CN106925278B - 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 PDF

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CN106925278B
CN106925278B CN201511030296.2A CN201511030296A CN106925278B CN 106925278 B CN106925278 B CN 106925278B CN 201511030296 A CN201511030296 A CN 201511030296A CN 106925278 B CN106925278 B CN 106925278B
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carbon material
metallic atom
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CN106925278A (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

The invention discloses a kind of nano-carbon material containing metallic atom and preparation method and application, the nano-carbon material contains the O element of 1-15 weight % and the metallic element of 1.1-20 weight %, the ratio of the content of the O element determined by the peak of 529.5-530.8eV in XPS and the total amount by the XPS O element determined is 0.02-0.5, and the ratio of the amount of the amount of the O element determined by the peak of 531.0-532.5eV and the O element determined by the peak of 532.6-533.5eV is 0.2-1.The present invention also provides the hydrocarbon dehydrogenation reaction method of the nano-carbon material containing metallic atom as catalyst is used, this method can obtain higher feed stock conversion and selectivity of product.

Description

One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon Dehydrogenation reaction method
Technical field
The present invention relates to a kind of nano-carbon 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 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.
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 the content of oxygen atom 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 and at least one metallic element, with the total of the nano-carbon material containing metallic atom On the basis of amount and based on the element, the content of O element is 1-15 weight %, and the total amount of the metallic element is 1.1-20 weight %, C The content of element is 65-97.9 weight %, this contains in metallic atom nano-carbon material, the oxygen determined by x-ray photoelectron spectroscopy The total content of element is IO t, by the content for the O element that the peak within the scope of 529.5-530.8eV in x-ray photoelectron spectroscopy determines For IO m, IO m/IO tIn the range of 0.02-0.5；This contains in metallic atom nano-carbon material, by x-ray photoelectron spectroscopy The amount for the O element that peak within the scope of 531.0-532.5eV determines is IO c, by 532.6-533.5eV model in x-ray photoelectron spectroscopy The amount for the O element that peak in enclosing determines is IO e, IO c/IO eIn the range of 0.2-1.
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 transistion metal compound and at least one alkali The aqueous dispersions of property metallic compound are reacted in closed container, and the metallic element in the alkaline metal cpds is selected from Group ia metal element and group iia metallic element, in reaction process, the temperature of the aqueous dispersions is maintained at 80-300 DEG C In range.
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 be by the nano-carbon material containing metallic atom in terms of first aspect according to the present invention or third into Prepared by row 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 The content of metallic atom and oxygen atom in nano-carbon material, at the same it is small on the influence of the structure of nano-carbon material itself, and preparation contains Metallic atom nano-carbon material has stable performance.
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 and at least one metallic element.In the present invention, "at least one" indicates a kind of Or it is two or more.
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 be 1-15 weight %, preferably 3-8 weight %, more preferably 4-7.5 weight %, further Preferably 4.5-7 weight %；The total amount of metallic element be 1.1-20 weight %, preferably 1.7-16 weight %, more preferably 2.4-13 weight %, further preferably 2.5-10 weight %；The content of C element is 65-97.9 weight %, preferably 76- 95.3 weight %, more preferably 79.5-93.6 weight %, further preferably 83-93 weight %.Wherein, the content of each element It is measured using X-ray photoelectron spectroscopy.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 0.02-0.5, preferably exist In the range of 0.05-0.4, more preferably in the range of 0.05-0.3.Nano-carbon material containing metallic atom according to the present invention, by The content for the O element that peak in x-ray photoelectron spectroscopy within the scope of 531.0-533.5eV determines is IO nm, IO nm/IO tIn 0.5- In the range of 0.98, preferably in the range of 0.6-0.95, more preferably in the range of 0.7-0.95.In the present invention, indicating When 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, C-O) is IO e, IO c/IO eIn the range of 0.2-1, preferably in the range of 0.25-0.85, more It is preferred that in the range of 0.4-0.8, further preferably in the range of 0.45-0.7.In the present invention, by x-ray photoelectron spectroscopy In spectral peak (corresponding to the oxygen species not being connected with metallic atom) within the scope of 531.0-533.5eV be further separated into two groups Peak, i.e., the spectral peak (corresponding to C=O species) within the scope of 531.0-532.5eV and the spectrum within the scope of 532.6-533.5eV Peak (corresponds to C-O species), and the area of the spectral peak within the scope of 531.0-532.5eV is denoted as AO 4, will be in 532.6-533.5eV The area of spectral peak in range 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 60-98 weight %, preferably 65-95 weight %, more preferably 70-90 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 2- 40 weight %, preferably 5-35 weight %, more preferably 10-30 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 0.4-2, preferably in the model of 0.45-1.8 In enclosing, more preferably in the range of 0.5-1.5.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。
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 531.0-532.5eV refers to that combination corresponding to summit can be in 531.0- Whole peaks in the range of 532.5eV.
Nano-carbon material containing metallic atom according to the present invention, the metallic element, which is selected from, has catalysis to hydrocarbon dehydrogenation reaction The metallic element of effect, such as: the metallic element can be group ia metal element, group iia metal in the periodic table of elements The combination of one or more of element and transition metal element.Preferably, the nano-carbon material containing metallic atom contains There are at least one first metallic element and at least one second metallic element, first metallic element is selected from transition metal member Element, second metallic element are selected from group ia metal element and group iia metallic element, this contains the nano carbon material of metallic atom Material shows higher catalytic activity in hydrocarbon dehydrogenation reaction.
