CN106925319B - One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method - Google Patents
One kind 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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- CN106925319B CN106925319B CN201511031571.2A CN201511031571A CN106925319B CN 106925319 B CN106925319 B CN 106925319B CN 201511031571 A CN201511031571 A CN 201511031571A CN 106925319 B CN106925319 B CN 106925319B
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 417
- 238000000034 method Methods 0.000 title claims abstract description 169
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 56
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 46
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- -1 nitrogenous compound Chemical class 0.000 claims description 59
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- 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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- 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 compound 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 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
- 239000000376 reactant Substances 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
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 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
- 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 materials containing metallic atom and its preparation method and application, the nano-carbon material containing metallic atom contains the O element 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 spectroscopy, the content for the O element that peak within the scope of 529.5-530.8eV determines is 0.02-0.2 weight %, the ratio of the amount of the O element determined by the peak within the scope of 531.0-532.5eV and the amount of the O element determined by the peak within the scope of 532.6-533.5eV is 0.2-1, the ratio of the total amount of the amount and N element of the N element determined by the peak within the scope of 398.5-400.1eV is 0.7-1.The hydrocarbon dehydrogenation reaction method of the nano-carbon material containing metallic atom as catalyst is used the present invention also provides a kind of.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 materials containing metallic atom, and the invention further relates to a kind of nano carbon materials containing metallic atom
The preparation method of material and the nano-carbon material containing metallic atom prepared by this method, the present invention further relates to a kind of pass through will be above-mentioned
Nano-carbon material containing metallic atom is roasted and the nano-carbon material containing metallic atom for preparing, and the invention further relates to bases
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 technique
The dehydrogenation reaction of hydrocarbons is a kind of important reaction type, such as most of low-carbon olefine is to pass through low-carbon
The dehydrogenation reaction of alkane and obtain.Whether dehydrogenation reaction participates in be divided into direct dehydrogenation reaction (that is, oxygen according to oxygen
Gas is not involved in) and oxidative dehydrogenation (that is, oxygen participation) two classes.
A plurality of types of nano-carbon materials have been demonstrated equal to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation
With catalytic effect, its catalytic activity can then be improved by introducing oxygen atom and/or nitrogen-atoms in nano-carbon material.
Oxygen atom is introduced in nano-carbon material, can form hydroxyl, carbonyl, carboxyl, ester group on nano-carbon material surface
With the oxygen-containing functional groups such as acid anhydrides.
Oxygen atom can be introduced in nano-carbon material by carrying out oxidation processes realization to nano-carbon material, 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 be assisted while back flow reaction carry out microwave heating
Or sonic oscillation, to enhance the effect of oxidation reaction.It can but carry out back flow reaction in strong acid and/or strong oxidizing solution
Can have an adverse effect to the skeleton structure of nano-carbon material, or even destroy the skeleton structure of nano-carbon material.Such as: it will receive
Rice carbon material carries out back flow reaction in nitric acid, although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface,
Nano-carbon material is easily caused to be cut off and/or obviously increase the defects of graphite network structure position, to reduce nano carbon material
The performance of material, such as thermal stability.In addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, to introduce oxygen original
The introduction volume of the period of the day from 11 p.m. to 1 a.m, 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, locating chemical environment is not in nano-carbon material
Together, nitrogen-atoms is usually divided into chemical nitrogen and structure nitrogen.Chemical nitrogen mainly appears in material in the form of surface functional group
Surface, such as amino or nitrosyl radical surface nitrogen-containing functional group.Structure nitrogen refer to skeleton structure into nano-carbon material with
The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly include graphite mould nitrogen (that is,), pyridine type nitrogen (that is,) and
Pyrroles's type nitrogen (that is,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen
It is unsaturated nitrogen atom with pyrroles's type nitrogen, while replacing carbon atom, often will cause the missing for closing on carbon atom, form defect
Position.
Can by introduced in nano-carbon material synthesis process nitrogenous functional atmosphere (such as ammonia, nitrogen, urea,
Melamine), nitrogen is introduced into nano carbon material simultaneously in the synthesis process of nano-carbon material using high temperature and/or high pressure
In the skeleton structure of material and/or surface；It can also be by the way that nano-carbon material to be placed in nitrogenous functional atmosphere (such as ammonia, nitrogen
Gas, urea, melamine) in, nitrogen is introduced into the surface of nano-carbon material using high temperature and/or high pressure.High temperature and/or
For high pressure although 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 so generated are unevenly distributed on the surface of nano-carbon material, lead to nitrogenous nanometer
The performance of carbon material is unstable.It then can also be reacted with amine, by the way that nano-carbon material is carried out oxidation processes thus in nanometer
Carbon material surface introduces nitrogen-atoms, and the nitrogen-atoms so introduced is essentially chemical nitrogen.
Although the research of doping vario-property and its catalytic performance in relation to 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.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of nano-carbon material containing metallic atom, using this method
Metallic atom can not only be introduced on nano-carbon material surface, and can steadily improve heteroatomic content in nano-carbon material,
The structure of nano-carbon material itself is influenced simultaneously little.
It is another object of the present invention to provide a kind of nano-carbon materials containing metallic atom, this contains metallic atom nano-sized carbon
When material is used for the dehydrogenation reaction of hydrocarbons, higher feed stock conversion and selectivity of product can be obtained.
Another object of the present invention is to provide a kind of hydrocarbon dehydrogenation reaction method, this method can obtain higher raw material conversion
Rate and selectivity of product.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material contains C element, O element, 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 based on the element, the content of O element is 2-15 weight %, and the content of N element is 0.8-10 weight %, institute
The total amount for stating metallic element is 1-10 weight %, and 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 spectroscopy is IO t, by
The content for the O element that peak in x-ray photoelectron spectroscopy within the scope 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, by within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy
The amount for the O element that peak determines is IO c, the O element that is determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy
Amount is IO e, IO c/IO eIn the range of 0.2-1；This contains in metallic atom nano-carbon material, determines this by x-ray photoelectron spectroscopy
The total amount of N element in nano-carbon material containing metallic atom is IN t, by 398.5-400.1eV range in x-ray photoelectron spectroscopy
The amount for 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 present invention provides a kind of preparation sides of nano-carbon material containing metallic atom
Method, this method include that one kind is dispersed with to raw material nano carbon material, at least one nitrogenous compound and at least one metallization
The aqueous dispersions for closing object are reacted in closed container, and the nitrogenous compound is selected from NH3, hydrazine and urea, in reaction process,
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 present invention provides a kind of method systems by the second aspect according to the present invention
Standby nano-carbon material containing metallic atom.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material is to carry out the nano-carbon material containing metallic atom in terms of first aspect according to the present invention or third
Prepared by roasting.
According to the fifth aspect of the present invention, receiving containing metallic atom the present invention provides first aspect according to the present invention
Rice carbon material, the according to the present invention nano-carbon material containing metallic atom of third aspect or according to the present invention the 4th aspect
Nano-carbon material containing metallic atom as hydrocarbon dehydrogenation reaction catalyst application.
According to the sixth aspect of the invention, the present invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, is deposited
Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with first aspect according to the present invention containing metal
Atom nano-carbon material, the according to the present invention nano-carbon material containing metallic atom in terms of third or according to the present invention the 4th
The nano-carbon material containing metallic atom of a aspect contacts.
The preparation method of the nano-carbon material according to the present invention containing metallic atom steadily can not only regulate and control and/or improve
Metallic atom and heteroatomic content in nano-carbon material, while the structure of nano-carbon material itself is influenced small.Also, according to
The nano-carbon material containing metallic atom of the preparation method of the nano-carbon material containing metallic atom of the invention, preparation has stable property
Energy.
Nano-carbon material containing metallic atom according to the present invention shows good urge in the dehydrogenation reaction of hydrocarbons
Change performance, feed stock conversion and selectivity of product can be significantly improved.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing metallic atom prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo for the raw material nano carbon material that embodiment 1 uses.
Specific embodiment
In the present invention, nano-carbon material refers to that dispersed phase scale at least one dimension is less than the carbon material of 100nm.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material contains C element, O element, 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 according to the present invention, the metallic element, which is selected from, has catalytic action to hydrocarbon dehydrogenation reaction
Metallic element, be preferably selected from transition metal element, such as in the periodic table of elements Group IIIB metallic element, group ivb gold
Belong to element, Group VB metallic element, vib metals element, V Group IIB metallic element, group VIII metallic element, I B
Race's metallic element and group iib metallic element.The specific example 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 is used as hydrocarbon dehydrogenation at this time
When the catalyst of reaction, higher catalytic activity can be obtained.It is highly preferred that the metallic element is selected from group VIII metal member
Element is more preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum, and the carbon material containing metal nano is used as urging for hydrocarbon dehydrogenation reaction at this time
When agent, the catalytic activity further increased can be obtained.
