight %；The content of C element is 65-96.2 weight %, preferably
It is 79-94.8 weight %, more preferably 82.5-93.4 weight %.Wherein, the content of each element uses x-ray photoelectron power spectrum
Method is determined.Sample is dried 3 hours at a temperature of 150 DEG C in helium atmosphere before testing.
In the present invention, 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-rays, energy is 1486.6eV, and power is 150W, and penetrating energy used by narrow scan is 30eV, base vacuum during analysis test
It is 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage softwares
On carry out data processing, quantitative analysis is carried out using sensitivity factor method in analysis module.
Nano-carbon material containing metallic atom of the invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity
The total content of the oxygen element that sub- power spectrum determines is IO t, determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum
O elements (that is, the oxygen atom being bonded with metallic atom) content be IO m, IO m/IO tIn the range of 0.02-0.2, preferably exist
In the range of 0.05-0.18, more preferably in the range of 0.08-0.15.Nano-carbon material containing metallic atom of the invention,
The content of the O elements determined by the peak in the range of 531.0-533.5eV in x-ray photoelectron power spectrum is IO nm, IO nm/IO tIn 0.8-
In the range of 0.98, preferably in the range of 0.82-0.95, more preferably in the range of 0.85-0.92.In the present invention, in table
When showing number range, " ×-× in the range of " include two 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
Peak, A is designated as by the area of the spectral peak (corresponding to the oxygen species being connected with metallic atom) in the range of 529.5-530.8eVO 2, will
The area of the spectral peak (corresponding to the oxygen species not being connected with metallic atom) in the range of 531.0-533.5eV is 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, by 531.0-532.5eV scopes in x-ray photoelectron power spectrum
The amount of the O elements (that is, C=O) that interior peak determines is IO c, by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum
The amount of the O elements (that is, CO) of determination is IO e, IO c/IO eIn the range of 0.2-1, preferably in the range of 0.45-0.99.This hair
In bright, the spectral peak in x-ray photoelectron power spectrum in the range of 531.0-533.5eV (is corresponded to what is be not connected with metallic atom
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, by the area of the spectral peak in the range of 531.0-532.5eV
It is designated as AO 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, with the nano-carbon material containing metallic atom by X-ray light
It is true by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum on the basis of the total amount of the C element that electron spectrum determines
The content of fixed C element (that is, graphite mould carbon) can be 50-95 weight %, preferably 60-95 weight %, more preferably 70-93
Weight %；The total content of the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum can be 5-
50 weight %, preferably 5-40 weight %, more preferably 7-30 weight %.In the present invention, by x-ray photoelectron power spectrum
The area A of C1s spectral peaksC 1Determine the total amount of C element, the C1s spectral peaks in x-ray photoelectron power spectrum are divided into two groups of peaks, that is, exist
Spectral peak (corresponding to graphite mould carbon species) in the range of 284.7-284.9eV and the spectral peak in the range of 286.0-288.8eV
(corresponding to non-graphite type carbon species), the area of the spectral peak in the range of 284.7-284.9eV is designated as AC 2, will be in 286.0-
The area of the spectral peak in the range of 288.8eV is designated as AC 3, it is true by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum
Content=the A of fixed C elementC 2/AC 1, the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum
Total content=AC 3/AC 1。
Nano-carbon material containing metallic atom of the invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity
The amount of the C element that the peak in sub- power spectrum in the range of 288.6-288.8eV determines is IC c, by 286.0- in x-ray photoelectron power spectrum
The amount of the C element that the peak in the range of 286.2eV determines is IC e, IC c/IC eIn the range of 0.3-2, preferably in the model of 0.4-1.5
In enclosing, more preferably in the range of 0.5-1.25.In the present invention, by x-ray photoelectron power spectrum in 286.0-288.8eV scopes
Interior spectral peak (corresponding to agraphitic carbon species) is further divided into two groups of peaks, i.e., the spectral peak in the range of 286.0-286.2eV
(corresponding to hydroxyl and ether type carbon species) and the spectral peak in the range of 288.6-288.8eV (correspond to carboxyl, acid anhydride and ester type carbon
Species), the area of the spectral peak in the range of 286.0-286.2eV is designated as AC 4, by the spectral peak in the range of 288.6-288.8eV
Area be designated as AC 5, IC c/IC e=AC 5/AC 4。
Nano-carbon material containing metallic atom of the invention, determines that this contains metallic atom and receives by x-ray photoelectron power spectrum
The total amount of the N element in rice carbon material is IN t, the N determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum
The amount of element is IN c, IN c/IN tIn the range of 0.7-1, preferably in the range of 0.8-0.95, more preferably 0.87-0.95's
In the range of.
Nano-carbon material containing metallic atom of the invention, by 400.6-401.5eV scopes in x-ray photoelectron power spectrum
Content is relatively low does not contain even for the N element (that is, graphite mould nitrogen) that interior peak determines.Usually, it is of the invention containing metallic atom
In nano-carbon material, 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 0.3, typically in the range of 0.05-0.2, preferably in the range of 0.05-0.13.
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
N1s spectral peaks in photoelectron spectroscopy are divided into two groups of peaks, i.e., the spectral peak in the range of 400.6-401.5eV (corresponds to graphite mould nitrogen
Species) and 398.5-400.1eV in the range of spectral peak (nitrogen species in addition to graphite mould nitrogen), will be in 400.6-401.5eV models
The area of the spectral peak in enclosing is designated as AN 2, the area of the spectral peak in the range of 398.5-400.1eV is designated as AN 3, IN c/IN t=AN 3/
AN 1, IN g/IN t=AN 2/AN 1, when the ratio for obtaining is less than 0.01, it is believed that without such species, and containing such species
Amount is 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 scope determines by mentioned earlier
Peak refer to peak that combination corresponding to summit can be in such range, a peak can be included within the range, it is also possible to wrap
Include more than two peaks.For example：Peak in the range of 398.5-400.1eV refers to that the combination corresponding to summit can be in 398.5-
Whole peaks in the range of 400.1eV.
Nano-carbon material containing metallic atom of the invention can exist with common various forms, be specifically as follows but
It is not limited to CNT containing metallic atom, Graphene containing metallic atom, thin layer graphite containing metallic atom, nano-sized carbon containing metallic atom
One kind in particle, carbon nano-fiber containing metallic atom, Nano diamond containing metallic atom and fullerene containing metallic atom or two
Plant the combination of the above.The CNT containing metallic atom can be SWCN containing metallic atom, containing metallic atom
One or more combination in double-walled carbon nano-tube and multi-walled carbon nano-tubes containing metallic atom.It is of the invention containing gold
Category atom nano-carbon material, preferably multi-walled carbon nano-tubes containing metallic atom.
Nano-carbon material containing metallic atom of the invention, it is preferable that described containing metallic atom multi-walled carbon nano-tubes
Specific surface area is in 50-500m2In the range of/g, the catalytic containing metallic atom nano-carbon material so can be further improved
Can, especially as the catalytic performance of the catalyst of hydrocarbons dehydrogenation reaction.It is highly preferred that this contains many wall carbon of metallic atom receiving
The specific surface area of mitron is in 80-300m2In the range of/g.It is further preferred that this contains the ratio of metallic atom multi-walled carbon nano-tubes
Surface area is in 95-260m2In the range of/g.It is further preferred that this contains the specific surface area of metallic atom multi-walled carbon nano-tubes
In 125-180m2In the range of/g.In the present invention, the specific surface area is determined by nitrogen adsorption BET method.