First metallic element can in the periodic table of elements Group IIIB metallic element, group ivb metallic element, Group VB metallic element, vib metals element, V Group IIB metallic element, group VIII metallic element, I B-group metal member Element and group iib metallic element.The specific example of first metallic element can include but is not limited to scandium, yttrium, rare earth metal Element (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, Jin Hexin.It is excellent Selection of land, first metallic element are selected from group VIII metallic element.It is highly preferred that first metallic element be selected from iron, ruthenium, Cobalt, rhodium, nickel, palladium and platinum.
Second metallic element is selected from group ia metal element and group iia metallic element, specific example and can wrap Include but be not limited to one or more of lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, second metallic element For one or more of sodium, potassium, magnesium, calcium and barium.The content of first metallic element and the second metallic element can be with It is made appropriate choice according to the type of the first metallic element and the second metallic element.Preferably, it is received with described containing metallic atom On the basis of the total amount of rice carbon material and based on the element, the content of first metallic element can be 1-10 weight %, preferably 1.5-8 weight %, more preferably 2-6 weight %, further preferably 2-5 weight %；The content of second metallic element can Think 0.1-10 weight %, preferably 0.2-8 weight %, more preferably 0.4-7 weight %, further preferably 0.5-5 weight Measure %.
Nano-carbon material containing metallic atom according to the present invention, in a preferred embodiment, first metal Element is selected from iron, cobalt and nickel, and second metallic element is selected from magnesium, calcium and barium, can be further improved so according to the present invention Catalytic activity of the nano-carbon material containing metallic atom in hydrocarbon dehydrogenation reaction.In the preferred embodiment, with described containing gold On the basis of the total amount for belonging to atom nano-carbon material, the content of first metallic element can be 1-10 weight %, preferably 1-5 Weight %, more preferably 2-4 weight %；The content of second metallic element can be 1-10 weight %, preferably 1-6 weight Measure %, more preferably 2.5-4 weight %.
Nano-carbon material containing metallic atom according to the present invention, in another preferred embodiment, first gold medal Belong to element and be selected from ruthenium, rhodium, palladium and platinum, second metallic element is selected from sodium and potassium, can be further improved so according to the present invention Catalytic activity of the nano-carbon material containing metallic atom in hydrocarbon dehydrogenation reaction.In the preferred embodiment, contained with described On the basis of the total amount of metallic atom nano-carbon material, the content of first metallic element can be 1-10 weight %, preferably 2-5 weight %；The content of second metallic element is preferably 0.5-8 weight %, preferably 0.6-3 weight %.
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 50-500m2/ g can be further improved the catalytic performance of the nano-carbon material containing metallic atom, especially in this way The catalytic performance of catalyst as hydrocarbons dehydrogenation reaction.It is highly preferred that this contains the ratio of metallic atom multi-walled carbon nanotube Surface area is 80-300m2/g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nanotube is 100-250m2/ g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nanotube is 110-180m2/g.In the present invention, institute Specific surface area is stated to be 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 0.05-0.3.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, which is 50-500m2/ g, preferably 80-300m2/ G, more preferably 100-250m2/ g, further preferably 110-180m2/g；Also, w500/w800In the range of 0.01-0.5, It is preferred that in the range of 0.05-0.3.
Nano-carbon material containing metallic atom according to the present invention, for oxygen atom outside other nonmetallic heteroatoms, such as Nitrogen-atoms, 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 nitrogen-atoms, sulphur atom and phosphorus atoms) outside oxygen atom can be 0.5 Weight % hereinafter, preferably 0.2 weight % hereinafter, more preferably 0.1 weight % hereinafter, further preferably 0.05 weight % with Under.Nano-carbon material containing metallic atom according to the present invention can also contain other metallic atoms in addition to aforesaid metal elements, Other metallic atoms for example can be for from the catalyst used when preparing nano-carbon material.Other metallic atoms Content be generally 2.5 weight % hereinafter, preferably 1.5 weight % hereinafter, further preferably 0.5 weight % hereinafter, more into One step is preferably 0.2 weight % hereinafter, particularly preferably 0.1 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 transistion metal compound and at least one alkali The aqueous dispersions of property metallic compound are reacted in closed container, and the metallic element in the alkaline metal cpds is selected from Group ia metal element and group iia metallic element.
According to the method for the present invention, the metallic element in the transistion metal compound is selected from transition metal element, specifically Can in the periodic table of elements Group IIIB metallic element, group ivb metallic element, Group VB metallic element, Vib metals element, V Group IIB metallic element, group VIII metallic element, I B-group metal element and group iib metal Element.The specific example of metallic element in the transistion metal compound can include but is not limited to scandium, yttrium, rare earth metal member Plain (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, Jin Hexin.It is preferred that Ground, the metallic element in the transistion metal compound are selected from group VIII metallic element.It is highly preferred that the transition metal The metallic element closed in object is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The transistion metal compound can be selected from metal nitrate, metal acetate salt, metal carbonate, metal sulfate Salt, basic metal carbonates, metal hydroxides, metal chloride and metal complex, further preferably metal nitrate Salt, metal acetate salt, metal carbonate, basic metal carbonates, metal hydroxides and metal complex.