Nano-carbon material containing metallic atom according to the present invention, on the basis of the total amount of the nano-carbon material containing metallic atom
And based on the element, the content of O element is 2-15 weight %, preferably 3-9 weight %, more preferably 4-8 weight %；N element
Content is 0.8-10 weight %, preferably 1-6 weight %, more preferably 1.1-5 weight %；The total amount of metallic element is 1-10 weight
Measure %, preferably 1.2-6 weight %, more preferably 1.5-4.5 weight %；The content of C element is 65-96.2 weight %, preferably
For 79-94.8 weight %, more preferably 82.5-93.4 weight %.Wherein, the content of each element uses x-ray photoelectron spectroscopy
Method measurement.Sample before testing 150 DEG C at a temperature of dry 3 hours in helium atmosphere.
In the present invention, X-ray photoelectron spectroscopic analysis is in Thermo Scientific company equipped with Thermo
It is tested on the ESCALab250 type x-ray photoelectron spectroscopy of Avantage V5.926 software, excitaton source is monochromatization Al
K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, base vacuum when analysis test
It is 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage software
Upper carry out data processing carries out quantitative analysis using sensitivity factor method in analysis module.
Nano-carbon material containing metallic atom according to the present invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity
The total content for the oxygen element that sub- power spectrum determines is IO t, determined by the peak within the scope of 529.5-530.8eV in x-ray photoelectron spectroscopy
O element (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 according to the present invention,
The content of the O element determined by the peak within the scope of 531.0-533.5eV in x-ray photoelectron spectroscopy 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 numberical range, " ×-× in the range of " it include two binary values.
In the present invention, the area of the O1s spectral peak in x-ray photoelectron spectroscopy is denoted as AO 1, O1s spectral peak is divided into two groups
The area of spectral peak (corresponding to the oxygen species being connected with metallic atom) within the scope of 529.5-530.8eV is denoted as A by peakO 2, will
The area of spectral peak (corresponding to the oxygen species not being connected with metallic atom) within the scope of 531.0-533.5eV is denoted 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 according to the present invention, by 531.0-532.5eV range in x-ray photoelectron spectroscopy
The amount for the O element (that is, C=O) that interior peak determines is IO c, by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy
The amount of determining O element (that is, CO) 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, by the spectral peak in x-ray photoelectron spectroscopy within the scope of 531.0-533.5eV (corresponding to what is be not connected with metallic atom
Oxygen species) be further separated into two groups of peaks, i.e., spectral peak within the scope of 531.0-532.5eV (corresponding to C=O species) and
Spectral peak (corresponding to C-O species) within the scope of 532.6-533.5eV, by the area of the spectral peak within the scope of 531.0-532.5eV
It is denoted as AO 4, the area of the spectral peak within the scope of 532.6-533.5eV is denoted as AO 5, IO c/IO e=AO 4/AO 5。
Nano-carbon material containing metallic atom according to the present invention, in the nano-carbon material containing metallic atom by X-ray light
It is true by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy on the basis of the total amount for 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 within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy can be 5-
50 weight %, preferably 5-40 weight %, more preferably 7-30 weight %.In the present invention, by x-ray photoelectron spectroscopy
The area A of C1s spectral peakC 1C1s spectral peak in x-ray photoelectron spectroscopy is divided into two groups of peaks, that is, existed by the total amount for determining C element
Spectral peak (corresponding to graphite mould carbon species) within the scope of 284.7-284.9eV and the spectral peak within the scope of 286.0-288.8eV
(corresponding to non-graphite type carbon species), the area of the spectral peak within the scope of 284.7-284.9eV is denoted as AC 2, will be in 286.0-
The area of spectral peak within the scope of 288.8eV is denoted as AC 3, true by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy
Content=A of fixed C elementC 2/AC 1, the C element that is determined by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy
Total content=AC 3/AC 1。
Nano-carbon material containing metallic atom according to the present invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity
The amount for the C element that peak in sub- power spectrum within the scope of 288.6-288.8eV determines is IC c, by 286.0- in x-ray photoelectron spectroscopy
The amount for the C element that peak within the scope 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 spectroscopy in 286.0-288.8eV range
Interior spectral peak (corresponding to agraphitic carbon species) is further divided into two groups of peaks, i.e., the spectral peak within the scope of 286.0-286.2eV
(corresponding to hydroxyl and ether type carbon species) and the spectral peak within the scope of 288.6-288.8eV (correspond to carboxyl, acid anhydride and ester type carbon
Species), the area of the spectral peak within the scope of 286.0-286.2eV is denoted as AC 4, by the spectral peak within the scope of 288.6-288.8eV
Area be denoted as AC 5, IC c/IC e=AC 5/AC 4。
Nano-carbon material containing metallic atom according to the present invention determines that this contains metallic atom and receives by x-ray photoelectron spectroscopy
The total amount of N element in rice carbon material is IN t, the N that is determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy
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 range.
Nano-carbon material containing metallic atom according to the present invention, by 400.6-401.5eV range in x-ray photoelectron spectroscopy
Content is lower or even is free of for the N element (that is, graphite mould nitrogen) that interior peak determines.Generally, according to the present invention to contain metallic atom
In nano-carbon material, the amount of the N element determined by the peak within the scope of 400.6-401.5eV in x-ray photoelectron spectroscopy is IN g,
IN g/IN tFor not higher than 0.3, generally 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 peak in x-ray photoelectron spectroscopyN 1, by X-ray
N1s spectral peak in photoelectron spectroscopy is divided into two groups of peaks, i.e., the spectral peak within the scope of 400.6-401.5eV (corresponds to graphite mould nitrogen
Species) and 398.5-400.1eV within the scope of spectral peak (nitrogen species in addition to graphite mould nitrogen), will be in 400.6-401.5eV model
The area of spectral peak in enclosing is denoted as AN 2, the area of the spectral peak within the scope of 398.5-400.1eV is denoted as AN 3, IN c/IN t=AN 3/
AN 1, IN g/IN t=AN 2/AN 1, when obtained ratio is lower than 0.01, it is believed that be free of such species, and containing such species
Amount is denoted as 0.
In the present invention, position combination as corresponding to the summit at the peak at each peak be can determine that, range determines by mentioned earlier
Peak refer to combination corresponding to summit can peak within that range, in the range may include a peak, also can wrap
Include more than two peaks.Such as: the peak within the scope of 398.5-400.1eV refers to that combination corresponding to summit can be in 398.5-
Whole peaks in the range of 400.1eV.
Nano-carbon material containing metallic atom according to the present invention can exist with common various forms, be specifically as follows but
It is not limited to carbon nanotube containing metallic atom, graphene containing metallic atom, thin layer graphite containing metallic atom, nano-sized carbon containing metallic atom
One of particle, carbon nano-fiber containing metallic atom, Nano diamond containing metallic atom and fullerene containing metallic atom or two
Kind or more combination.The carbon nanotube containing metallic atom can be single-walled carbon nanotube containing metallic atom, contain metallic atom
The combination of one or more of double-walled carbon nano-tube and multi-walled carbon nanotube containing metallic atom.It is according to the present invention to contain gold
Belong to atom nano-carbon material, preferably multi-walled carbon nanotube containing metallic atom.
Nano-carbon material containing metallic atom according to the present invention, it is preferable that the multi-walled carbon nanotube containing metallic atom
Specific surface area is in 50-500m2In the range of/g, the catalytic of the nano-carbon material containing metallic atom can be further improved in this way
Can, especially as the catalytic performance of the catalyst of hydrocarbons dehydrogenation reaction.It is received it is highly preferred that this contains metallic atom multi wall carbon
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 nanotube
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 nanotube
In 125-180m2In the range of/g.In the present invention, the specific surface area is measured by nitrogen adsorption BET method.
Nano-carbon material containing metallic atom according to the present invention, the multi-walled carbon nanotube 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, better catalytic effect, especially urging as hydrocarbons dehydrogenation reaction can be obtained in this way
When agent, preferably catalysis 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, W400For in 400 DEG C of the at a temperature of mass loss rate that measures, W800For at 800 DEG C
At a temperature of the mass loss rate that measures, W500For in 500 DEG C of the at a temperature of mass loss rate that measures；The weight-loss ratio uses
Thermogravimetric analyzer measures in air atmosphere, and test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample is before testing
It is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere.
In a preferred embodiment of the invention, the nano-carbon material containing metallic atom preferably contains metal original
Sub- multi-walled carbon nanotube, this contains the specific surface area of metallic atom multi-walled carbon nanotube 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 according to the present invention, for oxygen atom and nitrogen-atoms outside it is other nonmetallic miscellaneous
Atom, such as sulphur atom and phosphorus atoms, content can be customary amount.Generally, nanometer containing metallic atom according to the present invention
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
0.5 weight % hereinafter, preferably 0.2 weight % hereinafter, more preferably 0.1 weight % hereinafter, further preferably 0.05 weight
Measure % or less.Nano-carbon material containing metallic atom according to the present invention can also contain other metals in addition to aforesaid metal elements
Atom, other metallic atoms for example can be for from the catalyst used when preparing nano-carbon material.Other gold
The content for belonging to atom is generally 2.5 weight % hereinafter, preferably 2 weight % are hereinafter, further preferably 1 weight % is hereinafter, more
Further preferably 0.5 weight % is hereinafter, particularly preferably 0.2 weight % or less.
According to the second aspect of the invention, the present invention provides a kind of preparation sides of nano-carbon material containing metallic atom
Method, this method include that one kind is dispersed with to raw material nano carbon material, at least one nitrogenous compound and at least one metallization
The aqueous dispersions for closing object are reacted in closed container.