Nano-carbon material containing metallic atom of the invention, the multi-walled carbon nano-tubes containing metallic atom is 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 preferred that
In the range of 0.01-0.5, more preferable catalytic effect, particularly urging as hydrocarbons dehydrogenation reaction are so obtained in that
During agent, more preferable catalytic reaction effect can be obtained.It is highly preferred that w500/w800In the range of 0.04-0.18.In the present invention,
w800=W800- W400, w500=W500- W400, W400It is the mass loss rate determined at a temperature of 400 DEG C, W800It is at 800 DEG C
At a temperature of determine mass loss rate, W500It is the mass loss rate determined at a temperature of 500 DEG C；The weight-loss ratio is used
Thermogravimetric analyzer is determined in air atmosphere, and test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample is before testing
Depressed in 150 DEG C of temperature and 1 normal atmosphere 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 containing metal raw
Sub- multi-walled carbon nano-tubes, this contains the specific surface area of metallic atom multi-walled carbon nano-tubes in 50-500m2In the range of/g, preferably exist
80-300m2In the range of/g, more preferably in 95-260m2In the range of/g, further preferably in 125-180m2In the range of/g；
Also, w500/w800In the range of 0.01-0.5, preferably in the range of 0.04-0.18.
Nano-carbon material containing metallic atom of the invention, it is nonmetallic miscellaneous for other outside oxygen atom and nitrogen-atoms
Atom, such as sulphur atom and phosphorus atoms, its content can be customary amount.Usually, it is of the invention containing metallic atom nanometer
In carbon material, the total amount of other nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) outside oxygen atom and nitrogen-atoms can be
Below 0.5 weight %, preferably below 0.2 weight %, more preferably below 0.1 weight %, more preferably 0.05 weight
Amount below %.Nano-carbon material containing metallic atom of the invention, in addition to aforesaid metal elements, can also contain other metals
Atom, described other metallic atoms for example can be from the catalyst used when preparing nano-carbon material.Described other gold
The content for belonging to atom is generally below 2.5 weight %, preferably below 2 weight %, more preferably below 1 weight %, more
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 side containing metallic atom nano-carbon material
Method, the method includes for one kind being dispersed with raw material nano carbon material, at least one nitrogen-containing compound and at least one metallization
The aqueous dispersions of compound are reacted in closed container.
The nitrogen-containing compound is selected from NH3, hydrazine and urea.
The method according to the invention, the metallic element in the metallic compound is selected from there is catalysis to make hydrocarbon dehydrogenation reaction
Metallic element, (that is, described metallic compound is preferably selected from the chemical combination containing transition metal to be preferably selected from transition metal
Thing).Metallic element in the metallic compound can specifically be selected from, but not limited to, Group IIIB metal unit in the periodic table of elements
Element, group ivb metallic element, Group VB metallic element, vib metals element, VIIB races metallic element, group VIII gold
Category element, I B-group metal element and group iib metallic element.The instantiation of the metallic element in the metallic compound can
With 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, 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 higher and live in the catalyst as hydrocarbon dehydrogenation reaction
Property.It is highly preferred that the metallic element in the metallic compound is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum, what is thus prepared contains
When metal nano carbon 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, gold
Category subcarbonate, metal hydroxides, metal chloride, metal oxalate and metal complex, more preferably gold
Category acetate, metal oxalate, basic metal carbonates and metal complex (such as nitric acid ammonia palladium, acetylacetone,2,4-pentanedione ruthenium and acetyl
Acetone rhodium).
The metallic compound can specifically be selected from, but not limited to, nickel nitrate, nickel acetate, nickel sulfate, basic nickel carbonate, chlorine
Change nickel, nickel hydroxide, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, acetic acid sub-
Iron, ferric sulfate, basic carbonate iron, iron chloride, iron hydroxide, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, zinc chloride,
Zinc hydroxide, copper nitrate, copper acetate, copper sulphate, basic copper carbonate, copper chloride, Kocide SD, lanthanum nitrate, lanthanum carbonate, chlorination
Lanthanum, lanthanum hydroxide, cerous nitrate, cerous carbonate, cerium chloride, cerium hydroxide, nitric acid ruthenium, ruthenic chloride, hydroxide ruthenium, palladium nitrate, chlorination
Palladium, palladium dydroxide, platinum nitrate, platinum chloride, rhodium nitrate, nitric acid ammonia palladium (such as ammino palladium of nitric acid four), radium chloride, palladium acetylacetonate,
Ferric oxalate, nickel oxalate, acid chloride, ruthenium acetate, rhodium acetate, acetylacetone,2,4-pentanedione ruthenium and acetylacetone,2,4-pentanedione rhodium.
The method according to the invention, can also be carried out excellent according to the species of nitrogen-containing compound to the species of metallic compound
Change, further to improve catalysis activity of the nano-carbon material containing metallic atom for thus preparing when as hydrocarbon dehydrogenation reaction.
It is a kind of preferred embodiment in, the nitrogen-containing compound be NH3, the metallic element in the metallic compound is selected from iron, cobalt
And nickel, the metallic compound is preferably one or two in metal acetate, basic metal hydrochloride and metal oxalate
More than, more preferably metal acetate and/or metal oxalate.In another preferred embodiment, the nitrogenous chemical combination
Thing is hydrazine, and the metallic element in the metallic compound is selected from palladium and platinum, and the metallic compound is preferably metal acetate, gold
Draft a document one or more in hydrochlorate and metal complex, more preferably metal acetate and/or metal complex.Again
It is a kind of preferred embodiment in, the nitrogen-containing compound is urea, metallic element in the metallic compound be selected from ruthenium and
Rhodium, the metallic compound is preferably metal complex.
The consumption of the method according to the invention, the nitrogen-containing compound and the metallic compound can be according to it is contemplated that former
The content and species of the nitrogen, oxygen element and metallic element that are introduced in material nano-carbon material are selected.Finally making
Standby nano-carbon material containing metallic atom is in the catalyst as hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material：It is nitrogenous
Compound：The weight ratio of metallic compound is 1：0.01-10：In the range of 0.01-10, thus prepare containing metallic atom nanometer
Carbon material can obtain the catalytic effect of further raising in the catalyst as hydrocarbon dehydrogenation reaction.It is highly preferred that raw material nano
Carbon material：Nitrogen-containing compound：The weight ratio of metallic compound is 1：0.02-5：In the range of 0.05-8.It is further preferred that former
Material nano-carbon material：Nitrogen-containing compound：The weight ratio of metallic compound is 1：0.02-2：In the range of 0.06-6.Further
Preferably, raw material nano carbon material：Nitrogen-containing compound：The weight ratio of metallic compound is 1：0.02-1：In the range of 0.08-5.
It is particularly preferred that raw material nano carbon material：Nitrogen-containing compound：The weight ratio of metallic compound is 1：0.02-0.5：The model of 0.8-5
In enclosing.
The method according to the invention, the mol ratio of the nitrogen-containing compound and the metallic compound is preferably 1：0.001-
In the range of 10, metallic atom, oxygen atom and nitrogen-atoms are in nano-sized carbon 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.More
Preferably, the nitrogen-containing compound with the mol ratio of the metallic compound preferably 1：In the range of 0.03-6.
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-sized carbon
Structural form retentivity of the material in processing procedure is more preferable, for example：For CNT, in processing procedure substantially not
Can be cut off.It is highly preferred that raw material nano carbon material：H2The weight ratio of O is 1：In the range of 5-250.It is further preferred that former
Material nano-carbon material：H2The weight ratio of O is 1：In the range of 10-200.It is further preferred that raw material nano carbon material：H2O's
Weight ratio is 1：In the range of 20-200.It is particularly preferred that raw material nano carbon material：H2The weight ratio of O is 1：The model of 50-200
In enclosing.
The method according to the invention, can also be carried out excellent according to the species of nitrogen-containing compound and metallic compound to consumption
Change, further to improve catalysis of the nano-carbon material containing metallic atom for thus preparing in the catalyst as hydrocarbon dehydrogenation reaction
Activity.In a preferred embodiment, the nitrogen-containing compound is NH3, the metallic element choosing in the metallic compound
From iron, cobalt and nickel, the metallic compound is preferably selected from metal acetate, basic metal hydrochloride and metal oxalate
Plant or two or more, more preferably metal acetate and/or metal oxalate, raw material nano carbon material：Nitrogen-containing compound：Metal
The weight ratio of compound is preferably 1：0.01-1：In the range of 0.5-6, more preferably 1：0.01-0.2：In the range of 0.9-5.