The transistion metal compound can specifically be selected from but not limited to nickel nitrate, nickel acetate, nickel sulfate, basic carbonate Nickel, nickel chloride, nickel hydroxide, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, vinegar Sour ferrous iron, ferric sulfate, basic carbonate iron, iron chloride, iron hydroxide, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, chlorination Zinc, zinc hydroxide, copper nitrate, copper acetate, copper sulphate, basic copper carbonate, copper chloride, Kocide SD, lanthanum nitrate, lanthanum carbonate, chlorine Change lanthanum, lanthanum hydroxide, cerous nitrate, cerous carbonate, cerium chloride, cerium hydroxide, nitric acid ruthenium, ruthenic chloride, hydroxide ruthenium, palladium nitrate, chlorine Change palladium, palladium dydroxide, palladium acetate, platinum nitrate, platinum chloride, rhodium nitrate, nitric acid ammonia palladium (such as four ammino palladium of nitric acid), radium chloride and second Acyl acetone palladium.
According to the method for the present invention, the metallic element in the alkaline metal cpds is selected from group ia metal element and the Group IIA metal element, specific example can include but is not limited to lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, described Metallic element is selected from sodium, potassium, magnesium, calcium and barium.
Preferably, the alkaline metal cpds are selected from the hydroxide containing metallic element and the alkali containing the metallic element Property salt.It is highly preferred that the alkaline metal cpds are selected from the hydroxide containing metallic element, the carbonic acid containing the metallic element Salt, the acetate containing the metallic element and the bicarbonate containing the metallic element.The alkaline metal cpds it is specific Example can include but is not limited to: lithium hydroxide, sodium hydroxide, potassium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, hydrogen Barium monoxide, strontium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, calcium bicarbonate, saleratus and carbonic acid One or more of hydrogen barium.
According to the method for the present invention, the dosage of the transistion metal compound and alkaline metal cpds can be according to pre- The content and type of oxygen element and metallic element that phase introduces in raw material nano carbon material are selected.Finally preparing Nano-carbon material containing metallic atom be used as hydrocarbon dehydrogenation reaction catalyst when, it is preferable that raw material nano carbon material: transition gold Belong to compound: for the weight ratio of alkaline metal cpds in the range of 1:0.01-10:0.01-15, what is thus prepared is former containing metal Sub- nano-carbon material can obtain the catalytic effect further increased when being used as the catalyst of hydrocarbon dehydrogenation reaction.It is highly preferred that former Expect nano-carbon material: transistion metal compound: the weight ratio of alkaline metal cpds is in the range of 1:0.02-5:0.05-10. It is further preferred that raw material nano carbon material: transistion metal compound: the weight ratio of alkaline metal cpds is in 1:0.05-1: In the range of 0.08-4.
According to the method for the present invention, according to the method for the present invention, the transistion metal compound and the alkalinous metal The molar ratio of conjunction object is preferably in the range of 1:0.5-300, and the nano-carbon material containing metallic atom thus prepared is de- as hydrocarbon Also there is more excellent catalytic activity when the catalyst of hydrogen reaction.It is highly preferred that the transistion metal compound and the alkali The molar ratio of property metallic compound is in the range of 1:0.6-35.
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 1:5-1000, when within the scope of the dosage of water being in this, nanometer The structural form retentivity of carbon material during processing is more preferable, such as: for carbon nanotube, during processing substantially It is not cut off.It is highly preferred that raw material nano carbon material: H2The weight ratio of O is in the range of 1:50-500.Further preferably Ground, raw material nano carbon material: H2The weight ratio of O is in the range of 1:120-250.
According to the method for the present invention, in a preferred embodiment, the metal member in the transistion metal compound Element is selected from iron, cobalt and nickel, and the metallic element in the alkaline metal cpds is selected from magnesium, calcium and barium, and what is thus prepared contains metal Atom nano-carbon material can obtain preferably catalysis reaction effect when being used as the catalyst of hydrocarbon dehydrogenation reaction.Raw material nano carbon materials Material: transistion metal compound: the weight ratio of alkaline metal cpds preferably in the range of 1:0.02-2:2-10, more preferably exists In the range of 1:0.8-1.2:3-5.In the preferred embodiment, transistion metal compound: alkaline metal cpds rub You compare preferably in the range of 1:1-220, more preferably in the range of 1:3-5.In the preferred embodiment, raw material nano Carbon material: H2The weight ratio of O is preferably in the range of 1:150-300, more preferably in the range of 1:220-280.
According to the method for the present invention, in another preferred embodiment, the metal in the transistion metal compound Element is selected from ruthenium, rhodium, palladium and platinum, and the metallic element in the alkaline metal cpds is selected from sodium and potassium, and what is thus prepared contains gold Preferably catalysis reaction effect can be obtained when being used as the catalyst of hydrocarbon dehydrogenation reaction by belonging to atom nano-carbon material.Raw material nano carbon Material: transistion metal compound: the weight ratio of alkaline metal cpds is more excellent preferably in the range of 1:0.02-1:0.05-10 It is selected in the range of 1:0.02-0.3:0.06-0.2.In the preferred embodiment, transistion metal compound: alkalinous metal The molar ratio of compound is preferably in the range of 1:0.5-150, more preferably in the range of 1:0.8-35.Preferably implement at this In mode, raw material nano carbon material: H2The weight ratio of O is preferably in the range of 1:80-300, more preferably in the model of 1:100-200 In enclosing.