The nitrogenous compound is selected from NH3, hydrazine and urea.
According to the method for the present invention, the metallic element in the metallic compound, which is selected from, there is catalysis to make hydrocarbon dehydrogenation reaction
Metallic element is preferably selected from transition metal element (that is, the metallic compound is preferably selected from the chemical combination containing transition metal
Object).Metallic element in the metallic compound specifically can be selected from but not limited to Group IIIB metal member in the periodic table of elements
Element, group ivb metallic element, Group VB metallic element, vib metals element, V Group IIB metallic element, group VIII gold
Belong to element, I B-group metal element and group iib metallic element.The specific example of 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 thus prepared can obtain higher catalysis and live when being used as the catalyst of 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 catalytic activity further increased can be obtained.
The metallic compound can be selected from metal nitrate, metal acetate, metal carbonate, metal sulfate, gold
Belong to subcarbonate, metal hydroxides, metal chloride, metal oxalate and metal complex, it is further preferably golden
Belong to 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
It is sub- to change nickel, nickel hydroxide, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, acetic acid
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 four ammino palladium of nitric acid), 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.
According to the method for the present invention, the type of metallic compound can also be carried out according to the type of nitrogenous compound excellent
Change, to further increase catalytic activity of the nano-carbon material containing metallic atom thus prepared when being used as hydrocarbon dehydrogenation reaction.?
In a kind of preferred embodiment, the nitrogenous compound is NH3, the metallic element in the metallic compound is selected from iron, cobalt
And nickel, the metallic compound are preferably one or both of 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
Object 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 of hydrochlorate and metal complex, more preferably metal acetate and/or metal complex.Again
In a kind of preferred embodiment, the nitrogenous compound is urea, the metallic element in the metallic compound be selected from ruthenium and
Rhodium, the metallic compound are preferably metal complex.
According to the method for the present invention, the dosage of the nitrogenous compound and the metallic compound can be according to it is contemplated that former
The content and type of the nitrogen, oxygen element and the metallic element that introduce in material nano-carbon material are selected.Finally making
Standby nano-carbon material containing metallic atom is when being used as the catalyst of hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material: nitrogenous
Compound: the weight ratio of metallic compound is in the range of 1:0.01-10:0.01-10, the nanometer containing metallic atom that thus prepares
Carbon material can obtain the catalytic effect further increased when being used as the catalyst of hydrocarbon dehydrogenation reaction.It is highly preferred that raw material nano
Carbon material: nitrogenous compound: the weight ratio of metallic compound is in the range of 1:0.02-5:0.05-8.It is further preferred that former
Expect nano-carbon material: nitrogenous compound: the weight ratio of metallic compound is in the range of 1:0.02-2:0.06-6.Further
Preferably, raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in the range of 1:0.02-1:0.08-5.
It is particularly preferred that raw material nano carbon material: nitrogenous compound: model of the weight ratio of metallic compound in 1:0.02-0.5:0.8-5
In enclosing.
According to the method for the present invention, the molar ratio of the nitrogenous compound and the metallic compound is preferably in 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 that thus prepares
Material surface is more uniformly spread, and also has more excellent catalytic activity when being used as the catalyst of hydrocarbon dehydrogenation reaction.More
Preferably, the molar ratio of the nitrogenous compound and the metallic compound is preferably in the range of 1:0.03-6.
Method according to the invention it is possible to be selected according to dosage of the amount of raw material nano carbon material to water.Preferably,
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:2-500, when within the scope of the dosage of water being in this, nano-sized carbon
The structural form retentivity of material during processing is more preferable, such as: for carbon nanotube, during processing substantially not
It is cut off.It is highly preferred that raw material nano carbon material: H2The weight ratio of O is in the range of 1:5-250.It is further preferred that former
Expect nano-carbon material: H2The weight ratio of O is in the range of 1:10-200.It is further preferred that raw material nano carbon material: H2O's
Weight ratio is in the range of 1:20-200.It is particularly preferred that raw material nano carbon material: H2Model of the weight ratio of O in 1:50-200
In enclosing.
According to the method for the present invention, dosage can also be carried out according to the type of nitrogenous compound and metallic compound excellent
Change, to further increase catalysis of the nano-carbon material containing metallic atom thus prepared when being used as the catalyst of hydrocarbon dehydrogenation reaction
Activity.In a preferred embodiment, the nitrogenous compound is NH3, metallic element choosing in the metallic compound
From iron, cobalt and nickel, the metallic compound is preferably selected from one in metal acetate, basic metal hydrochloride and metal oxalate
Kind is two or more, more preferably metal acetate and/or metal oxalate, raw material nano carbon material: nitrogenous compound: metal
The weight ratio of compound is preferably in the range of 1:0.01-1:0.5-6, more preferably in the range of 1:0.01-0.2:0.9-5.
In the preferred embodiment, nitrogenous compound: the molar ratio of metallic compound is more excellent preferably in the range of 1:0.1-10
It is selected in the range of 1:2-6.In the preferred embodiment, raw material nano carbon material: H2The weight ratio of O is preferably in 1:20-
In the range of 100, more preferably in the range of 1:40-80.
In another preferred embodiment, the nitrogenous compound is hydrazine, the metal member 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
One or more of four ammino palladium of palladium and nitric acid), more preferably metal acetate and/or metal complex, raw material are received
Rice carbon material: nitrogenous compound: the weight ratio of metallic compound is preferably in the range of 1:0.05-3:2-6, more preferably 1:
In the range of 0.2-0.5:4-5.In the preferred embodiment, nitrogenous compound: the molar ratio of metallic compound preferably exists
In the range of 1:0.2-10, more preferably in the range of 1:0.6-1.In the preferred embodiment, raw material nano carbon material:
H2The weight ratio of O is preferably in the range of 1:20-250, more preferably in the range of 1:50-100.
In another preferred embodiment, the nitrogenous compound is 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: nitrogenous compound: the weight ratio of metallic compound is preferably in the range of 1:0.08-6:0.02-2, more preferably
In the range of 1:0.3-0.6:0.1-1.In the preferred embodiment, nitrogenous compound: the molar ratio of metallic compound
It is preferred that in the range of 1:0.02-2, more preferably in the range of 1:0.02-0.4.In the preferred embodiment, raw material is received
Rice carbon material: H2The weight ratio of O is preferably in the range of 1:20-100, more preferably in the range of 1:40-80.
According to the method for the present invention, the condition of the reaction is to be enough to improve oxygen atom, nitrogen in raw material nano carbon material
Subject to the content of atom and metallic atom.Preferably, in reaction process, range 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, can not only effectively improve in raw material nano carbon material
Oxygen atom, nitrogen-atoms and metal atom content, and the structural form of raw material nano carbon material will not be generated and be significantly affected.More
Preferably, in reaction process, the temperature of the aqueous dispersions is in the range of 120-240 DEG C.
According to the method for the present invention, the duration of the reaction can be selected according to the temperature of reaction, with can
It is introduced in raw material nano carbon material subject to enough oxygen atoms, nitrogen-atoms and metallic atom.Generally, 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 common various methods, such as can incite somebody to action
Raw material nano carbon material is dispersed in water (preferably deionized water), and the nitrogenous compound and the metal compound is then added
Object, to obtain the aqueous dispersions.In order to further increase the dispersion effect of raw material nano carbon material, while shortening dispersion
Raw material nano carbon material can be dispersed in water by the time using the method for sonic oscillation.The condition of the sonic oscillation can be with
For conventional selection, generally, the frequency of the sonic oscillation can be 10-200kHz, preferably 90-140kHz；The ultrasound
The duration of oscillation can be 0.1-6 hours, preferably 0.5-4 hours.According to the method for the present invention, the nitrogenous compound
And the metallic compound can be provided according to specific type in the form of solution (preferred aqueous solutions), it can also be with pure material
Form provide, be not particularly limited.
According to the method for the present invention, the content of oxygen element and nitrogen does not limit especially in the raw material nano carbon material
It is fixed, it can be conventional selection.Generally, in the raw material nano carbon material content of oxygen element be not higher than 1.5 weight %, it is excellent
It is selected as further preferably being not higher than 0.3 weight % not higher than 1.2 weight %, more preferably not above 0.5 weight %；Nitrogen member
The content of element is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, into one
Step is preferably not higher than 0.05 weight %, still more preferably for not higher than 0.02 weight %.According to the method for the present invention, described
The total amount of oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms in raw material nano carbon material
It (based on the element) can be customary amount.Generally, remaining in the raw material nano carbon material in addition to oxygen element and nitrogen
The total amount (based on the element) of nonmetallic heteroatoms is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably
Not higher than 0.1 weight %, it is further preferably not higher than 0.05 weight %.According to the method for the present invention, the raw material nano carbon
Material may contain some metallic elements according to the difference in source, such as from using when preparing raw material nano carbon material
Metallic atom in catalyst.The content (based on the element) of metallic atom is generally 2.5 weights in the raw material nano carbon material
Measure % hereinafter, preferably 1.8 weight % hereinafter, further preferably 0.5 weight % hereinafter, still more preferably be 0.1 weight
Measure % or less.