This preferred embodiment in, nitrogen-containing compound：The mol ratio of metallic compound is preferably 1：It is more excellent in the range of 0.1-10
It is selected in 1：In the range of 2-6.This preferred embodiment in, raw material nano carbon material：H2The weight ratio of O is preferably 1：20-
In the range of 100, more preferably 1：In the range of 40-80.
In another preferred embodiment, the nitrogen-containing compound is hydrazine, the metal unit in the metallic compound
Element is selected from palladium and platinum, and the metallic compound is preferably metal acetate, metal oxalate and metal complex (such as acetylacetone,2,4-pentanedione
Palladium and the ammino palladium of nitric acid four) in one or more, more preferably metal acetate and/or metal complex, raw material are received
Rice carbon material：Nitrogen-containing compound：The weight ratio of metallic compound is preferably 1：0.05-3：In the range of 2-6, more preferably 1：
0.2-0.5：In the range of 4-5.This preferred embodiment in, nitrogen-containing compound：The mol ratio of metallic compound preferably exists
1：In the range of 0.2-10, more preferably 1：In the range of 0.6-1.This preferred embodiment in, raw material nano carbon material：
H2The weight ratio of O is preferably 1：In the range of 20-250, more preferably 1：In the range of 50-100.
Another preferred embodiment in, the nitrogen-containing compound be urea, the metal in the metallic compound
Element is selected from ruthenium and rhodium, and the metallic compound is preferably metal complex (such as acetylacetone,2,4-pentanedione ruthenium and acetylacetone,2,4-pentanedione rhodium), raw material
Nano-carbon material：Nitrogen-containing compound：The weight ratio of metallic compound is preferably 1：0.08-6：In the range of 0.02-2, more preferably
1：0.3-0.6：In the range of 0.1-1.This preferred embodiment in, nitrogen-containing compound：The mol ratio of metallic compound
It is preferred that 1：In the range of 0.02-2, more preferably 1：In the range of 0.02-0.4.This preferred embodiment in, raw material is received
Rice carbon material：H2The weight ratio of O is preferably 1：In the range of 20-100, more preferably 1：In the range of 40-80.
The method according to the invention, oxygen atom, the nitrogen of the condition of the reaction to be enough to improve in raw material nano carbon material
The content of atom and metallic atom is defined.Preferably, in course of reaction, the scope of the temperature of the aqueous dispersions at 60-300 DEG C
It is interior.When the temperature of the aqueous dispersions is within above range, in can not only effectively improving raw material nano carbon material
Oxygen atom, nitrogen-atoms and metal atom content, and the generation of the structural form of raw material nano carbon material will not be significantly affected.More
Preferably, in course of reaction, the temperature of the aqueous dispersions is in the range of 120-240 DEG C.
The method according to the invention, duration of the reaction can be selected according to the temperature of reaction, with can
Enough oxygen atoms, nitrogen-atoms and metallic atom is introduced in raw material nano carbon material to be defined.Usually, the reaction continues
Time can be in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably in the range of 8-36 hours.
Method according to the invention it is possible to form the aqueous dispersions using conventional various methods, for example can be by
Raw material nano carbon material is dispersed in water (preferably deionized water), is subsequently adding the nitrogen-containing compound and the metal compound
Thing, so as to obtain the aqueous dispersions.In order to further improve the dispersion effect of raw material nano carbon material, while shortening scattered
Time, raw material nano carbon material can be dispersed in water using the method for sonic oscillation.The condition of the sonic oscillation can be with
It is conventional selection, usually, the frequency of the sonic oscillation can be 10-200kHz, preferably 90-140kHz；The ultrasound
The duration of vibration can be 0.1-6 hours, preferably 0.5-4 hours.The method according to the invention, the nitrogen-containing compound
And the metallic compound is according to specific species, can be provided in the form of solution (preferred aqueous solutions), it is also possible to pure material
Form provide, be not particularly limited.
The method according to the invention, the content of oxygen element and nitrogen is not limited especially in the raw material nano carbon material
It is fixed, can be conventional selection.Usually, the content of oxygen element is not higher than 1.5 weight % in the raw material nano carbon material, excellent
Elect not higher than 1.2 weight %, more preferably not above 0.5 weight %, more preferably not higher than 0.3 weight % as；Nitrogen unit
The content of element is not higher than 0.5 weight %, more preferably not above preferably not higher than 0.2 weight %, 0.1 weight %, enters one
Step is preferably not higher than 0.05 weight %, still more preferably to be not higher than 0.02 weight %.The method according to the invention, it is described
The total amount of remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) in raw material nano carbon material outside oxygen atom and nitrogen-atoms
(in terms of element) can be as customary amount.Usually, remaining in the raw material nano carbon material in addition to oxygen element and nitrogen
The total amount (in terms of element) of nonmetallic heteroatoms be not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably
Not higher than 0.1 weight %, more preferably not higher than 0.05 weight %.The method according to the invention, the raw material nano carbon
Material may contain some metallic elements according to the difference in source, such as used when from preparing raw material nano-carbon material
Metallic atom in catalyst.The content (in terms of element) of metallic atom is generally 2.5 weights in the raw material nano carbon material
Amount below %, more preferably preferably below 1.8 weight %, below 0.5 weight %, are still more preferably 0.1 weight
Amount below %.
The method according to the invention, raw material nano carbon material using it is preceding can be carried out using method commonly used in the art it is pre-
Treatment (as washed), to remove some impurity of raw material nano carbon material surface；Can not also be pre-processed, directly be used.
In embodiment disclosed by the invention, 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 as to improve this receive
Oxygen atom, nitrogen-atoms and metal atom content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon and receive
In mitron, Graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene one or two with
On combination.The CNT can be SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes in one kind or
Two or more combinations.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 received for many wall carbon
Mitron, the specific surface area of the multi-walled carbon nano-tubes can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-
260m2/ g, more preferably 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nano-tubes, temperature of the multi-walled carbon nano-tubes at 400-800 DEG C
Weight-loss ratio in degree interval is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800Can be in 0.01-
In the range of 0.5, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably exist
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,
The specific surface area of the multi-walled carbon nano-tubes is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, enters
One step is preferably 120-190m2/g；Weight-loss ratio of the multi-walled carbon nano-tubes in 400-800 DEG C of temperature range is w800,
Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, preferably 0.02-0.4's
In the range of, more preferably in the range of 0.05-0.35, 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 can be in self-generated pressure (i.e.,
Do not apply pressure additionally) under carry out, it is also possible to carry out under pressure.Preferably, the reaction is entered at autogenous pressures
OK.The closed container can be the common reactor that can realize sealing and heating, such as autoclave.
The method according to the invention, isolates solid matter, and will divide in can also including the mixture obtained from reaction
The solid matter for separating out 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, be such as centrifuged,
One or more combination in filtering and decantation.
The dry condition can be conventional selection, be can remove the volatile materials in the solid matter isolated
It is accurate.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 excellent
Carried out at a temperature of being selected in 120-160 DEG C.The dry duration can be selected according to dry temperature and mode.
Usually, the dry duration can be 0.5-48 hours, preferably 6-24 hours, more preferably 8-12 hours.Institute
Stating drying can be carried out under normal pressure (that is, 1 standard atmospheric pressure), it is also possible to be carried out at reduced pressure.From further raising
The angle of dry efficiency is set out, and the drying is preferably carried out at reduced pressure.
The method according to the invention, can effectively improve oxygen atom in raw material nano carbon material, nitrogen-atoms and metal raw
Sub- content, while will not be produced to the structural form of raw material nano carbon material significantly affecting.