According to the method for the present invention, the condition of the reaction is to be enough to improve oxygen atom and gold in raw material nano carbon material Subject to the content for belonging to atom.Preferably, in reaction process, the temperature of the aqueous dispersions is in the range of 80-300 DEG C.Institute When stating the temperature of aqueous dispersions and being within above range, can not only effectively improve oxygen atom in raw material nano carbon material and Metal atom content, and the structural form of raw material nano carbon material will not be generated and be significantly affected.It is highly preferred that reaction process In, 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 atom and metallic atom.Generally, the duration of the reaction can With in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably in the range of 12-48 hours.
Method according to the invention it is possible to 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 transistion metal compound and the alkalinity gold is then added Belong to compound, to obtain the aqueous dispersions.In order to further increase the dispersion effect of raw material nano carbon material, shorten simultaneously Raw material nano carbon material can be dispersed in water by the time of dispersion using the method for sonic oscillation.The item of the sonic oscillation Part can be conventional selection, and generally, the frequency of the sonic oscillation can be 20-200kHz, preferably 80-150kHz；Institute The duration for stating sonic oscillation can be 0.1-12 hours, preferably 0.2-6 hours, more preferably 1-4 hours.According to this hair Bright method, the transistion metal compound and the alkaline metal cpds can be with the shapes of solution (preferably aqueous solution) Formula provides, and can also be provided, is not particularly limited in the form of pure material.
According to the method for the present invention, the content of O element is not particularly limited in the raw material nano carbon material, can be normal Rule selection.Generally, the content of O element is not higher than 1 weight % preferably not higher than 0.8 in the raw material nano carbon material Weight %, more preferably not above 0.5 weight % are further preferably not higher than 0.3 weight %.According to the method for the present invention, Remaining nonmetallic heteroatoms (such as nitrogen-atoms, phosphorus atoms and sulphur atom) in the raw material nano carbon material outside oxygen atom it is total Measuring (based on the element) can be customary amount.Generally, remaining in the raw material nano carbon material outside oxygen atom is nonmetallic Heteroatomic total amount be not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, Still more preferably for not higher than 0.05 weight %.According to the method for the present invention, the raw material nano carbon material is according to source Difference may contain some metallic elements, such as the metal in the catalyst used when preparing raw material nano carbon material Element.The content (based on the element) of metallic element is generally in 2 weight % hereinafter, it is preferred that 1.8 weights in the raw material nano carbon material Measure % hereinafter, more preferably 1 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 and metal atom content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon nanotube, stone The group of one or more of black alkene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene It closes.The carbon nanotube can for one or both of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube with On combination.Preferably, the raw material nano carbon material is carbon nanotube, more preferably multi-walled carbon nanotube.
In a preferred embodiment, the raw material nano carbon material is multi-walled carbon nanotube, and the multi wall carbon is received The specific surface area of mitron can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, further preferably For 120-190m2/g.It is finally obtained containing gold when the specific surface area of the multi-wall carbon nano-tube material is within above range Belonging to atom nano-carbon material has better catalytic activity, especially when being used as the catalyst of dehydrogenation reaction of hydrocarbons, Show higher catalytic activity.
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 4-24 hours, more preferably 6-12 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, the oxygen atom and metal atom content in raw material nano carbon material can be effectively improved, The structural form of raw material nano carbon material will not be generated and be significantly affected simultaneously.
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 350-450 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, and preferably 2-12 hours, more preferably 2-4 was small When.The roasting can carry out in oxygen-containing atmosphere, can also carry out in the atmosphere formed by inert gas.It is described oxygenous Atmosphere can be air atmosphere；It can also be the mixed atmosphere that oxygen and inert gas are mixed to form, in the mixed atmosphere, oxygen Content can be 0.1-22 volume %.The inert gas can include but is not limited to nitrogen and/or rare gas, described dilute Having gas can be argon gas and/or helium.Angularly consider from convenience and cost, it is preferable that the roasting is in oxygen-containing atmosphere It is carried out in (such as air atmosphere).
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 0.5-2: 1。
Hydrocarbon dehydrogenation reaction method according to the present invention, can by carrier gas by hydrocarbon and optional oxygen be sent into reactor with The haptoreaction of nano-carbon material containing metallic atom.The carrier gas can for it is common at reaction conditions will not with reactant and instead The gas answered product that chemical interaction occurs and will not decomposed, as nitrogen, carbon dioxide, rare gas and water steam The combination of one or more of gas.The dosage of the carrier gas can be conventional selection.Generally, the content of carrier gas can be with For 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 1000-1500h-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 of 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. of U.S. production And the microscopic appearance of the nano-carbon material containing metallic atom.
In following embodiment and comparative example, alkaline metal cpds and transistion metal compound are respectively with the shape of solid matter Formula provides.
Embodiment 1-31 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 %, the total content of remaining nonmetallic heteroatoms (nitrogen-atoms, phosphorus atoms and sulphur atom) outside oxygen atom is 0.03 Weight %, metallic atom total content are 0.1 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w800, in 400-500 Weight-loss ratio in DEG C temperature range is w500, w500/w800It is 0.12, is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) point It dissipates in deionized water, is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes: that frequency is 140kHz, time 1 Hour.Then, the ferrous acetate as transistion metal compound and the barium hydroxide as alkaline metal cpds is added, thus Obtain aqueous dispersions, wherein press raw material nano carbon material: transistion metal compound: alkaline metal cpds: H2The weight ratio of O It feeds intake for the ratio of 1:1:4:250.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 120 DEG C of temperature Under, it reacts 48 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 120 DEG C, back flow reaction 48 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 Composition, specific surface area and w500/w800It is listed in table 1.