According to the method for the present invention, raw material nano carbon material can be carried out pre- before use using method commonly used in the art
Processing (as washed), to remove some impurity of raw material nano carbon material surface；It can also directly be used without pretreatment.
In embodiment disclosed by the invention, raw material nano carbon material is not pre-processed using preceding.
Method according to the invention it is possible to handle the nano-carbon material of various existing forms, received to improve this
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
One or both of mitron, graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene with
On combination.The carbon nanotube can for one of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube or
Two or more combinations.Preferably, the raw material nano carbon material is carbon nanotube, more preferably multi-walled carbon nanotube.
According to the method for the present invention, in a preferred embodiment, the raw material nano carbon material is that multi wall carbon is received
Mitron, the specific surface area of the multi-walled carbon nanotube can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-
260m2/ g, further preferably 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nanotube, temperature of the multi-walled carbon nanotube at 400-800 DEG C
The weight-loss ratio spent in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It can 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 more preferably embodiment of the invention, the raw material nano carbon material is multi-walled carbon nanotube,
The specific surface area of the multi-walled carbon nanotube is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, into
One step is preferably 120-190m2/g；Weight-loss ratio of the multi-walled carbon nanotube 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 range, more preferably in the range of 0.05-0.35, further preferably in the range of 0.05-0.15.
According to the method for the present invention, the reaction carries out in closed container.The reaction can self-generated pressure (that is,
Do not apply pressure additionally) under carry out, can also carry out under pressure.Preferably, it is described reaction at autogenous pressures into
Row.The closed container can be the common reactor for being able to achieve sealing and heating, such as autoclave.
It according to the method for the present invention, can also include solid matter being isolated from the mixture that reaction obtains, and will divide
The solid matter separated out is dried, to obtain the nano-carbon material containing metallic atom.
Solid matter can be isolated from the mixture that reaction obtains using common solid-liquid separating method, such as centrifugation,
Filtering and decantation one or more of combination.
The condition of the drying can be conventional selection, be can remove the volatile materials in the solid matter isolated
It is quasi-.Generally, the drying can 50-200 DEG C at a temperature of carry out, preferably 80-180 DEG C at a temperature of carry out, it is more excellent
It is carried out at a temperature of being selected in 120-160 DEG C.The duration of the drying can be selected according to dry temperature and mode.
Generally, the duration of the drying can be 0.5-48 hours, preferably 6-24 hours, more preferably 8-12 hours.Institute
Stating drying can carry out under normal pressure (that is, 1 standard atmospheric pressure), can also carry out at reduced pressure.From further increasing
The angle of dry efficiency is set out, and the drying preferably carries out at reduced pressure.
According to the method for the present invention, oxygen atom, nitrogen-atoms and the metal that can be effectively improved in raw material nano carbon material are former
Sub- content, while the structural form of raw material nano carbon material will not be generated and be significantly affected.
According to the third aspect of the present invention, the present invention provides one kind contains metal by prepared according to the methods of the invention
Atom nano-carbon material.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal
Atom nano-carbon material is by the nano-carbon material containing metallic atom of first aspect according to the present invention or according to the present invention
Prepared by the nano-carbon material containing metallic atom of three aspects is roasted.
The roasting can carry out under normal conditions.Preferably, it is described roasting 250-500 DEG C at a temperature of carry out.
It is highly preferred that it is described roasting 300-450 DEG C at a temperature of carry out.The duration of the roasting can be according to the temperature of roasting
It is selected.Generally, the duration of the roasting can be 1-24 hours, preferably 2-12 hours, such as 4-12 hours.Institute
Stating roasting can carry out in oxygen-containing atmosphere, can also carry out in the atmosphere formed by inert gas.The oxygen-containing atmosphere can
Think air atmosphere；It can also be the mixed atmosphere that oxygen and inert gas are mixed to form, in the mixed atmosphere, oxygen contains
Amount can be 0.1-22 volume %.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 according to the present invention is received by prepared by method of the invention containing metallic atom
Rice carbon material has good catalytic performance, and higher catalytic activity is especially shown in hydrocarbons dehydrogenation reaction.
Nano-carbon material containing metallic atom according to the present invention is received by prepared by method of the invention containing metallic atom
Rice carbon material can be directly used as catalyst, can also 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 method of the invention
Material and binder.The binder can be selected according to the specifically used occasion of the preformed catalyst, can satisfy
It subject to requirement, such as can be organic binder and/or inorganic binder.The organic binder can be common each
Kind polymer-type binder, the inorganic binder can be common various heat-resistant inorganic oxides, such as aluminium 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 binder is preferably inorganic binder.The shaped catalyst
In agent, the content of the nano-carbon material containing metallic atom can be selected according to specifically used requirement, be not particularly limited, generally
Ground, on the basis of the total amount of the preformed catalyst, the content of the nano-carbon material containing metallic atom can be 5-95 weight
Measure %.
According to the fifth aspect of the present invention, receiving containing metallic atom the present invention provides first aspect according to the present invention
Rice carbon material, the according to the present invention nano-carbon material containing metallic atom of third aspect or according to the present invention the 4th aspect
Nano-carbon material containing metallic atom as hydrocarbon dehydrogenation reaction catalyst application.
Application according to the present invention, the nano-carbon material containing metallic atom are used directly for hydrocarbon dehydrogenation reaction, can also
To be used for hydrocarbon dehydrogenation reaction after molding.The dehydrogenation reaction can carry out in the presence of oxygen, can not also be in the presence of oxygen
It carries out.Preferably, the dehydrogenation reaction carries out in the presence of oxygen, can obtain better catalytic effect in this way.
According to the sixth aspect of the invention, the present invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, is deposited
Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with first aspect according to the present invention containing metal
Atom nano-carbon material, the according to the present invention nano-carbon material containing metallic atom in terms of third or according to the present invention the 4th
The nano-carbon material containing metallic atom of a aspect contacts.
Hydrocarbon dehydrogenation reaction method according to the present invention, the nano-carbon material containing metallic atom are used directly for connecing with hydrocarbon
Touching is used to contact with hydrocarbon after can also forming the nano-carbon material containing metallic atom.
Hydrocarbon dehydrogenation reaction method according to the present invention can carry out dehydrogenation to a plurality of types of hydrocarbon, to obtain unsaturation
Hydrocarbon, such as alkene.According to the method for the present invention particularly suitable for carrying out dehydrogenation to alkane, to obtain alkene.
According to the method for the present 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- methylpentane,
3- methylpentane, 2,3- dimethylbutane, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- second
Base pentane, 3- ethylpentane, 2,3- dimethyl pentane, 2,4- dimethyl pentane, normal octane, 2- methyl heptane, 3- methyl heptane,
4- methyl heptane, 2,3- dimethylhexane, 2,4- dimethylhexane, 2,5- dimethylhexane, 3- ethyl hexane, 2,2,3- front three
Base pentane, 2,3,3- trimethylpentane, 2,4,4- trimethylpentane, 2- methyl -3- ethylpentane, n -nonane, 2- methyloctane,
3- methyloctane, 4- methyloctane, 2,3- dimethyl heptane, 2,4- dimethyl heptane, 3- ethyl heptane, 4- ethyl heptane, 2,
3,4- trimethyl cyclohexane, 2,3,5- trimethyl cyclohexane, 2,4,5- trimethyl cyclohexane, 2,2,3- trimethyl cyclohexane, 2,2,4- front three
Base hexane, 2,2,5- trimethyl cyclohexane, 2,3,3- trimethyl cyclohexane, 2,4,4- trimethyl cyclohexane, 2- methyl -3- ethyl hexane,
2- methyl -4- ethyl hexane, 3- methyl -3- ethyl hexane, 3- methyl -4- ethyl hexane, 3,3- diethylpentane, 1- methyl -
2- ethyl cyclohexane, 1- methyl -3- ethyl cyclohexane, 1- methyl -4- ethyl cyclohexane, n-propyl hexamethylene, isopropyl hexamethylene
Alkane, trimethyl-cyclohexane (the various isomers including trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- front threes
Butylcyclohexane, 1,2,5- trimethyl-cyclohexane, 1,3,5- trimethyl-cyclohexane), n-decane, 2- methylnonane, 3- methylnonane,
4- methylnonane, 5- methylnonane, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyl octane, 4- ethyl octane, 2,
3,4- trimethylheptane, 2,3,5- trimethylheptane, 2,3,6- trimethylheptane, 2,4,5- trimethylheptane, 2,4,6- front three
Base heptane, 2,2,3- trimethylheptane, 2,2,4- trimethylheptane, 2,2,5- trimethylheptane, 2,2,6- trimethylheptane, 2,
3,3- trimethylheptane, 2,4,4- trimethylheptane, 2- methyl -3- ethyl heptane, 2- methyl -4- ethyl heptane, 2- methyl -5-
Ethyl heptane, 3- methyl -3- ethyl heptane, 4- methyl -3- ethyl heptane, 5- methyl -3- ethyl heptane, 4- methyl -4- ethyl
Heptane, 4- propyl heptane, 3,3- diethylhexane, 3,4- diethylhexane, 2- methyl -3,3- diethylpentane, vinylbenzene, 1-
In phenyl-propane, 2- phenyl-propane, 1- phenyl butane, 2- phenyl butane, 1- phenyl pentane, 2- phenyl pentane and 3- phenyl pentane
A combination of one or more.It is highly preferred that the hydrocarbon be one of propane, normal butane, iso-butane and vinylbenzene or
It is two or more.It is further preferred that the hydrocarbon is normal butane.