According to the third aspect of the present invention, the invention provides one kind by prepared according to the methods of the invention containing metal
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 metal
Atom nano-carbon material is by according to the nano-carbon material containing metallic atom of one side of the invention or according to the present invention the
Prepared by three nano-carbon materials containing metallic atom of aspect are 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.The duration of the roasting can be according to the temperature of roasting
Selected.Usually, the duration of the roasting can be 1-24 hours, preferably 2-12 hours, such as 4-12 hours.Institute
Stating 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 can
Think air atmosphere；Can also be mixed atmosphere that oxygen and inert gas are mixed to form, in the mixed atmosphere, oxygen contains
Amount can be 0.1-22 volumes %.The inert gas can include but is not limited to nitrogen and/or rare gas, the rare gas
Body can be argon gas and/or helium.Angularly consider from convenience and cost, it is preferable that the roasting is in oxygen-containing atmosphere (such as sky
Gas atmosphere) in carry out.
Nano-carbon material containing metallic atom of the invention is received by prepared by the method for the present invention containing metallic atom
Rice carbon material has good catalytic performance, and catalysis activity higher is particularly shown in hydrocarbons dehydrogenation reaction.
Nano-carbon material containing metallic atom of the invention is received by prepared by the method for the present invention containing metallic atom
Rice carbon material can be directly used as catalyst, it is also possible to be used in the form of preformed catalyst.The preformed catalyst can contain
With good grounds nano-carbon material containing metallic atom of the invention or the nano carbon material containing metallic atom prepared by the method for the present invention
Material and binding agent.The binding agent can be selected according to the specifically used occasion of the preformed catalyst, disclosure satisfy that
Use requirement is defined, for example, can be organic binder bond and/or inorganic binder.The organic binder bond can be common each
Polymer-type binding agent is planted, the inorganic binder can be common various heat-resistant inorganic oxides, such as aluminum oxide and/or oxygen
SiClx.It is to hydrocarbon dehydrogenation reaction (such as direct dehydrogenation reaction and oxidative dehydrogenation), particularly to oxygen in the preformed catalyst
When fluidized dehydrogenation reaction has the preformed catalyst of catalytic action, the binding agent is preferably inorganic binder.The shaped catalyst
In agent, the content containing metallic atom nano-carbon material can be selected according to specifically used requirement, be not particularly limited, typically
Ground, 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 being received containing metallic atom according to one side of the invention
Rice carbon material, according to third aspect of the present invention nano-carbon material containing metallic atom or according to 4th aspect of the invention
Nano-carbon material containing metallic atom as the catalyst of hydrocarbon dehydrogenation reaction application.
Application according to the present invention, the nano-carbon material containing metallic atom is used directly for hydrocarbon dehydrogenation reaction, also may be used
To be used for hydrocarbon dehydrogenation reaction after shaping.The dehydrogenation reaction can be carried out in the presence of oxygen, it is also possible to not in the presence of oxygen
Carry out.Preferably, the dehydrogenation 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 deposits
Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with according to one side of the invention containing metal
Atom nano-carbon material, according to third aspect of the present invention nano-carbon material containing metallic atom or according to the present invention the 4th
The contact of nano-carbon material containing metallic atom of individual aspect.
Hydrocarbon dehydrogenation reaction method of the invention, the nano-carbon material containing metallic atom is used directly for being connect with hydrocarbon
Touch, it is also possible to for being contacted with hydrocarbon after the nano-carbon material containing metallic atom is molded.
Hydrocarbon dehydrogenation reaction method of the invention can carry out dehydrogenation to polytype hydrocarbon, so as to obtain unsaturation
Hydrocarbon, such as alkene.The method according to the invention is particularly suitable for carrying out dehydrogenation to alkane, so as to obtain 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 ethane, 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- second
Base pentane, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- dimethyl pentanes, normal octane, 2- methyl heptanes, 3- methyl heptanes,
4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- front threes
Base pentane, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 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- front threes
Base hexane, 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 hexamethylene
Alkane, trimethyl-cyclohexane (including various isomers of trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- front threes
Butylcyclohexane, 1,2,5- trimethyl-cyclohexanes, 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- front threes
Base heptane, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- trimethylheptanes, 2,2,6- trimethylheptanes, 2,
3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 2- methyl -4- ethyl heptanes, 2- methyl -5-
Ethyl heptane, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyl heptanes, 4- methyl -4- ethyls
Heptane, 4- propyl group heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- diethylpentanes, vinylbenzene, 1-
In phenyl-propane, 2- phenyl-propanes, 1- phenyl butanes, 2- phenyl butanes, 1- phenyl pentanes, 2- phenyl pentanes and 3- phenyl pentanes
One or more combination.It is highly preferred that the hydrocarbon be propane, normal butane, iso-butane and vinylbenzene in one kind or
It is two 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 to
Under conditions of in the absence of oxygen.Preferably, hydrocarbon dehydrogenation reaction method of the invention, enters under conditions of it there is oxygen
OK.In the method for the present invention when being carried out under conditions of there is oxygen, the consumption of oxygen can be conventional selection.Usually, hydrocarbon
Can be 0.01-100 with the mol ratio of oxygen：1, preferably 0.1-10：1, more preferably 0.2-5：1, most preferably 0.3-2：
1。
Hydrocarbon dehydrogenation reaction method of the invention, can be by carrier gas by hydrocarbon and oxygen feeding reactor and containing metal
Atom nano-carbon material haptoreaction.The carrier gas will not can be generated with reactant and reaction at reaction conditions for conventional
There is chemical interaction and the gas that will not be decomposed in thing, in nitrogen, carbon dioxide, rare gas and vapor
One or more combination.The consumption of the carrier gas can be conventional selection.Usually, the content of carrier gas can be with 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 send out hydrocarbon
Raw dehydrogenation reaction is defined.Usually, the contact can be carried out at a temperature of 200-650 DEG C, preferably in 300-600 DEG C of temperature
Carried out under degree, carried out more preferably 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 to
Carried out in fluidized-bed reactor, 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
Select, contact as described when being carried out in fixed bed reactors, holding for contact can be represented with the volume space velocity of the gas of charging
The continuous time.Usually, the volume space velocity of the gas of charging can be 0.1-10000h-1, preferably 1-6000h-1, more preferably
5-5000h-1, more preferably 10-4000h-1, such as 800-1200h-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, outfit of the X-ray photoelectron spectroscopic analysis in Thermo Scientific companies
Have on the ESCALab250 type x-ray photoelectron spectroscopies of Thermo Avantage V5.926 softwares and tested, excitaton source
It is monochromatization Al K α X-rays, energy is 1486.6eV, and power is 150W, penetrating energy used by narrow scan is 30eV, analysis test
When base vacuum be 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, in Thermo
Data processing is carried out on Avantage softwares, quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is being surveyed
Depressed in 150 DEG C of temperature and 1 normal atmosphere before examination and dried 3 hours in helium atmosphere.
In following examples and comparative example, thermogravimetric analysis is carried out on TA5000 thermal analyzers, and test condition is air gas
Atmosphere, programming rate is 10 DEG C/min, and temperature range is room temperature (25 DEG C) to 1000 DEG C.Sample is before testing in 150 DEG C of temperature
Depressed with 1 normal atmosphere and dried 3 hours in helium atmosphere.Using the ASAP2000 types N of Micromertrics companies of the U.S.2
Physical adsorption appearance measurement the specific area.The high-resolution-ration transmission electric-lens produced using FEI Co. of the U.S. analyze raw material nano carbon material
And the microscopic appearance containing metallic atom nano-carbon material.
Embodiment 1-45 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
It is 0.3 weight %, nitrogen atom content is 0.02 weight %, (phosphorus is former for remaining nonmetallic heteroatoms in addition to nitrogen-atoms and oxygen atom
Son and sulphur atom) total content be 0.01 weight %, metallic atom total content be 0.1 weight %, in 400-800 DEG C of temperature range
Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, purchased from Chinese science
Chengdu organic chemistry Co., Ltd of institute) dispersion in deionized water, being dispersed under the conditions of sonic oscillation is carried out, sonic oscillation condition
Including：Frequency is 140kHz, and the time is 0.5 hour.Then, NH is added3(in the form of the aqueous solution of 36 weight % provide) and
As the nickel acetate of metallic compound, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：NH3：Metallic compound：
H2The weight ratio of O is 1：0.2：5：50 ratio feeds intake.