Comparative example 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), hydrogen The barium chloride of barium monoxide equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and w500/w800It is listed in table 1.
Comparative example 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, step (1) is prepared Aqueous dispersions be free of ferrous acetate, the total moles of ferrous acetate and barium hydroxide in the mole of barium hydroxide and embodiment 1 It measures identical.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Comparative example 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, step (1) is prepared Aqueous dispersions be free of barium hydroxide, the total moles of ferrous acetate and barium hydroxide in the mole of ferrous acetate and embodiment 1 It measures identical.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), make 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/w800It is 0.33, oxygen atom content is 0.62 weight %, and (nitrogen is former for remaining nonmetallic heteroatoms outside oxygen atom Son, phosphorus atoms and sulphur atom) total content be 0.02 weight %, metallic atom total content is 0.08 weight %.Preparation contains gold Belong to composition, specific surface area and the w of atom nano-carbon material500/w800It is 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 in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, at autogenous pressures Reaction 48 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is 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: transistion metal compound: alkaline metal cpds: H2The weight ratio of O is the ratio of 1:0.02:4:250 It feeds intake.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is 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: transistion metal compound: alkaline metal cpds: H2The ratio that the weight ratio of O is 1:1:8:250 is thrown Material.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is 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 %, the total content of remaining nonmetallic heteroatoms (nitrogen-atoms, phosphorus atoms and sulphur atom) outside oxygen atom are 0.05 weight % is measured, metallic atom total content is 0.03 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w800, in 400- Weight-loss ratio in 500 DEG C of temperature range is w500, w500/w800It is 0.07, is purchased from the limited public affairs of Chinese Academy of Sciences Chengdu organic chemistry Department) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition includes: that frequency is 90kHz, when Between be 4 hours.Then, the palladium acetate as transistion metal compound and the potassium carbonate as alkaline metal cpds is added, from And obtain aqueous dispersions, wherein press raw material nano carbon material: transistion metal compound: alkaline metal cpds: H2The weight of O Than feeding intake for the ratio of 1:0.2:0.1:150.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 220 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, this contains the composition of metallic atom nano-carbon material, compares table Area and w500/w800It is listed in table 1.
Comparative example 5
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), carbon Sour potassium with etc. the potassium chloride of weight replace.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800 It 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/w800It is 0.23, oxygen atom content is 1.1 weight %, and (nitrogen is former for remaining nonmetallic heteroatoms outside oxygen atom Son, phosphorus atoms and sulphur atom) total content be 0.04 weight %, metallic atom total content is 1.6 weight %.Preparation contains metal Composition, specific surface area and the w of atom nano-carbon material500/w800It is 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.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 9
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), obtain To aqueous dispersions in, under conditions of the total weight of transistion metal compound and alkaline metal cpds remains unchanged, make transition Metallic compound: the molar ratio of alkaline metal cpds is 1:10.The composition of the nano-carbon material containing metallic atom of preparation compares table Area and w500/w800It is listed in table 1.
Embodiment 10
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), carbon Sour potassium is replaced with potassium hydroxide, and the mole of potassium hydroxide is 2 times of the mole of potassium carbonate.The nanometer containing metallic atom of preparation Composition, specific surface area and the w of carbon material500/w800It is listed in table 1.
Embodiment 11
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), carbon Sour potassium is replaced with sodium bicarbonate, and the mole of sodium bicarbonate is 2 times of the mole of potassium carbonate in embodiment 6.Preparation contains gold Belong to composition, specific surface area and the w of atom nano-carbon material500/w800It is listed in table 1.
Embodiment 12
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), vinegar The palladium acetylacetonate of sour palladium equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and w500/w800It is listed in table 1.
Embodiment 13
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), vinegar The cobalt acetate of sour palladium equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/ w800It is listed in table 1.
Embodiment 14
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), vinegar The nickel acetate of sour palladium equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/ w800It is listed in table 1.
Embodiment 15
Nano-carbon material containing metallic atom is prepared using method same as Example 1, difference is as follows:
In step (1), in deionized water by the dispersion of raw material nano carbon material, then it is added and is used as transistion metal compound Palladium acetylacetonate and sodium hydroxide as alkaline metal cpds, to obtain aqueous dispersions, wherein press raw material nano carbon Material: transistion metal compound: alkaline metal cpds: H2The weight ratio of O is that the ratio of 1:0.05:0.2:120 feeds intake；
In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 120 DEG C At a temperature of, it reacts 36 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Comparative example 6
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 120 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 Composition, specific surface area and w500/w800It is listed in table 2.
Comparative example 7
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 15, unlike, in step (1), The sodium sulphate of sodium hydroxide equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and w500/w800It is listed in table 2.
Embodiment 16
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 15, unlike, in step (2), By obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, in self-generated pressure Lower reaction 36 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is 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 the same as embodiment 2.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and w500/w800It is listed in table 2.
Embodiment 18
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 15, unlike, in step (1), Under conditions of the total weight of transistion metal compound and transistion metal compound remains unchanged, make transistion metal compound: alkalinity The molar ratio of metallic compound is 1:20.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800 It is listed in table 2.