Hydrocarbon dehydrogenation reaction method according to the present invention, the reaction can carry out under conditions of there are oxygen, can also be with
Under conditions of oxygen is not present.Preferably, hydrocarbon dehydrogenation reaction method according to the present invention, under conditions of there are oxygen into
Row.When method of the invention carries out under conditions of there are oxygen, the dosage of oxygen can be conventional selection.Generally, hydrocarbon
Molar ratio with oxygen can be 0.01-100:1, preferably 0.1-10:1, more preferably 0.2-5:1, most preferably 0.3-2:
1。
Hydrocarbon and oxygen can be sent into reactor by carrier gas and contain metal by hydrocarbon dehydrogenation reaction method according to the present invention
Atom nano-carbon material haptoreaction.The carrier gas can for it is common at reaction conditions will not with reactant and react generation
The gas that object occurs chemical interaction and will not decompose, in nitrogen, carbon dioxide, rare gas and vapor
A combination of one or more.The dosage of the carrier gas can be conventional selection.Generally, the content of carrier gas can be with 30-
99.5 volume %, preferably 50-99 volume %, more preferably 70-98 volume %.
The temperature of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be conventional selection, to be enough to send out hydrocarbon
Subject to raw dehydrogenation reaction.Generally, the contact can 200-650 DEG C at a temperature of carry out, preferably in 300-600 DEG C of temperature
Degree is lower to carry out, more preferably 350-550 DEG C at a temperature of carry out, further preferably 400-450 DEG C at a temperature of carry out.
Hydrocarbon dehydrogenation reaction method according to the present invention, the contact can carry out in fixed bed reactors, can also be
It carries out, is not particularly limited in fluidized-bed reactor.Preferably, the contact carries out in fixed bed reactors.
The duration of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be selected according to the temperature of contact
It selects, when such as described contact carries out in fixed bed reactors, holding for contact can be indicated with the volume space velocity of the gas of charging
The continuous time.Generally, the volume space velocity of the gas of charging can be 0.1-10000h-1, preferably 1-6000h-1, more preferably
5-5000h-1, further preferably 10-4000h-1, such as 800-1200h-1。
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, outfit of the X-ray photoelectron spectroscopic analysis in Thermo Scientific company
It is tested on the ESCALab250 type x-ray photoelectron spectroscopy for having Thermo Avantage V5.926 software, excitaton source
For monochromatization Al K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, analysis test
When base vacuum be 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo
Data processing is carried out on Avantage software, and quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is being surveyed
It is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before examination.
In following embodiment and comparative example, thermogravimetric analysis carries out on TA5000 thermal analyzer, and test condition is air gas
Atmosphere, heating rate are 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
It is 3 hours dry in helium atmosphere with the pressure of 1 normal atmosphere.Using the ASAP2000 type N of Micromertrics company, the U.S.2
Physical adsorption appearance measurement the specific area.Raw material nano carbon material is analyzed using the high-resolution-ration transmission electric-lens of FEI Co., U.S. production
And the microscopic appearance of the nano-carbon material containing metallic atom.
Embodiment 1-45 is for illustrating nano-carbon material containing metallic atom and preparation method thereof of the invention.
Embodiment 1
(1) using 20g as multi-walled carbon nanotube (the specific surface area 136m of raw material nano carbon material2/ g, oxygen atom content
For 0.3 weight %, nitrogen atom content is 0.02 weight %, and (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, is purchased from Chinese science
Chengdu organic chemistry Co., Ltd, institute) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition
It include: frequency for 140kHz, 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, to obtain aqueous dispersions, wherein press raw material nano carbon material: NH3: metallic compound:
H2The weight ratio of O is that the ratio of 1:0.2:5:50 feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 140 DEG C of temperature
Under, it reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction
Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big
Air pressure, similarly hereinafter), after 12 hours dry at a temperature of 120 DEG C, nano-carbon material containing metallic atom is obtained, this contains metallic atom and receives
Composition, specific surface area and the w of rice carbon material500/w800It is listed in table 1.
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing metallic atom of preparation, and Fig. 2 is as the more of raw material
The transmission electron microscope photo of wall carbon nano tube.It can be seen that the microcosmic of the nano-carbon material containing metallic atom from Fig. 1 and Fig. 2
Form is good, and it is little to show that reaction process influences the structure of nano-carbon material.
Comparative example 1
Aqueous dispersions same as Example 1 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in
In the oil bath that temperature is 140 DEG C, back flow reaction 24 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask
After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120
DEG C after dry 12 hours, nano-carbon material containing metallic atom is obtained.The nature parameters of the nano-carbon material containing metallic atom of preparation
It is 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, in deionized water by the dispersion of raw material nano carbon material, being then added
NH3, to obtain aqueous dispersions, wherein press raw material nano carbon material: NH3: metallic compound: H2The weight ratio of O is 1:0.2:
The ratio of 0:50 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 raw material nano carbon material dispersion in deionized water, then plus
Enter metallic compound, to obtain aqueous dispersions, wherein press raw material nano carbon material: NH3: metallic compound: H2The weight ratio of O
It feeds intake for the ratio of 1:0:5:50.The nature parameters of the nano-carbon material containing metallic atom of preparation 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 raw material nano carbon material dispersion in deionized water, then plus
Enter metallic compound, to obtain aqueous dispersions, wherein NH in the mole and embodiment 1 of nickel acetate3With always rubbing for nickel acetate
Your amount is identical, and the dosage of raw material nano carbon material and water is same as Example 1.The nano-carbon material containing metallic atom of preparation
Nature parameters are listed in table 1.
Comparative example 5
Ultrasound in deionized water, will be dispersed in using the nano-carbon material dispersion of method identical with comparative example 2 preparation
It is carried out under oscillating condition, sonic oscillation condition includes: that frequency is 140kHz, and the time is 0.5 hour.Then, metal compound is added
Object, to obtain aqueous dispersions, wherein (nano carbon material is prepared using method identical with comparative example 2 by raw material nano carbon material
The raw material nano carbon material used when material): metallic compound: H2The weight ratio of O is that the ratio of 1:0.2:50 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, it is cooled to room temperature to the temperature in autoclave, opens reaction kettle, reaction mixture is carried out
Filtering and washing, and collect solid matter.By the solid matter being collected into normal pressure, 120 DEG C at a temperature of it is 12 hours dry after,
Nano-carbon material containing metallic atom is obtained, which lists in table 1.
Embodiment 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), make
Specific surface area for the multi-walled carbon nanotube (be purchased from Shandong great Zhan nano material Co., Ltd) of raw material nano carbon material is
251m2/ g, the weight-loss ratio in 400-800 DEG C of temperature range are w800, weight-loss ratio in 400-500 DEG C of temperature range
For w500, w500/w800Be 0.33, oxygen atom content is 0.62 weight %, and 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
For 0.08 weight %.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 1.
Embodiment 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, it, will in step (2)
Obtained aqueous dispersions 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 of the nano-carbon material containing metallic atom of preparation 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 that the ratio of 1:1:2:50 feeds intake.Preparation contains 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 that the ratio of 1:0.05:5:50 feeds intake.Preparation contains metal
The nature parameters of atom nano-carbon material are listed in table 1.
Embodiment 6
Using 20g as multi-walled carbon nanotube (the specific surface area 183m of raw material nano carbon material2/ g, oxygen atom content are
0.2 weight %, nitrogen atom content are 0.01 weight %, remaining 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, the academy of sciences) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation
Condition includes: that frequency is 90kHz, and the time is 4 hours.Then, NH is added3(being provided in the form of 36 weight % aqueous solutions) and make
For the ferric oxalate of metallic compound, to obtain aqueous dispersions, wherein press raw material nano carbon material: NH3: metallic compound: H2O
Weight ratio be 1:0.02:2.5:50 ratio feed intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 240 DEG C of temperature
Under, it reacts 12 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction
Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into normal pressure, 160 DEG C
At a temperature of after dry 8 hours, obtain nano-carbon material containing metallic atom, which exists
It is 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 raw material nano carbon material dispersion in deionized water, then plus
Enter ferric oxalate, to obtain aqueous dispersions, wherein NH in the mole and embodiment 6 of ferric oxalate3With the integral molar quantity of ferric oxalate
Identical, the dosage of raw material nano carbon material and water is same as Example 6.The property ginseng of the nano-carbon material containing metallic atom of preparation
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
Specific surface area for the multi-walled carbon nanotube (be purchased from Shandong great Zhan nano material 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 s) total content be 0.01 weight %, metallic atom total content be 1.6 weight %.Preparation
The nature parameters of the nano-carbon material containing metallic atom listed in table 1.
