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CN106925326B - 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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CN106925326B
CN106925326B CN201511032378.0A CN201511032378A CN106925326B CN 106925326 B CN106925326 B CN 106925326B CN 201511032378 A CN201511032378 A CN 201511032378A CN 106925326 B CN106925326 B CN 106925326B
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nano
carbon material
weight
metallic atom
range
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CN106925326A (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds

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  • Engineering & Computer Science (AREA)
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  • Crystallography & Structural Chemistry (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 metallic element of the O element of 1-12 weight %, the N element of 0.1-6 weight % and 0.2-15 weight %, and at least partly metallic element is group ia metal element and group iia metallic element.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 and/or nitrogen-atoms in nano-carbon material.
Oxygen atom is introduced in nano-carbon material, can form hydroxyl, carbonyl, carboxyl, ester group on nano-carbon material surface With the oxygen-containing functional groups such as acid anhydrides.
Oxygen atom can be introduced in nano-carbon material by carrying out oxidation processes realization to nano-carbon material, to increase The content of oxygen-containing functional group in nano-carbon material.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or it is strong Oxidizing solution (such as H2O2、KMnO4) in carry out back flow reaction, can also be assisted while back flow reaction carry out microwave heating Or sonic oscillation, to enhance the effect of oxidation reaction.It can but carry out back flow reaction in strong acid and/or strong oxidizing solution Can have an adverse effect to the skeleton structure of nano-carbon material, or even destroy the skeleton structure of nano-carbon material.Such as: it will receive Rice carbon material carries out back flow reaction in nitric acid, although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, Nano-carbon material is easily caused to be cut off and/or obviously increase the defects of graphite network structure position, to reduce nano carbon material The performance of material, such as thermal stability.In addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, to introduce oxygen original The introduction volume of the period of the day from 11 p.m. to 1 a.m, oxygen atom is high to the dependence of operation condition, and fluctuation range is wider.
When introducing nitrogen-atoms in nano-carbon material, according to nitrogen-atoms, locating chemical environment is not in nano-carbon material Together, nitrogen-atoms is usually divided into chemical nitrogen and structure nitrogen.Chemical nitrogen mainly appears in material in the form of surface functional group Surface, such as amino or nitrosyl radical surface nitrogen-containing functional group.Structure nitrogen refer to skeleton structure into nano-carbon material with The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly include graphite mould nitrogen (that is,), pyridine type nitrogen (that is,) and Pyrroles's type nitrogen (that is,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen It is unsaturated nitrogen atom with pyrroles's type nitrogen, while replacing carbon atom, often will cause the missing for closing on carbon atom, form defect Position.
Can by introduced in nano-carbon material synthesis process nitrogenous functional atmosphere (such as ammonia, nitrogen, urea, Melamine), nitrogen is introduced into nano carbon material simultaneously in the synthesis process of nano-carbon material using high temperature and/or high pressure In the skeleton structure of material and/or surface；It can also be by the way that nano-carbon material to be placed in nitrogenous functional atmosphere (such as ammonia, nitrogen Gas, urea, melamine) in, nitrogen is introduced into the surface of nano-carbon material using high temperature and/or high pressure.High temperature and/or For high pressure although can form structure nitrogen in nano-carbon material, the type of nitrogen containing species depends on reaction condition, not easily-controllable System；Also, the different types of nitrogen containing species so generated are unevenly distributed on the surface of nano-carbon material, lead to nitrogenous nanometer The performance of carbon material is unstable.It then can also be reacted with amine, by the way that nano-carbon material is carried out oxidation processes thus in nanometer Carbon material surface introduces nitrogen-atoms, and the nitrogen-atoms so introduced is essentially chemical nitrogen.
Although the research of doping vario-property and its catalytic performance in relation to nano-carbon material achieves many progress, for Some of which basic problem is not built consensus yet, is still needed to doping vario-property nano-carbon material and preparation method thereof and catalysis Performance is furtherd investigate.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of nano-carbon material containing metallic atom, using this method Metallic atom can not only be introduced on nano-carbon material surface, and can steadily improve heteroatomic content in nano-carbon material, The structure of nano-carbon material itself is influenced simultaneously little.
It is another object of the present invention to provide a kind of nano-carbon materials containing metallic atom, this contains metallic atom nano-sized carbon When material is used for the dehydrogenation reaction of hydrocarbons, higher feed stock conversion and selectivity of product can be obtained.