Embodiment 19
Nano-carbon material containing metallic atom is prepared using method same as Example 6, difference is as follows:
In step (1), the aqueous solution for preparing aqueous dispersions contains the palladium acetate and work as transistion metal compound For the sodium bicarbonate of alkaline metal cpds, wherein press raw material nano carbon material: transistion metal compound: alkalinous metal chemical combination Object: H2The weight ratio of O is that the ratio of 1:0.4:1:150 feeds intake；
In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 240 DEG C At a temperature of, it reacts 12 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 20
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 19, unlike, in step (1), Multi-walled carbon nanotube as raw material nano carbon material is the same as embodiment 7.Composition, the ratio of the nano-carbon material containing metallic atom of preparation Surface area and w500/w800It is listed in table 2.
Embodiment 21
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 19, unlike, in step (1), By raw material nano carbon material: transistion metal compound: alkaline metal cpds: H2The weight ratio of O is the ratio of 1:0.02:1:150 Example feeds intake.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 22
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 19, unlike, in step (1), By raw material nano carbon material: transistion metal compound: alkaline metal cpds: H2The weight ratio of O is the ratio of 1:0.1:10:150 Example feeds intake.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 23
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 19, unlike, in step (2), By obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, at a temperature of 270 DEG C, in self-generated pressure Lower reaction 12 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 24
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 19, unlike, in step (1), The nickelous carbonate of palladium acetate equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and w500/w800It is listed in table 2.
Embodiment 25
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 19, unlike, in step (1), The magnesium hydroxide of sodium bicarbonate equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area with And w500/w800It is listed in table 2.
Embodiment 26
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 8
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 9
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 10
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 11
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.
Embodiment 27
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 28
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 29
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 30
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 31
Nano-carbon material containing metallic atom prepared by embodiment 19 450 DEG C at a temperature of air atmosphere in roasting it is 2 small When.
Embodiment 32-62 is used to illustrate application and the hydrocarbon dehydrogenation reaction side of the nano-carbon material of the invention containing metallic atom Method.
Embodiment 32-56
Respectively using the nano-carbon material containing metallic atom of 0.2g (admission space 1.9mL) embodiment 1-25 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 0.1MPa and 435 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 1.98 volume %, normal butane and oxygen Gas molar ratio 0.5:1, surplus are nitrogen as carrier gas) it with total volume air speed is 1200h-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 1- Butylene selectivity, the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 12-18
It is reacted using method identical with embodiment 32-56, unlike, it is prepared respectively using comparative example 1-7 Nano-carbon material containing metallic atom is as catalyst.Reaction result is listed in table 3.
Comparative example 19
It is reacted using method identical with embodiment 32-56, unlike, use raw material same as Example 1 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Comparative example 20
It is reacted using method identical with embodiment 32-56, unlike, use raw material same as Example 6 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Embodiment 57-62
It is reacted using method identical with embodiment 32-56, unlike, contained using prepared by embodiment 26-31 Metallic atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 21-24
It is reacted using method identical with embodiment 32-56, unlike, contain gold using prepared by comparative example 8-11 Belong to atom carbon nanotube as catalyst.Reaction result is listed in table 4.
Comparative example 25
It is reacted using method identical with embodiment 32-56, unlike, catalyst is will be same as Example 1 Raw material nano carbon material roasted 4 hours in 350 DEG C of air atmospheres obtained from.Reaction result is listed in table 4.
Comparative example 26
It is reacted using method identical with embodiment 32-56, unlike, catalyst is will be same as Example 5 Raw material nano carbon material roasted 12 hours in 300 DEG C of air atmospheres obtained from.Reaction result is listed in table 4.
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 (73)

1. a kind of nano-carbon material containing metallic atom, this contains metallic atom nano-carbon material and contains C element, O element and at least one Kind 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 1-15 weight % is measured, the total amount of the metallic element is 1.1-20 weight %, and the content of C element is 65-97.9 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 t0.02-0.5'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, is determined by the peak within the scope of 288.6-288.8eV in x-ray photoelectron spectroscopy The amount of C element is IC c, the amount of the C element determined by the peak within the scope of 286.0-286.2eV in x-ray photoelectron spectroscopy is IC e, IC c/IC eIn the range of 0.4-2；
This contains metallic atom nano-carbon material and contains at least one first metallic element and at least one second metallic element, described First metallic element is selected from transition metal element；Second metallic element is selected from group ia metal element and group iia metal Element；
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 transistion metal compound and at least one alkaline metal cpds carry out in closed container It reacts, the metallic element in the alkaline metal cpds is selected from group ia metal element and group iia metallic element, reacts The temperature of Cheng Zhong, the aqueous dispersions are maintained in the range of 80-300 DEG C.
2. nano-carbon material containing metallic atom according to claim 1, wherein IO m/IO tIn the range of 0.05-0.4； IO c/IO eIn the range of 0.25-0.85.
3. nano-carbon material containing metallic atom according to claim 2, wherein IO m/IO tIn the range of 0.05-0.3； IO c/IO eIn the range of 0.4-0.8.
4. nano-carbon material containing metallic atom according to claim 3, wherein IO c/IO eIn the range of 0.45-0.7.
5. nano-carbon material containing metallic atom described in any one of -4 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 e0.45-1.8's In range.
6. nano-carbon material containing metallic atom according to claim 5, wherein IC c/IC eIn the range of 0.5-1.5.