Embodiment 8
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, it, will in step (2)
Obtained aqueous dispersions 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 of the nano-carbon material containing metallic atom of preparation 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 remaining unchanged with the total weight of ferric oxalate, make NH3: the molar ratio of ferric oxalate is 1:8.Preparation contains 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
The nickel oxalate of sour iron equimolar amounts replaces.The nature parameters of the nano-carbon material containing metallic atom of preparation 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
The basic nickel carbonate of sour iron equimolar amounts replaces.The nature parameters of the nano-carbon material containing metallic atom of preparation arrange in table 1
Out.
Embodiment 12
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), grass
The cobalt acetate of sour iron equimolar amounts replaces.The nature parameters of the nano-carbon material containing metallic atom of preparation 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
The acid chloride of sour iron equimolar amounts replaces.The nature parameters of the nano-carbon material containing metallic atom of preparation 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
The ruthenium acetate of sour iron equimolar amounts replaces.The nature parameters of the nano-carbon material containing metallic atom of preparation 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, in deionized water by the dispersion of raw material nano carbon material, be then added hydrazine (in the form of 50 weight % aqueous solutions provide) and
As the acid chloride of metallic compound, to obtain aqueous dispersions, wherein press raw material nano carbon material: hydrazine: metallic compound:
H2The weight ratio of O is that the ratio of 1:0.2:4.5:100 feeds intake；In step (2), obtained aqueous dispersions are placed in polytetrafluoro
In the autoclave of ethylene liner, at a temperature of 180 DEG C, react 24 hours at autogenous pressures.Preparation contains metal original
The nature parameters of sub- nano-carbon material are listed in table 2.
Comparative example 7
Aqueous dispersions identical with embodiment 15 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in
In the oil bath that temperature is 180 DEG C, back flow reaction 24 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask
After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120
At a temperature of DEG C after drying 12 hours, nano-carbon material containing metallic atom is obtained.The nano-carbon material containing metallic atom of preparation
Nature parameters are listed in table 2.
Comparative example 8
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 15, unlike, step (1) configuration
Aqueous dispersions be free of hydrazine, it is, by raw material nano carbon material dispersion in deionized water, acid chloride is then added, thus
Obtain aqueous dispersions, wherein press raw material nano carbon material: hydrazine: metallic compound: H2The weight ratio of O is the ratio of 1:0:4.5:100
Example feeds intake.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Comparative example 9
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 15, unlike, step (1) configuration
Aqueous dispersions be free of hydrazine, it is, by raw material nano carbon material dispersion in deionized water, acid chloride is then added, thus
Obtain aqueous dispersions, wherein the mole of acid chloride is identical as the integral molar quantity of hydrazine and acid chloride in embodiment 15, raw material nano
The dosage of carbon material and water is identical as embodiment 15.The nature parameters of the nano-carbon material containing metallic atom of preparation are in table 2
It lists.
Comparative example 10
Nano-carbon material is prepared using method identical with embodiment 15, unlike, aqueous solution used in step (1)
Not metal-containing compound, it is, in deionized water by the dispersion of raw material nano carbon material, hydrazine is then added, to obtain water
Dispersion liquid, wherein press raw material nano carbon material: hydrazine: metallic compound: H2The ratio that the weight ratio of O is 1:0.2:0:100 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 method identical with embodiment 15, unlike, in step (2),
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 260 DEG C, in spontaneous pressure
It is reacted 24 hours under power.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 17
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 15, unlike, it is received as raw material
The multi-walled carbon nanotube of rice carbon material is same as Example 2.The nature parameters of the nano-carbon material containing metallic atom of preparation are in table 2
In list.
Embodiment 18
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 15, unlike, in step (1),
By raw material nano carbon material: hydrazine: metallic compound: H2The weight ratio of O is that the ratio of 1:2:5:100 feeds intake.Preparation contains 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 method identical with embodiment 15, unlike, in step (1),
By raw material nano carbon material: hydrazine: metallic compound: H2The weight ratio of O is that the ratio of 1:0.08:4.8:200 feeds intake.Preparation 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, in deionized water by the dispersion of raw material nano carbon material, hydrazine and the palladium acetylacetonate as metallic compound is then added, from
And obtain aqueous dispersions, wherein press 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), obtained aqueous dispersions 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 of the nano-carbon material containing metallic atom of preparation are in table
It is listed in 2.
Embodiment 21
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, unlike, in step (1),
Multi-walled carbon nanotube as raw material nano carbon material is same as Example 7.The property of the nano-carbon material containing metallic atom of preparation
Matter parameter is listed in table 2.
Embodiment 22
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, unlike, in step (1),
Under conditions of the total weight of hydrazine and metallic compound is constant, hydrazine: the molar ratio of metallic compound is 1:5.Preparation contains metal original
The nature parameters of sub- nano-carbon material are listed in table 2.
Embodiment 23
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, unlike, in step (1),
Under conditions of the integral molar quantity of hydrazine and metallic compound is constant, hydrazine: the molar ratio of metallic compound is 10:1.Preparation contains 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 method identical with embodiment 20, unlike, in step (2),
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 60 DEG C, in spontaneous pressure
It is reacted 72 hours under power.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 25
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, unlike, palladium acetylacetonate
It is replaced with the nickel oxalate of equimolar amounts.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 26
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, unlike, palladium acetylacetonate
It is replaced with the ruthenium acetate of equimolar amounts.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 27
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, unlike, palladium acetylacetonate
It is replaced with the rhodium acetate of equimolar amounts.The nature parameters of the nano-carbon material containing metallic atom of preparation 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, in deionized water by the dispersion of raw material nano carbon material, urea and the acetylacetone,2,4-pentanedione ruthenium as metallic compound is then added,
To obtain aqueous dispersions, wherein press raw material nano carbon material: urea: metallic compound: H2The weight ratio of O is 1:0.5:
The ratio of 0.1:80 feeds intake；In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining
In, at a temperature of 180 DEG C, react 36 hours at autogenous pressures.The property ginseng of the nano-carbon material containing metallic atom of preparation
Number is listed in table 2.
Comparative example 11
Aqueous dispersions identical with embodiment 28 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in
In the oil bath that temperature is 180 DEG C, back flow reaction 36 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask
After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120
At a temperature of DEG C after drying 12 hours, nano-carbon material containing metallic atom is obtained.The nano-carbon material containing metallic atom of preparation
Nature parameters are listed in table 2.
Comparative example 12
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 28, unlike, step makes in (1)
Aqueous solution is free of urea, it is, in deionized water by the dispersion of raw material nano carbon material, metal compound is then added
Object, to obtain aqueous dispersions, wherein press raw material nano carbon material: urea: metallic compound: H2The weight ratio of O is 1:0:
The ratio of 0.1:80 feeds intake.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Comparative example 13
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 28, unlike, step makes in (1)
Aqueous solution is free of urea, it is, raw material nano carbon material point is spread in deionized water, metal compound is then added
Object, 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 dosage of raw material nano carbon material and water is identical as embodiment 28.The nano carbon material containing metallic atom of preparation
The nature parameters of material are listed in table 2.
Comparative example 14
Nano-carbon material is prepared using method identical with embodiment 28, unlike, aqueous solution used in step (1)
Not metal-containing compound, it is, in deionized water by the dispersion of raw material nano carbon material, urea is then added, to obtain
Aqueous dispersions, wherein press raw material nano carbon material: urea: metallic compound: H2The weight ratio of O is the ratio of 1:0.5:0:80
It feeds 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 method identical with embodiment 28, unlike, in step (2),
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in spontaneous pressure
It is reacted 36 hours under power.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 30
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 28, unlike, it is received as raw material
Rice carbon material is same as Example 2.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 31
Nano-carbon material containing metallic atom is prepared using method identical with 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 of preparation
The nature parameters of material are listed in table 2.
Embodiment 32
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 28, unlike, in step (1),
By raw material nano carbon material: urea: metallic compound: H2The weight ratio of O is that the ratio of 1:0.5:0.02:80 feeds intake.Preparation
The nature parameters of the nano-carbon material containing metallic atom 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, in deionized water by the dispersion of raw material nano carbon material, urea and the acetylacetone,2,4-pentanedione rhodium as metallic compound is then added,
To obtain aqueous dispersions, wherein press 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), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining,
At a temperature of 150 DEG C, react 12 hours at autogenous pressures.The nature parameters of the nano-carbon material containing metallic atom of preparation exist
It is listed in table 2.
Embodiment 34
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 33, unlike, in step (1),
Raw material nano carbon material is same as Example 7.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 35
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 33, unlike, in step (1),
Under conditions of the total weight of urea and metallic compound remains unchanged, make urea: the molar ratio 1:2 of metallic compound.Preparation
The nature parameters of the nano-carbon material containing metallic atom listed in table 2.
Embodiment 36
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 33, unlike, in step (2),
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 70 DEG C, in spontaneous pressure
It is reacted 12 hours under power.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 37
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 33, unlike, acetylacetone,2,4-pentanedione rhodium
It is replaced with the ferrous acetate of equimolar amounts.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 38
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 33, unlike, acetylacetone,2,4-pentanedione rhodium
It is replaced with the acid chloride of equimolar amounts.The nature parameters of the nano-carbon material containing metallic atom of preparation are listed in table 2.