(2) aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, in 140 DEG C of temperature
Under, react 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened
Kettle, reactant mixture is filtered and washed, and collected solid matter.(1 standard is big in normal pressure for the solid matter that will be collected into
Air pressure, similarly hereinafter), after drying 12 hours at a temperature of 120 DEG C, nano-carbon material containing metallic atom is obtained, this contains metallic atom and receives
The rice composition of 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 many of raw material
The transmission electron microscope photo of wall carbon nano tube.Be can be seen that containing the microcosmic of metallic atom nano-carbon material from Fig. 1 and Fig. 2
Form is good, shows that course of reaction is 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
During temperature is 140 DEG C of oil bath, in back flow reaction under normal pressure 24 hours.After reaction terminates, treat that the temperature in there-necked flask is down to
After room temperature, reactant mixture is filtered and washed, and is collected solid matter.The solid matter that will be collected into is in normal pressure, 120
After DEG C drying 12 hours, nano-carbon material containing metallic atom is obtained.The nature parameters containing metallic atom nano-carbon material for preparing
Listed in table 1.
Comparative example 2
Nano-carbon material is prepared using method same as Example 1, unlike, in step (1), for preparing moisture
The aqueous solution of dispersion liquid not metal-containing compound, it is, by the dispersion of raw material nano carbon material in deionized water, being subsequently adding
NH3, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：NH3：Metallic compound：H2The weight ratio of O is 1：0.2：
0：50 ratio feeds intake.The nature parameters of the nano-carbon material of preparation are listed in table 1.
Comparative example 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), use
NH is free of in the aqueous solution for preparing aqueous dispersions3, it is, by the dispersion of raw material nano carbon material in deionized water, Ran Houjia
Enter metallic compound, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：NH3：Metallic compound：H2The weight ratio of O
It is 1：0：5：50 ratio feeds intake.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 1.
Comparative example 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), use
NH is free of in the aqueous solution for preparing aqueous dispersions3, it is, by the dispersion of raw material nano carbon material in deionized water, Ran Houjia
Enter metallic compound, so as to obtain aqueous dispersions, wherein, mole and the NH in embodiment 1 of nickel acetate3With always rubbing for nickel acetate
Your amount is identical, and the consumption of raw material nano carbon material and water is same as Example 1.Prepare containing metallic atom nano-carbon material
Nature parameters are listed in table 1.
Comparative example 5
In deionized water, ultrasound is dispersed in by using the nano-carbon material dispersion prepared with the identical method of comparative example 2
Carried out under oscillating condition, sonic oscillation condition includes：Frequency is 140kHz, and the time is 0.5 hour.Then, metal compound is added
Thing, so as to obtain aqueous dispersions, wherein, (used and prepare nano carbon material with the identical method of comparative example 2 by raw material nano carbon material
The raw material nano carbon material used during material)：Metallic compound：H2The weight ratio of O is 1：0.2：50 ratio feeds intake.By what is obtained
Aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 140 DEG C, are reacted at autogenous pressures
24 hours.After reaction terminates, after the temperature in autoclave is down to room temperature, reactor is opened, reactant mixture is carried 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,
Nano-carbon material containing metallic atom is obtained, the nature parameters for containing metallic atom nano-carbon material are listed in table 1.
Embodiment 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), make
For the specific surface area of the multi-walled carbon nano-tubes (being purchased from Shandong great Zhan nano materials Co., Ltd) of raw material nano carbon material is
251m2/ g, the 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
It is w500, w500/w800Be 0.33, oxygen atom content is 0.62 weight %, nitrogen atom content is 0.01 weight %, except nitrogen-atoms and
The total content of remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) outside oxygen atom is 0.01 weight %, metallic atom total content
It is 0.08 weight %.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 1.
Embodiment 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (2), will
The aqueous dispersions for obtaining are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 70 DEG C, in self-generated pressure
Lower reaction 24 hours.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 1.
Embodiment 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), press
Raw material nano carbon material：NH3：Metallic compound：H2The weight ratio of O is 1：1：2：50 ratio feeds intake.Prepare containing metallic atom
The nature parameters of nano-carbon material are listed in table 1.
Embodiment 5
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), press
Raw material nano carbon material：NH3：Metallic compound：H2The weight ratio of O is 1：0.05：5：50 ratio feeds intake.Prepare containing metal
The nature parameters of atom nano-carbon material are listed 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 %, remaining the nonmetallic heteroatoms (phosphorus atoms in addition to nitrogen-atoms and oxygen atom
And sulphur atom) total content be 0.04 weight %, metallic atom total content be 0.03 weight %, 400-800 DEG C of humidity province
Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.07, purchased from China
Chengdu organic chemistry Co., Ltd of the academy of sciences) dispersion in deionized water, being dispersed under the conditions of sonic oscillation is carried out, sonic oscillation
Condition includes：Frequency is 90kHz, and the time is 4 hours.Then, NH is added3(being provided in the form of the 36 weight % aqueous solution) and make
It is the ferric oxalate of metallic compound, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：NH3：Metallic compound：H2O
Weight ratio be 1：0.02：2.5：50 ratio feeds intake.
(2) aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, in 240 DEG C of temperature
Under, react 12 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened
Kettle, reactant mixture is filtered and washed, and collected solid matter.The solid matter that will be collected into normal pressure, 160 DEG C
At a temperature of dry 8 hours after, obtain nano-carbon material containing metallic atom, the nature parameters for containing metallic atom nano-carbon material exist
Listed in table 1.
Comparative example 6
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), use
NH is free of in the aqueous solution for preparing aqueous dispersions3, it is, by the dispersion of raw material nano carbon material in deionized water, Ran Houjia
Enter ferric oxalate, so as to obtain aqueous dispersions, wherein, mole and the NH in embodiment 6 of ferric oxalate3With the integral molar quantity of ferric oxalate
Identical, the consumption of raw material nano carbon material and water is same as Example 6.The ginseng of the property containing metallic atom nano-carbon material for preparing
Number is listed in table 1.
Embodiment 7
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), make
For the specific surface area of the multi-walled carbon nano-tubes (being purchased from Shandong great Zhan nano materials Co., Ltd) of raw material nano carbon material is
103m2/ g, w500/w800Be 0.23, oxygen atom content be 1.1 weight %, nitrogen atom content be 0.03 weight %, denitrogenate with outside oxygen
Remaining nonmetallic heteroatoms (p and ses) total content be 0.01 weight %, metallic atom total content be 1.6 weight %.Prepare
The nature parameters containing metallic atom nano-carbon material listed in table 1.
Embodiment 8
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (2), will
The aqueous dispersions for obtaining are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 280 DEG C, in self-generated pressure
Lower reaction 12 hours.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 1.
Embodiment 9
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1),
NH3Under conditions of keeping constant with the gross weight of ferric oxalate, make NH3：The mol ratio of ferric oxalate is 1：8.Prepare containing metallic atom
The nature parameters of nano-carbon material are listed in table 1.
Embodiment 10
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), grass
Sour iron is replaced with the nickel oxalate of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 1.
Embodiment 11
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), grass
Sour iron is replaced with the basic nickel carbonate of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are arranged in table 1
Go out.
Embodiment 12
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), grass
Sour iron is replaced with the cobalt acetate of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 1.
Embodiment 13
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), grass
Sour iron is replaced with the acid chloride of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 1.
Embodiment 14
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), grass
Sour iron is replaced with the ruthenium acetate of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 1.