7. nano-carbon material containing metallic atom described in any one of -4 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 60-98 weight %, by x-ray photoelectron spectroscopy The content for the C element that peak within the scope of 286.0-288.8eV determines is 2-40 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 65-95 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 5-35 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 70-90 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 10-30 weight %.
10. nano-carbon material containing metallic atom described in any one of -4 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 3-8 weight %, and the content of C element is 76- 95.3 weight %, the total amount of the metallic element are 1.7-16 weight %.
11. nano-carbon material containing metallic atom according to claim 10, 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 4-7.5 weight %, and the content of C element is 79.5-93.6 weight %, The total amount of the metallic element is 2.4-13 weight %.
12. nano-carbon material containing metallic atom according to claim 11, 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 4.5-7 weight %, and the content of C element is 83-93 weight %, described The total amount of metallic element is 2.5-10 weight %.
13. nano-carbon material containing metallic atom according to claim 1, wherein first metallic element is selected from the Group VIII metal element；Second metallic element is selected from sodium, potassium, magnesium, calcium and barium.
14. nano-carbon material containing metallic atom according to claim 13, wherein first metallic element be selected from iron, Ruthenium, cobalt, rhodium, nickel, palladium and platinum.
15. according to claim 1, nano-carbon material containing metallic atom described in any one of 13 and 14, wherein with this containing gold On the basis of the total amount of category atom nano-carbon material and based on the element, the content of first metallic element is 1-10 weight %, institute The content for stating the second metallic element is 0.1-10 weight %.
16. nano-carbon material containing metallic atom according to claim 15, wherein with the nano-carbon material containing metallic atom Total amount on the basis of and based on the element, the content of first metallic element is 1.5-8 weight %, second metallic element Content is 0.2-8 weight %.
17. nano-carbon material containing metallic atom according to claim 16, wherein with the nano-carbon material containing metallic atom Total amount on the basis of and based on the element, the content of first metallic element is 2-6 weight %, and second metallic element contains Amount is 0.4-7 weight %.
18. nano-carbon material containing metallic atom according to claim 17, wherein with the nano-carbon material containing metallic atom Total amount on the basis of and based on the element, the content of first metallic element is 2-5 weight %, and second metallic element contains Amount is 0.5-5 weight %.
19. nano-carbon material containing metallic atom described in any one of -4,13 and 14 according to claim 1, wherein this contains gold Category atom nano-carbon material is carbon nanotube containing metallic atom.
20. nano-carbon material containing metallic atom according to claim 19, wherein this contains metallic atom nano-carbon material and is Multi-walled carbon nanotube containing metallic atom.
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 50-500m2/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 80-300m2/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 100-250m2/g。
24. nano-carbon material containing metallic atom according to claim 23, wherein the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 110-180m2/g。
25. nano-carbon material containing metallic atom according to claim 20, 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.
26. nano-carbon material containing metallic atom according to claim 25, wherein w500/w800In the range of 0.05-0.3 It is interior.
27. a kind of preparation method of the nano-carbon material containing metallic atom as described in claim 1, this method includes by one kind point Dissipate the aqueous dispersions for having raw material nano carbon material, at least one transistion metal compound and at least one alkaline metal cpds It is reacted in closed container, the metallic element in the alkaline metal cpds is selected from group ia metal element and Section II A Race's metallic element, in reaction process, the temperature of the aqueous dispersions is maintained in the range of 80-300 DEG C.
28. according to the method for claim 27, wherein the metallic element in the transistion metal compound is selected from Section VIII Race's metallic element；Metallic element in the alkaline metal cpds is selected from group ia metal element and group iia metallic element.
29. according to the method for claim 28, wherein metallic element in the transistion metal compound be selected from iron, ruthenium, Cobalt, rhodium, nickel, palladium and platinum；Metallic element in the alkaline metal cpds is selected from sodium, potassium, magnesium, calcium and barium.
30. the method according to any one of claim 27-29, wherein the transistion metal compound is selected from metal Nitrate, metal acetate salt, metal carbonate, basic metal carbonates, metal hydroxides and metal complex；The alkali Property metallic compound be selected from the hydroxide containing metallic element, the carbonate containing the metallic element, containing the metallic element Acetate and bicarbonate containing the metallic element.
31. according to the method for claim 27, wherein raw material nano carbon material: transistion metal compound: alkalinous metal The weight ratio of object is closed in the range of 1:0.01-10:0.01-15；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:5-1000.
32. according to the method for claim 31, wherein raw material nano carbon material: transistion metal compound: alkalinous metal The weight ratio of object is closed in the range of 1:0.02-5:0.05-10；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:50-500.
33. according to the method for claim 32, wherein raw material nano carbon material: transistion metal compound: alkalinous metal The weight ratio of object is closed in the range of 1:0.05-1:0.08-4；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:120-250.
34. the method according to any one of claim 27-29 and 31-33, wherein transistion metal compound: alkalinity The molar ratio of metallic compound is in the range of 1:0.5-300.
35. according to the method for claim 34, wherein transistion metal compound: the molar ratio of alkaline metal cpds exists In the range of 1:0.6-35.
36. the method according to any one of claim 31-33, wherein the metal in the transistion metal compound Element is selected from iron, cobalt and nickel, and the metallic element in the alkaline metal cpds is selected from magnesium, calcium and barium, raw material nano carbon material: Transistion metal compound: the weight ratio of alkaline metal cpds is in the range of 1:0.02-2:2-10, transistion metal compound: The molar ratio of alkaline metal cpds is in the range of 1:1-220, raw material nano carbon material: H2The weight ratio of O is in 1:150-300 In the range of.