Embodiment 39
Nano-carbon material containing metallic atom prepared by embodiment 1 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 15
Nano-carbon material containing metallic atom prepared by comparative example 1 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 16
Nano-carbon material containing metallic atom prepared by comparative example 2 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 17
Nano-carbon material containing metallic atom prepared by comparative example 3 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 18
Nano-carbon material containing metallic atom prepared by comparative example 4 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Comparative example 19
Nano-carbon material containing metallic atom prepared by comparative example 5 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 40
Nano-carbon material containing metallic atom prepared by embodiment 2 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 41
Nano-carbon material containing metallic atom prepared by embodiment 3 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 42
Nano-carbon material containing metallic atom prepared by embodiment 4 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 43
Nano-carbon material containing metallic atom prepared by embodiment 5 350 DEG C at a temperature of air atmosphere in roasting it is 4 small
When.
Embodiment 44
Nano-carbon material containing metallic atom prepared by embodiment 15 450 DEG C at a temperature of air atmosphere in roasting it is 2 small
When.
Embodiment 45
Nano-carbon material containing metallic atom prepared by embodiment 33 300 DEG C at a temperature of air atmosphere in roasting it is 12 small
When.
Embodiment 46-90 is for illustrating the present invention.
Embodiment 46-83
Respectively using the nano-carbon material containing metallic atom of 0.2g (admission space 1.9mL) embodiment 1-38 preparation as urging
Agent is seated in universal fixed bed miniature quartz pipe reactor, and two end seal of miniature quartz pipe reactor 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 molar ratio 0.5:1, surplus are nitrogen as carrier gas) it with total volume air speed is 1000h-1It is passed through in reactor and is reacted,
The composition of the reaction mixture exported from reactor is continuously monitored, and calculates n-butane conversion, total olefin selectivity and fourth
Alkene selectivity (for the overall selectivity of 1- butylene and 2- butylene), the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 20-33
It is reacted using method identical with embodiment 46-83, unlike, it is prepared respectively using comparative example 1-14
Nano-carbon material containing metallic atom is as catalyst.Reaction result is listed in table 3.
Comparative example 34
It is reacted using method identical with embodiment 46-83, unlike, use raw material same as Example 1
Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Comparative example 35
It is reacted using method identical with embodiment 46-83, unlike, use raw material same as Example 5
Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Embodiment 84-90
It is reacted using method identical with embodiment 46-83, unlike, contained using prepared by embodiment 39-45
Metallic atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 36-40
It is reacted using method identical with embodiment 46-83, unlike, contained using prepared by comparative example 15-19
Metallic atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 41
It is reacted using method identical with embodiment 46-83, unlike, catalyst is will be same as Example 1
Raw material nano carbon material 350 DEG C at a temperature of air atmosphere in roast 4 hours obtained from.Reaction result arranges in table 4
Out.
Comparative example 42
It is reacted using method identical with embodiment 46-83, unlike, catalyst is will be same as Example 5
Raw material nano carbon material 300 DEG C at a temperature of air atmosphere in roast 12 hours obtained from.Reaction result arranges in table 4
Out.
Table 3
Table 4
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (81)
1. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material contain C element, O element, N element and
At least one metallic element, on the basis of the total amount of the nano-carbon material containing metallic atom and based on the element, the content of O element is
2-15 weight %, the content of N element are 0.8-10 weight %, and the total amount of the metallic element is 1-10 weight %, and C element contains
Amount 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 spectroscopy is IO t, penetrated by X
The content for the O element that peak in photoelectron spectra within the scope of 529.5-530.8eV determines is IO m, IO m/IO t0.02-0.2's
In range；
This contains in metallic atom nano-carbon material, is determined by the peak within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy
The amount of O element is IO c, the amount of the O element determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is IO e,
IO c/IO eIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, determines the N in the nano-carbon material containing metallic atom by x-ray photoelectron spectroscopy
The total amount of element is IN t, the amount of the N element determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy is
IN c, IN c/IN tIn the range of 0.7-1；
This is contained metallic atom nano-carbon material and is prepared using method comprising the following steps: one kind being dispersed with raw material nano carbon materials
The aqueous dispersions of material, at least one nitrogenous compound and at least one metallic compound are reacted in closed container, institute
It states nitrogenous compound and is selected from NH3, hydrazine and urea, in reaction process, the temperature of the aqueous dispersions is maintained at 60-300 DEG C of model
In enclosing.
2. nano-carbon material containing metallic atom according to claim 1, wherein IO m/IO tIn the range of 0.05-0.18；
IO c/IO eIn the range of 0.45-0.99；IN c/IN tIn the range of 0.8-0.95.
3. nano-carbon material containing metallic atom according to claim 2, wherein IO m/IO tIn the range of 0.08-0.15；
IN c/IN tIn the range of 0.87-0.95.
4. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein this contains metallic atom and receives
In rice carbon material, the amount of the C element determined by the peak within the scope of 288.6-288.8eV in x-ray photoelectron spectroscopy is IC c, by X
The amount for the C element that peak in X-ray photoelectron spectroscopy X within the scope of 286.0-286.2eV determines is IC e, IC c/IC eIn the model of 0.3-2
In enclosing.
5. nano-carbon material containing metallic atom according to claim 4, wherein IC c/IC eIn the range of 0.4-1.5.
6. nano-carbon material containing metallic atom according to claim 5, wherein IC c/IC eIn the range of 0.5-1.25.
7. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein contain metallic atom with this
On the basis of the total amount of the C element determined in nano-carbon material by x-ray photoelectron spectroscopy, by x-ray photoelectron spectroscopy
The content for the C element that peak within the scope of 284.7-284.9eV determines is 50-95 weight %, by x-ray photoelectron spectroscopy
The content for the C element that peak within the scope of 286.0-288.8eV determines is 5-50 weight %.
8. nano-carbon material containing metallic atom according to claim 7, wherein in the nano-carbon material containing metallic atom
On the basis of the total amount of the C element determined by x-ray photoelectron spectroscopy, by 284.7-284.9eV range in x-ray photoelectron spectroscopy
The content for the C element that interior peak determines is 60-95 weight %, by within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy
The content for the C element that peak determines is 5-40 weight %.
9. nano-carbon material containing metallic atom according to claim 8, wherein in the nano-carbon material containing metallic atom
On the basis of the total amount of the C element determined by x-ray photoelectron spectroscopy, by 284.7-284.9eV range in x-ray photoelectron spectroscopy
The content for the C element that interior peak determines is 70-93 weight %, by within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy
The content for the C element that peak determines is 7-30 weight %.
10. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, 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 spectroscopy
The amount for the N element that peak within the scope of 401.5eV determines is IN g, IN g/IN tFor not higher than 0.3.
11. nano-carbon material containing metallic atom according to claim 10, wherein IN g/IN tIn the range of 0.05-0.2.
12. nano-carbon material containing metallic atom according to claim 11, wherein IN g/IN tIn the range of 0.05-0.13
It is interior.
13. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein former containing metal with this
On the basis of the total amount of sub- nano-carbon material and based on the element, the content of O element is 3-9 weight %, and the content of C element is 79-
94.8 weight %, the content of N element are 1-6 weight %, and the total amount of the metallic element is 1.2-6 weight %.
14. nano-carbon material containing metallic atom according to claim 13, wherein with the nano-carbon material containing metallic atom
Total amount on the basis of and based on the element, the content of O element is 4-8 weight %, and the content of C element is 82.5-93.4 weight %, N
The content of element is 1.1-5 weight %, and the total amount of the metallic element is 1.5-4.5 weight %.
15. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein the metallic element
Selected from transition metal.
16. nano-carbon material containing metallic atom according to claim 15, wherein the metallic element is selected from group VIII
Metal.
17. nano-carbon material containing metallic atom according to claim 16, wherein the metallic element be selected from iron, ruthenium,
Cobalt, rhodium, nickel, palladium and platinum.
18. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein this contains metallic atom
Nano-carbon material is carbon nanotube containing metallic atom.
19. nano-carbon material containing metallic atom according to claim 18, wherein this contains metallic atom nano-carbon material and is
Multi-walled carbon nanotube containing metallic atom.
20. nano-carbon material containing metallic atom according to claim 19, wherein the multi-wall carbon nano-tube containing metallic atom
The specific surface area of pipe is in 50-500m2In the range of/g.
21. nano-carbon material containing metallic atom according to claim 20, wherein the multi-wall carbon nano-tube containing metallic atom
The specific surface area of pipe is in 80-300m2In the range of/g.
22. nano-carbon material containing metallic atom according to claim 21, wherein the multi-wall carbon nano-tube containing metallic atom
The specific surface area of pipe is in 95-260m2In the range of/g.
23. nano-carbon material containing metallic atom according to claim 22, wherein the multi-wall carbon nano-tube containing metallic atom
The specific surface area of pipe is in 125-180m2In the range of/g.
24. nano-carbon material containing metallic atom according to claim 19, wherein the multi-wall carbon nano-tube containing metallic atom
Weight-loss ratio of the pipe 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, the weight-loss ratio measures in air atmosphere.
25. nano-carbon material containing metallic atom according to claim 24, wherein w500/w800In the range of 0.04-0.18
It is interior.