Embodiment 15
Nano-carbon material containing metallic atom is prepared using method same as Example 1, difference is as follows：Step (1)
In, by the dispersion of raw material nano carbon material in deionized water, be subsequently adding hydrazine (in the form of the 50 weight % aqueous solution provide) and
As the acid chloride of metallic compound, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Hydrazine：Metallic compound：
H2The weight ratio of O is 1：0.2：4.5：100 ratio feeds intake；In step (2), the aqueous dispersions that will be obtained are placed in polytetrafluoro
In the autoclave of ethene liner, at a temperature of 180 DEG C, react 24 hours at autogenous pressures.Prepare containing metal raw
The nature parameters of sub- nano-carbon material are listed in table 2.
Comparative example 7
It is equipped with being placed in the identical aqueous dispersions of embodiment 15 in the there-necked flask of condenser pipe, the there-necked flask is placed in
During temperature is 180 DEG C of oil bath, in back flow reaction under normal pressure 24 hours.After reaction terminates, treat that the temperature in there-necked flask is down to
After room temperature, reactant mixture is filtered and washed, and is collected solid matter.The solid matter that will be collected into is in normal pressure, 120
After being dried 12 hours at a temperature of DEG C, nano-carbon material containing metallic atom is obtained.Prepare containing metallic atom nano-carbon material
Nature parameters are listed in table 2.
Comparative example 8
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, step (1) configuration
Aqueous dispersions be free of hydrazine, it is, by raw material nano carbon material dispersion in deionized water, be subsequently adding acid chloride so that
Aqueous dispersions are obtained, wherein, by raw material nano carbon material：Hydrazine：Metallic compound：H2The weight ratio of O is 1：0：4.5：100 ratio
Example feeds intake.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Comparative example 9
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, step (1) configuration
Aqueous dispersions be free of hydrazine, it is, by raw material nano carbon material dispersion in deionized water, be subsequently adding acid chloride so that
Aqueous dispersions are obtained, wherein, the mole of acid chloride is identical with the integral molar quantity of hydrazine and acid chloride in embodiment 15, raw material nano
The consumption of carbon material and water is identical with embodiment 15.The nature parameters containing metallic atom nano-carbon material for preparing are in table 2
List.
Comparative example 10
Nano-carbon material is prepared using with the identical method of embodiment 15, unlike, the aqueous solution used in step (1)
Not metal-containing compound, it is, by the dispersion of raw material nano carbon material in deionized water, hydrazine is subsequently adding, so as to obtain water
Dispersion liquid, wherein, by raw material nano carbon material：Hydrazine：Metallic compound：H2The weight ratio of O is 1：0.2：0：100 ratio is thrown
Material.The nature parameters of the nano-carbon material of preparation are listed 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),
The aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 260 DEG C, in spontaneous pressure
Reacted 24 hours under power.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 17
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, received as raw material
The multi-walled carbon nano-tubes of rice carbon material is same as Example 2.The nature parameters containing metallic atom nano-carbon material for preparing are in table 2
In list.
Embodiment 18
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, in step (1),
By raw material nano carbon material：Hydrazine：Metallic compound：H2The weight ratio of O is 1：2：5：100 ratio feeds intake.Prepare containing metal
The nature parameters of atom nano-carbon material are listed in table 2.
Embodiment 19
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, in step (1),
By raw material nano carbon material：Hydrazine：Metallic compound：H2The weight ratio of O is 1：0.08：4.8：200 ratio feeds intake.What is prepared contains
The nature parameters of metallic atom nano-carbon material are listed in table 2.
Embodiment 20
Nano-carbon material containing metallic atom is prepared using method same as Example 6, difference is as follows：Step (1)
In, by the dispersion of raw material nano carbon material in deionized water, hydrazine and the palladium acetylacetonate as metallic compound are subsequently adding, from
And aqueous dispersions are obtained, wherein, by raw material nano carbon material：Hydrazine：Metallic compound：H2The weight ratio of O is 1：0.5：4.5：50
Ratio feed intake；In step (2), the aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, in
At a temperature of 120 DEG C, react 72 hours at autogenous pressures.The nature parameters containing metallic atom nano-carbon material for preparing are in table
Listed in 2.
Embodiment 21
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, in step (1),
Multi-walled carbon nano-tubes as raw material nano carbon material is same as Example 7.The property containing metallic atom nano-carbon material for preparing
Matter parameter is listed in table 2.
Embodiment 22
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, in step (1),
Under conditions of the gross weight of hydrazine and metallic compound is constant, hydrazine：The mol ratio of metallic compound is 1：5.Prepare containing metal raw
The nature parameters of sub- nano-carbon material are listed in table 2.
Embodiment 23
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, in step (1),
Under conditions of the integral molar quantity of hydrazine and metallic compound is constant, hydrazine：The mol ratio of metallic compound is 10：1.Prepare containing metal
The nature parameters of atom nano-carbon material are listed in table 2.
Embodiment 24
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, in step (2),
The aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 60 DEG C, in spontaneous pressure
Reacted 72 hours under power.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 25
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, palladium acetylacetonate
Replaced with the nickel oxalate of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 26
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, palladium acetylacetonate
Replaced with the ruthenium acetate of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 27
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, palladium acetylacetonate
Replaced with the rhodium acetate of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 28
Nano-carbon material containing metallic atom is prepared using method same as Example 1, difference is as follows：Step (1)
In, by the dispersion of raw material nano carbon material in deionized water, urea and the acetylacetone,2,4-pentanedione ruthenium as metallic compound are subsequently adding,
So as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Urea：Metallic compound：H2The weight ratio of O is 1：0.5：
0.1：80 ratio feeds intake；In step (2), the aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining
In, at a temperature of 180 DEG C, react 36 hours at autogenous pressures.The ginseng of the property containing metallic atom nano-carbon material for preparing
Number is listed in table 2.
Comparative example 11
It is equipped with being placed in the identical aqueous dispersions of embodiment 28 in the there-necked flask of condenser pipe, the there-necked flask is placed in
During temperature is 180 DEG C of oil bath, in back flow reaction under normal pressure 36 hours.After reaction terminates, treat that the temperature in there-necked flask is down to
After room temperature, reactant mixture is filtered and washed, and is collected solid matter.The solid matter that will be collected into is in normal pressure, 120
After being dried 12 hours at a temperature of DEG C, nano-carbon material containing metallic atom is obtained.Prepare containing metallic atom nano-carbon material
Nature parameters are listed in table 2.
Comparative example 12
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 28, unlike, step makes in (1)
The aqueous solution is free of urea, it is, by the dispersion of raw material nano carbon material in deionized water, being subsequently adding metal compound
Thing, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Urea：Metallic compound：H2The weight ratio of O is 1：0：
0.1：80 ratio feeds intake.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Comparative example 13
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 28, unlike, step makes in (1)
The aqueous solution is free of urea, it is, raw material nano carbon material point is spread in deionized water, is subsequently adding metal compound
Thing, so as to obtain aqueous dispersions, wherein, the mole of metallic compound is total with urea in embodiment 28 and metallic compound
Mole is identical, and the consumption of raw material nano carbon material and water is identical with embodiment 28.The nano carbon material containing metallic atom for preparing
The nature parameters of material are listed in table 2.
Comparative example 14
Nano-carbon material is prepared using with the identical method of embodiment 28, unlike, the aqueous solution used in step (1)
Not metal-containing compound, it is, by the dispersion of raw material nano carbon material in deionized water, urea is subsequently adding, so as to obtain
Aqueous dispersions, wherein, by raw material nano carbon material：Urea：Metallic compound：H2The weight ratio of O is 1：0.5：0：80 ratio
Feed intake.The nature parameters of the nano-carbon material of preparation are listed in table 2.
Embodiment 29
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 28, unlike, in step (2),
The aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in spontaneous pressure
Reacted 36 hours under power.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 30
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 28, unlike, received as raw material
Rice carbon material is same as Example 2.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 31
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 28, unlike, in step (1),
Raw material nano carbon material：Urea：Metallic compound：H2The weight ratio of O is 1：6：0.1：80.The nano-sized carbon containing metallic atom for preparing
The nature parameters of material are listed in table 2.