37. according to the method for claim 36, wherein raw material nano carbon material: transistion metal compound: alkalinous metal The weight ratio of object is closed in the range of 1:0.8-1.2:3-5, transistion metal compound: the molar ratio of alkaline metal cpds is 1: In the range of 3-5, raw material nano carbon material: H2The weight ratio of O is in the range of 1:220-280.
38. the method according to any one of claim 31-33, wherein the metal in the transistion metal compound Element is selected from ruthenium, rhodium, palladium and platinum, and the metallic element in the alkaline metal cpds is selected from sodium and potassium, raw material nano carbon material: Transistion metal compound: the weight ratio of alkaline metal cpds is in the range of 1:0.02-1:0.05-10, transition metal compound Object: the molar ratio of alkaline metal cpds is in the range of 1:0.5-150, raw material nano carbon material: H2The weight ratio of O is 1: In the range of 80-300.
39. according to the method for claim 38, wherein raw material nano carbon material: transistion metal compound: alkalinous metal The weight ratio of object is closed in the range of 1:0.02-0.3:0.06-0.2, transistion metal compound: mole of alkaline metal cpds Than in the range of 1:0.8-35, raw material nano carbon material: H2The weight ratio of O is in the range of 1:100-200.
40. according to the method for claim 27, wherein in reaction process, the temperature of the aqueous dispersions is maintained at 120- In the range of 240 DEG C.
41. the method according to any one of claim 27 and 40, wherein the duration of the reaction is in 0.5-96 In the range of hour.
42. according to the method for claim 41, wherein the duration of the reaction is in the range of 2-72 hours.
43. according to the method for claim 42, wherein the duration of the reaction is in the range of 12-48 hours.
44. the method according to any one of claim 27-29,31-33 and 40, wherein the raw material nano carbon materials In material, the content of O element is not higher than 1 weight %, and the total amount of metallic element is below 2 weight %.
45. according to the method for claim 44, wherein in the raw material nano carbon material, the content of O element be not higher than 0.8 weight %, the total amount of metallic element is below 1.8 weight %.
46. according to the method for claim 45, wherein in the raw material nano carbon material, the content of O element be not higher than 0.5 weight %, the total amount of metallic element are 1 weight % or less.
47. according to the method for claim 46, wherein in the raw material nano carbon material, the content of O element be not higher than 0.3 weight %, the total amount of metallic element are 0.5 weight % or less.
48. according to the method for claim 47, wherein in the raw material nano carbon material, the total amount of metallic element is 0.1 Weight % or less.
49. the method according to any one of claim 27-29,31-33 and 40, wherein the raw material nano carbon materials Material is carbon nanotube.
50. according to the method for claim 49, wherein the raw material nano carbon material is multi-walled carbon nanotube.
51. according to the method for claim 50, wherein the specific surface area of the multi-walled carbon nanotube is 50-500m2/g。
52. method according to claim 51, wherein the specific surface area of the multi-walled carbon nanotube is 80-300m2/g。
53. method according to claim 52, wherein the specific surface area of the multi-walled carbon nanotube is 100-260m2/g。
54. method according to claim 53, wherein the specific surface area of the multi-walled carbon nanotube is 120-190m2/g。
55. according to the method for claim 50, 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.
56. method according to claim 55, wherein w500/w800In the range of 0.02-0.4.
57. the method according to any one of claim 27-29,31-33 and 40, wherein this method further includes from anti- Solid matter is isolated in the mixture that should be obtained, and the solid matter isolated is dried.
58. method according to claim 57, wherein the drying 50-200 DEG C at a temperature of carry out, the drying Duration be 0.5-48 hours.
59. method according to claim 58, wherein the drying 80-180 DEG C at a temperature of carry out, the drying Duration be 4-24 hours.
60. method according to claim 59, wherein the drying 120-160 DEG C at a temperature of carry out, the drying Duration be 6-12 hours.
61. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material be will be in claim 1-26 arbitrarily Prepared by nano-carbon material containing metallic atom described in one is roasted.
62. nano-carbon material containing metallic atom according to claim 61, 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.
63. nano-carbon material containing metallic atom according to claim 62, wherein temperature of the roasting at 350-450 DEG C Degree is lower to carry out, and the duration of the roasting is 2-12 hours.
64. nano-carbon material containing metallic atom according to claim 63, wherein the duration of the roasting is 2-4 Hour.
65. appointing in nano-carbon material containing metallic atom described in any one of claim 1-26 or claim 61-64 Application of the nano-carbon material containing metallic atom as the catalyst of hydrocarbon dehydrogenation reaction described in meaning one.
66. application according to claim 65, wherein the dehydrogenation reaction carries out in the presence of oxygen.
67. the application according to claim 65 or 66, wherein the hydrocarbon is alkane.
68. application according to claim 67, wherein the hydrocarbon is C2-C12Alkane.
69. application according to claim 68, wherein the hydrocarbon is normal butane.
70. 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 61-64 described in any one of hydrocarbon and claim 1-26 Any one of described in nano-carbon material containing metallic atom contact.
71. method according to claim 70, wherein the hydrocarbon is alkane.
72. method according to claim 71, wherein the hydrocarbon is C2-C12Alkane.
73. the method according to claim 72, wherein the hydrocarbon is normal butane.
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