26. a kind of preparation method of the nano-carbon material containing metallic atom described in claim 1, this method include being dispersed with one kind
The aqueous dispersions of raw material nano carbon material, at least one nitrogenous compound and at least one metallic compound are in closed container
It is reacted, the nitrogenous compound is selected from NH3, hydrazine and urea, in reaction process, the temperature of the aqueous dispersions is maintained at
In the range of 60-300 DEG C.
27. according to the method for claim 26, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound
Ratio is measured in the range of 1:0.01-10:0.01-10；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:2-500.
28. according to the method for claim 27, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound
Ratio is measured in the range of 1:0.02-5:0.05-8；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:5-250.
29. according to the method for claim 28, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound
Ratio is measured in the range of 1:0.02-2:0.06-6；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:10-200.
30. according to the method for claim 29, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound
Ratio is measured in the range of 1:0.02-1:0.08-5；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:20-200.
31. according to the method for claim 30, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound
Ratio is measured in the range of 1:0.02-0.5:0.8-5；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:50-200.
32. the method according to any one of claim 26-31, wherein nitrogenous compound: mole of metallic compound
Than in the range of 1:0.001-10.
33. according to the method for claim 32, wherein nitrogenous compound: the molar ratio of metallic compound is in 1:0.03-6
In the range of.
34. the method according to any one of claim 26-31, wherein the metallic element in the metallic compound
Selected from transition metal element.
35. according to the method for claim 34, wherein the metallic element in the metallic compound is selected from group VIII gold
Belong to element.
36. according to the method for claim 35, wherein metallic element in the metallic compound be selected from iron, ruthenium, cobalt,
Rhodium, nickel, palladium and platinum.
37. the method according to any one of claim 26-31, wherein the metallic compound is selected from metal acetic acid
Salt, metal oxalate, basic metal carbonates and metal complex.
38. according to the method for claim 26, wherein the nitrogenous compound is NH3, gold in the metallic compound
Belong to element and be selected from iron, cobalt and nickel, raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in 1:0.01-1:
In the range of 0.5-6, nitrogenous compound: the molar ratio of metallic compound is in the range of 1:0.1-10, raw material nano carbon material:
H2The weight ratio of O is in the range of 1:20-100.
39. according to the method for claim 38, wherein the metallic compound is metal acetate, basic metal hydrochloric acid
One or more of salt and metal oxalate.
40. according to the method for claim 39, wherein the metallic compound is metal acetate and/or metal oxalic acid
Salt.
41. the method according to any one of claim 38-40, wherein raw material nano carbon material: nitrogenous compound:
The weight ratio of metallic compound is in the range of 1:0.01-0.2:0.9-5, nitrogenous compound: the molar ratio of metallic compound exists
In the range of 1:2-6, raw material nano carbon material: H2The weight ratio of O is in the range of 1:40-80.
42. according to the method for claim 26, wherein the nitrogenous compound is hydrazine, the gold in the metallic compound
Belong to element and be selected from palladium and platinum, the metallic compound be one of metal acetate, metal oxalate and metal complex or
It is two or more, raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound in the range of 1:0.05-3:2-6,
Nitrogenous compound: the molar ratio of metallic compound is in the range of 1:0.2-10, raw material nano carbon material: H2The weight ratio of O exists
In the range of 1:20-250.
43. according to the method for claim 42, wherein the metallic compound is metal acetate and/or metal complex
Object.
44. the method according to claim 42 or 43, wherein raw material nano carbon material: nitrogenous compound: metallic compound
Weight ratio in the range of 1:0.2-0.5:4-5, nitrogenous compound: range of the molar ratio of metallic compound in 1:0.6-1
It is interior, raw material nano carbon material: H2The weight ratio of O is preferably in the range of 1:50-100.
45. according to the method for claim 26, wherein the nitrogenous compound is urea, in the metallic compound
Metallic element is selected from ruthenium and rhodium, and raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in 1:0.08-6:
In the range of 0.02-2, nitrogenous compound: the molar ratio of metallic compound is in the range of 1:0.02-2, raw material nano carbon materials
Material: H2The weight ratio of O is in the range of 1:20-100.
46. according to the method for claim 45, wherein the metallic compound is metal complex.
47. the method according to claim 45 or 46, wherein raw material nano carbon material: nitrogenous compound: metallic compound
Weight ratio in the range of 1:0.3-0.6:0.1-1, nitrogenous compound: the molar ratio of metallic compound is 1:0.02-0.4's
In range, raw material nano carbon material: H2The weight ratio of O is in the range of 1:40-80.
48. the method according to any one of claim 26-31,38-40,42,43,45 and 46, wherein reaction process
In, the temperature of the aqueous dispersions is maintained in the range of 120-240 DEG C.
49. the method according to any one of claim 26-31,38-40,42,43,45 and 46, wherein the reaction
Duration in the range of 0.5-96 hours.
50. according to the method for claim 49, wherein the duration of the reaction is in the range of 2-72 hours.
51. according to the method for claim 50, wherein the duration of the reaction is in the range of 8-36 hours.
52. the method according to any one of claim 26-31,38-40,42,43,45 and 46, wherein the raw material
In nano-carbon material, the content of N element is the content not higher than 0.5 weight %, O element for not higher than 1.5 weight %, metal member
The total amount of element is 2.5 weight % or less.
53. method according to claim 52, wherein in the raw material nano carbon material, the content of N element be not higher than
The content of 0.2 weight %, O element is not higher than 1.2 weight %, and the total amount of metallic element is 1.8 weight % or less.
54. method according to claim 53, wherein in the raw material nano carbon material, the content of N element be not higher than
The content of 0.1 weight %, O element is not higher than 0.5 weight %, and the total amount of metallic element is 0.5 weight % or less.
55. method according to claim 54, wherein in the raw material nano carbon material, the content of N element be not higher than
The content of 0.05 weight %, O element is not higher than 0.3 weight %, and the total amount of metallic element is 0.1 weight % or less.
56. method according to claim 55, wherein in the raw material nano carbon material, the content of N element be not higher than
0.02 weight %.
57. the method according to any one of claim 26-31,38-40,42,43,45 and 46, wherein the raw material
Nano-carbon material is carbon nanotube.
58. method according to claim 57, wherein the raw material nano carbon material is multi-walled carbon nanotube.
59. method according to claim 58, wherein the specific surface area of the multi-walled carbon nanotube is 50-500m2/g。
60. method according to claim 59, wherein the specific surface area of the multi-walled carbon nanotube is 80-300m2/g。
61. method according to claim 60, wherein the specific surface area of the multi-walled carbon nanotube is 100-260m2/g。
62. method according to claim 61, wherein the specific surface area of the multi-walled carbon nanotube is 120-190m2/g。
63. method according to claim 58, wherein the multi-walled carbon nanotube is in 400-800 DEG C of temperature range
Weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5,
The weight-loss ratio measures in air atmosphere.
64. method according to claim 63, wherein w500/w800In the range of 0.02-0.4.
65. the method according to any one of claim 26-31,38-40,42,43,45 and 46, wherein this method is also
Including isolating solid matter from the mixture that reaction obtains, and the solid matter isolated is dried.
66. method according to claim 65, wherein the drying 50-200 DEG C at a temperature of carry out, the drying
Duration be 0.5-48 hours.
67. method according to claim 66, wherein the drying 80-180 DEG C at a temperature of carry out, the drying
Duration be 6-24 hours.
68. method according to claim 67, wherein the drying 120-160 DEG C at a temperature of carry out, the drying
Duration be 8-12 hours.
69. a kind of nano-carbon material containing metallic atom of the preparation of the method as described in any one of claim 26-68.
70. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material be will be in claim 1-25 arbitrarily
Nano-carbon material containing metallic atom described in nano-carbon material containing metallic atom described in one or claim 69 is roasted
Prepared by burning.
71. nano-carbon material containing metallic atom according to claim 70, wherein temperature of the roasting at 250-500 DEG C
Degree is lower to carry out, and the duration of the roasting is 1-24 hours.
72. nano-carbon material containing metallic atom according to claim 71, wherein temperature of the roasting at 300-450 DEG C
Degree is lower to carry out, and the duration of the roasting is 2-12 hours.
73. nano-carbon material containing metallic atom described in any one of claim 1-25 and 69 or claim 70-72
Any one of described in nano-carbon material containing metallic atom as hydrocarbon dehydrogenation reaction catalyst application.
74. the application according to claim 73, wherein the dehydrogenation reaction carries out in the presence of oxygen.
75. the application according to claim 73 or 74, wherein the hydrocarbon is alkane.
76. the application according to claim 75, wherein the hydrocarbon is C2-C12Alkane.
77. the application according to claim 76, wherein the hydrocarbon is normal butane.
78. a kind of hydrocarbon dehydrogenation reaction method, this method is included under conditions of existence or non-existence oxygen, in hydrocarbon dehydrogenation reaction item
Under part, by nano-carbon material containing metallic atom or claim described in any one of hydrocarbon and claim 1-25 and 69
The contact of nano-carbon material containing metallic atom described in any one of 70-72.
79. the method according to claim 78, wherein the hydrocarbon is alkane.
80. the method according to claim 79, wherein the hydrocarbon is C2-C12Alkane.
81. the method according to claim 80, wherein the hydrocarbon is normal butane.
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