Embodiment 32
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 28, unlike, in step (1),
By raw material nano carbon material：Urea：Metallic compound：H2The weight ratio of O is 1：0.5：0.02：80 ratio feeds intake.Prepare
Nature parameters containing metallic atom nano-carbon material are listed in table 2.
Embodiment 33
Nano-carbon material containing metallic atom is prepared using method same as Example 6, difference is as follows：Step (1)
In, by the dispersion of raw material nano carbon material in deionized water, urea and the acetylacetone,2,4-pentanedione rhodium as metallic compound are subsequently adding,
So as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Urea：Metallic compound：H2The weight ratio of O is 1：0.4：1：
40 ratio feeds intake；In step (2), the aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining,
At a temperature of 150 DEG C, react 12 hours at autogenous pressures.The nature parameters containing metallic atom nano-carbon material for preparing exist
Listed in table 2.
Embodiment 34
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 33, unlike, in step (1),
Raw material nano carbon material is same as Example 7.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 35
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 33, unlike, in step (1),
Under conditions of the gross weight of urea and metallic compound keeps constant, make urea：The mol ratio of metallic compound is 1：2.Prepare
The nature parameters containing metallic atom nano-carbon material listed in table 2.
Embodiment 36
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 33, unlike, in step (2),
The aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 70 DEG C, in spontaneous pressure
Reacted 12 hours under power.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 37
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 33, unlike, acetylacetone,2,4-pentanedione rhodium
Replaced with the ferrous acetate of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 38
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 33, unlike, acetylacetone,2,4-pentanedione rhodium
Replaced with the acid chloride of equimolar amounts.The nature parameters containing metallic atom nano-carbon material for preparing are listed in table 2.
Embodiment 39
It is small that nano-carbon material containing metallic atom prepared by embodiment 1 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Comparative example 15
It is small that nano-carbon material containing metallic atom prepared by comparative example 1 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Comparative example 16
It is small that nano-carbon material containing metallic atom prepared by comparative example 2 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Comparative example 17
It is small that nano-carbon material containing metallic atom prepared by comparative example 3 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Comparative example 18
It is small that nano-carbon material containing metallic atom prepared by comparative example 4 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Comparative example 19
It is small that nano-carbon material containing metallic atom prepared by comparative example 5 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Embodiment 40
It is small that nano-carbon material containing metallic atom prepared by embodiment 2 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Embodiment 41
It is small that nano-carbon material containing metallic atom prepared by embodiment 3 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Embodiment 42
It is small that nano-carbon material containing metallic atom prepared by embodiment 4 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Embodiment 43
It is small that nano-carbon material containing metallic atom prepared by embodiment 5 is calcined 4 in air atmosphere at a temperature of 350 DEG C
When.
Embodiment 44
It is small that nano-carbon material containing metallic atom prepared by embodiment 15 is calcined 2 in air atmosphere at a temperature of 450 DEG C
When.
Embodiment 45
It is small that nano-carbon material containing metallic atom prepared by embodiment 33 is calcined 12 in air atmosphere at a temperature of 300 DEG C
When.
Embodiment 46-90 is used to illustrate the present invention.
Embodiment 46-83
The nano-carbon material containing metallic atom for respectively being prepared by 0.2g (admission space is 1.9mL) embodiment 1-38 is used as urging
Agent is seated in universal fixed bed miniature quartz pipe reactor, and the end seal of miniature quartz pipe reactor two has quartz sand,
Under the conditions of 0.12MPa and 440 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 1.5 volume %, normal butane and oxygen
Gas mol ratio 0.5：1, the balance of nitrogen as carrier gas) with cumulative volume air speed as 1000h-1It is passed through in reactor and is reacted,
The composition of the reactant mixture that continuous monitoring is exported from reactor, and calculate n-butane conversion, total olefin selectivity and fourth
Alkene selectivity (being 1- butylene and the overall selectivity of 2- butylene), the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 20-33
Reacted using with embodiment 46-83 identical methods, unlike, prepared using comparative example 1-14 respectively
Nano-carbon material containing metallic atom is used as catalyst.Reaction result is listed in table 3.
Comparative example 34
Reacted using with embodiment 46-83 identical methods, unlike, use raw material same as Example 1
Nano-carbon material is used as catalyst.Reaction result is listed in table 3.
Comparative example 35
Reacted using with embodiment 46-83 identical methods, unlike, use raw material same as Example 5
Nano-carbon material is used as catalyst.Reaction result is listed in table 3.
Embodiment 84-90
Reacted using with embodiment 46-83 identical methods, unlike, use prepared by embodiment 39-45 containing
Metallic atom CNT is used as catalyst.Reaction result is listed in table 4.
Comparative example 36-40
Reacted using with embodiment 46-83 identical methods, unlike, use prepared by comparative example 15-19 containing
Metallic atom CNT is used as catalyst.Reaction result is listed in table 4.
Comparative example 41
Reacted using with embodiment 46-83 identical methods, unlike, catalyst is will be same as Example 1
Raw material nano carbon material in the air atmosphere at a temperature of 350 DEG C obtained from roasting 4 hours.Reaction result is arranged in table 4
Go out.
Comparative example 42
Reacted using with embodiment 46-83 identical methods, unlike, catalyst is will be same as Example 5
Raw material nano carbon material in the air atmosphere at a temperature of 300 DEG C obtained from roasting 12 hours.Reaction result is arranged in table 4
Go out.
Table 3
Table 4
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of 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 contain metallic atom nano-carbon material contain 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 and in terms of element, the content of O elements is
2-15 weight %, the content of N element is 0.8-10 weight %, the total amount of the metallic element is 1-10 weight %, and C element contains
It is 65-96.2 weight % to measure；
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, penetrated by X
The content of the O elements that the peak in photoelectron spectra in the range of 529.5-530.8eV determines is IO m, IO m/IO t0.02-0.2's
In the range of；
This contains in metallic atom nano-carbon material, is determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum
The amount of O elements 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 eIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, and the N in the nano-carbon material containing metallic atom is 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 tIn the range of 0.7-1.
2. nano-carbon material containing metallic atom according to claim 1, wherein, IO m/IO tIn the range of 0.05-0.18,
It is preferred that in the range of 0.08-0.15；IO c/IO eIn the range of 0.45-0.99；IN c/IN tIt is excellent in the range of 0.8-0.95
It is selected in the range of 0.87-0.95.
3. nano-carbon material containing metallic atom according to claim 1 and 2, wherein, this contains metallic atom nano-carbon material
In, 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 photoelectricity
The amount of the C element that the peak in sub- power spectrum in the range of 286.0-286.2eV determines is IC e, IC c/IC eIn the range of 0.3-2, preferably
In the range of 0.4-1.5, more preferably in the range of 0.5-1.25.
4. the nano-carbon material containing metallic atom according to any one in claim 1-3, wherein, metallic atom is contained with this
On the basis of the total amount of the C element determined by x-ray photoelectron power spectrum in nano-carbon material, by x-ray photoelectron power spectrum
The content of the C element that peak in the range of 284.7-284.9eV determines is 50-95 weight %, preferably 60-95 weight %, more excellent
Elect 70-93 weight % as, the content of the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum is
5-50 weight %, preferably 5-40 weight %, more preferably 7-30 weight %.
5. the nano-carbon material containing metallic atom according to any one in claim 1-4, wherein, by x-ray photoelectron
Power spectrum determines that the total amount of the N element in the nano-carbon material containing metallic atom is IN t, by 400.6- in x-ray photoelectron power spectrum
The amount of the N element that the peak in the range of 401.5eV determines is IN g, IN g/IN tTo be not higher than 0.3, preferably in the scope of 0.05-0.2
It is interior, more preferably in the range of 0.05-0.13.
6. the nano-carbon material containing metallic atom according to any one in claim 1-5, wherein, metallic atom is contained with this
On the basis of the total amount of nano-carbon material and in terms of element, the content of O elements is 3-9 weight %, preferably 4-8 weight %, C element
Content be 79-94.8 weight %, preferably 82.5-93.4 weight %, the content of N element is 1-6 weight %, preferably 1.1-
5 weight %, the total amount of the metallic element is 1.2-6 weight %, preferably 1.5-4.5 weight %.
7. the nano-carbon material containing metallic atom according to any one in claim 1-6, wherein, the metallic element choosing
From transition metal, group VIII metal is preferably selected from, 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 and receives
Rice carbon material is CNT containing metallic atom；Preferably, it is containing many wall carbon of metallic atom that this contains metallic atom nano-carbon material
Nanotube.
9. nano-carbon material containing metallic atom according to claim 8, wherein, the multi-walled carbon nano-tubes containing metallic atom
Specific surface area in 50-500m2In the range of/g, preferably in 80-300m2In the range of/g, more preferably in 95-260m2The model of/g
In enclosing, further preferably in 125-180m2In the range of/g.
10. nano-carbon material containing metallic atom according to claim 8 or claim 9, wherein, many wall carbon containing metallic atom are received
Weight-loss ratio of the mitron 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/w800In the range of 0.01-0.5, preferably in the range of 0.04-0.18, the weight-loss ratio is in air atmosphere
Determine.
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 materials
The aqueous dispersions of material, at least one nitrogen-containing compound and at least one metallic compound are reacted in closed container, institute
State nitrogen-containing compound and be selected from NH3, hydrazine and urea, in course of reaction, the temperature of the aqueous dispersions is maintained at 60-300 DEG C of model
In enclosing.
12. methods according to claim 11, wherein, raw material nano carbon material：Nitrogen-containing compound：The weight of metallic compound
Amount ratio is 1：0.01-10：In the range of 0.01-10, preferably 1：0.02-5：In the range of 0.05-8, more preferably 1：0.02-
2：In the range of 0.06-6, further preferably 1：0.02-1：In the range of 0.08-5, still more preferably 1：0.02-
0.5：In the range of 0.8-5；
Raw material nano carbon material：H2The weight ratio of O is 1：In the range of 2-500, preferably 1：In the range of 5-250, more preferably exist
1：In the range of 10-200, further preferably 1：In the range of 20-200, still more preferably 1：In the range of 50-200.
13. method according to claim 11 or 12, wherein, nitrogen-containing compound：The mol ratio of metallic compound is 1：
In the range of 0.001-10, preferably 1：In the range of 0.03-6.
14. method according to any one in claim 11-13, wherein, the metallic element in the metallic compound
Selected from transition metal, group VIII metallic element is preferably selected from, is more preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
15. method according to any one in claim 11-14, wherein, the metallic compound is selected from metal acetic acid
Salt, metal oxalate, basic metal carbonates and metal complex.
16. methods according to claim 11, wherein, the nitrogen-containing compound is NH3, the gold in the metallic compound
Category element is selected from iron, cobalt and nickel, and the metallic compound is preferably metal acetate, basic metal hydrochloride and metal oxalate
In one or more, more preferably metal acetate and/or metal oxalate, raw material nano carbon material：Nitrogenous chemical combination
Thing：The weight ratio of metallic compound is 1：0.01-1：In the range of 0.5-6, preferably 1：0.01-0.2：In the range of 0.9-5,
Nitrogen-containing compound：The mol ratio of metallic compound is 1：In the range of 0.1-10, preferably 1：In the range of 2-6, raw material nano
Carbon material：H2The weight ratio of O is 1：In the range of 20-100, preferably 1：In the range of 40-80；Or
The nitrogen-containing compound is hydrazine, and the metallic element in the metallic compound is selected from palladium and platinum, and the metallic compound is
One or more in metal acetate, metal oxalate and metal complex, preferably metal acetate and/or metal
Complex compound, raw material nano carbon material：Nitrogen-containing compound：The weight ratio of metallic compound is 1：0.05-3：It is excellent in the range of 2-6
It is selected in 1：0.2-0.5：In the range of 4-5, nitrogen-containing compound：The mol ratio of metallic compound is 1：It is excellent in the range of 0.2-10
It is selected in 1：In the range of 0.6-1, raw material nano carbon material：H2The weight ratio of O is preferably 1：In the range of 20-250, preferably 1：
In the range of 50-100；Or
The nitrogen-containing compound is urea, and the metallic element in the metallic compound is selected from ruthenium and rhodium, the metallic compound
Preferably metal complex, raw material nano carbon material：Nitrogen-containing compound：The weight ratio of metallic compound is 1：0.08-6：0.02-
In the range of 2, preferably 1：0.3-0.6：In the range of 0.1-1, nitrogen-containing compound：The mol ratio of metallic compound is 1：
In the range of 0.02-2, preferably 1：In the range of 0.02-0.4, raw material nano carbon material：H2The weight ratio of O is 1：20-100
In the range of, preferably 1：In the range of 40-80.
17. method according to any one in claim 11-16, wherein, in course of reaction, the temperature of the aqueous dispersions
Degree is maintained in the range of 120-240 DEG C.
18. method according to any one in claim 11-17, wherein, the duration of the reaction is in 0.5-96
In the range of hour, preferably in the range of 2-72 hours, more preferably in the range of 8-36 hours.
19. method according to any one in claim 11-18, wherein, in the raw material nano carbon material, N element
Content be not higher than 0.5 weight %, more preferably not above preferably not higher than 0.2 weight %, 0.1 weight %, further
Preferably not higher than 0.05 weight %, is not higher than 1.5 still more preferably to be not higher than the content of 0.02 weight %, O element
Weight %, preferably not higher than 1.2 weight %, more preferably not above 0.5 weight %, more preferably not higher than 0.3 weight
Amount %, the total amount of metallic element is below 2.5 weight %, more preferably preferably below 1.8 weight %, 0.5 weight %
Hereinafter, still more preferably it is below 0.1 weight %.
20. method according to any one in claim 11-19, wherein, the raw material nano carbon material is carbon nanometer
Pipe；Preferably, 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, it is excellent
Elect 80-300m as2/ g, more preferably 100-260m2/ g, more preferably 120-190m2/g。
22. method according to claim 20 or 21, wherein, humidity province of the multi-walled carbon nano-tubes 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/w800In the model of 0.01-0.5
In enclosing, preferably in the range of 0.02-0.4, the weight-loss ratio is determined in air atmosphere.
23. method according to any one in claim 11-22, wherein, the method is also included from mixing that reaction is obtained
Solid matter is isolated in compound, 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-
Carried out at a temperature of 180 DEG C, carried out more preferably at a temperature of 120-160 DEG C, the dry duration is that 0.5-48 is small
When, preferably 6-24 hours, more preferably 8-12 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, this contain metallic atom nano-carbon material be will be in claim 1-10 arbitrarily
The nano-carbon material containing metallic atom described in nano-carbon material containing metallic atom or claim 25 described in one is roasted
Prepared by burning.
27. nano-carbon materials containing metallic atom according to claim 26, wherein, temperature of the roasting at 250-500 DEG C
Carried out under degree, carried out preferably at a temperature of 300-450 DEG C, the duration of the roasting is 1-24 hours, preferably 2-12
Hour.
Nano-carbon material containing metallic atom or claim 26-27 in 28. claim 1-10 and 25 described in any one
Nano-carbon material containing metallic atom described in middle any one 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, it is more excellent
Elect normal butane as.
A kind of 31. hydrocarbon dehydrogenation reaction methods, the method is included in presence or absence of under conditions of oxygen, in hydrocarbon dehydrogenation reaction bar
Under part, by nano-carbon material containing metallic atom or claim described in any one in hydrocarbon and claim 1-10 and 25
The contact of nano-carbon material containing metallic atom in 26-27 described in any one.
32. methods according to claim 31, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably
Normal butane.
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