Another object of the present invention is to provide a kind of hydrocarbon dehydrogenation reaction method, this method can obtain higher raw material conversion Rate and selectivity of product.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material contains C element, O element, N element and at least one metallic element, with the nano carbon material containing metallic atom On the basis of the total amount of material and based on the element, the content of O element is 1-12 weight %, and the content of N element is 0.1-6 weight %, institute The total amount for stating metallic element is 0.2-15 weight %, and the content of C element is 67-98.7 weight %, and at least partly metallic element is Group ia metal element and group iia metallic element,
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron spectroscopy is IO t, by The content for the O element that peak in x-ray photoelectron spectroscopy within the scope of 529.5-530.8eV determines is IO m, IO m/IO tIn 0.05- In the range of 0.6；
This contains in metallic atom nano-carbon material, true by the peak within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy The amount of fixed O element is IO c, the amount of the O element determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is IO e, IO c/IO eIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, determines that this contains metallic atom nano-carbon material by x-ray photoelectron spectroscopy In N element total amount be IN t, by the amount for the N element that the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy determines For IN c, IN c/IN tIn the range of 0-0.5, the N that is determined by the peak within the scope of 403.5-406.5eV in x-ray photoelectron spectroscopy The content of element is IN n, IN n/IN tIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, true by the peak within the scope of 288.6-288.8eV in x-ray photoelectron spectroscopy The amount of fixed 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 1-5.
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 alkaline metal cpds and at least one nitre The aqueous dispersions of acid metal salt are reacted in closed container, and the metallic element in the alkaline metal cpds is selected from I A Race's metallic element and group iia metallic element, in reaction process, the temperature of the aqueous dispersions is maintained at 80-300 DEG C of range It is interior.
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 Metallic atom and heteroatomic content in nano-carbon material, while the structure of nano-carbon material itself is influenced small.Also, according to The nano-carbon material containing metallic atom of the preparation method of the nano-carbon material containing metallic atom of the invention, preparation has stable property Energy.
Nano-carbon material containing metallic atom according to the present invention shows good urge in the dehydrogenation reaction of hydrocarbons Change performance, feed stock conversion and selectivity of product can be significantly improved.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing metallic atom prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo for the raw material nano carbon material that embodiment 1 uses.
Specific embodiment
In the present invention, nano-carbon material refers to that dispersed phase scale at least one dimension is less than the carbon material of 100nm.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material contains C element, O element, N element and at least one metallic element.In the present invention, "at least one" table Show one or more.
Nano-carbon material containing metallic atom according to the present invention, at least partly described metallic element are in the periodic table of elements Group ia metal element and group iia metallic element, specific example can include but is not limited to lithium, sodium, potassium, beryllium, magnesium, calcium, One or more of barium and strontium.Preferably, at least partly described metallic element is one of sodium, potassium, magnesium, calcium and barium Or it is two or more.
According to specific needs, the nano-carbon material containing metallic atom can also contain other metallic elements.In the present invention A kind of embodiment in, the nano-carbon material containing metallic atom contain at least one first metallic element and it is optional extremely The second metallic element of few one kind.
First metallic element group ia metal element and group iia metallic element in the periodic table of elements, tool Body example can include but is not limited to one or more of lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, described First metallic element is one or more of sodium, potassium, magnesium, calcium and barium.
Second metallic element is the metallic element in addition to group ia metal element and group iia metallic element, is such as selected Group IIIB metallic element, group ivb metallic element, Group VB metallic element, vib metals member from the periodic table of elements Element, V Group IIB metallic element, group VIII metallic element, I B-group metal element, group iib metallic element, group III A Metallic element, group IVA metallic element and V A race metallic element.The specific example of second metallic element may include but Be not limited to scandium, yttrium, thulium (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, Palladium, platinum, copper, silver, gold, zinc, aluminium, germanium, tin, lead and antimony.Preferably, second metallic element is selected from group VIII metal member Element, group IVA metallic element, I B-group metal element and group iib metallic element.It is highly preferred that second metallic element Selected from group VIII metallic element.It is further preferred that second metallic element is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The content of first metallic element and the second metallic element can contain metallic atom nano-carbon material according to this Concrete application occasion is selected.When the nano-carbon material containing metallic atom is used as the catalyst of hydrocarbon dehydrogenation reaction, with this On the basis of the total amount of metallic element in nano-carbon material containing metallic atom and based on the element, the content of first metallic element For 20-100 weight %, preferably 40-95 weight %, more preferably 60-90 weight %；The content of second metallic element is 0-80 weight %, preferably 5-60 weight %, more preferably 10-40 weight %.
In a kind of more preferably embodiment of the invention, first metallic element is selected from magnesium, calcium and barium, described Second metallic element is selected from iron, cobalt and nickel.In this more preferably embodiment, in the nano-carbon material containing metallic atom Metallic element total amount on the basis of and based on the element, the content of first metallic element is preferably 25-85 weight %, more excellent It is selected as 60-75 weight %；The content of second metallic element is preferably 15-75 weight %, more preferably 25-40 weight %. It is shown more according to the nano-carbon material containing metallic atom of the preferred embodiment when being used as the catalyst of hydrocarbon dehydrogenation reaction Excellent catalytic activity.
In another more preferably embodiment, first metallic element is selected from sodium and potassium, second metal Element is selected from ruthenium, rhodium, palladium and platinum.In this more preferably embodiment, with the gold in the nano-carbon material containing metallic atom On the basis of the total amount of category element and based on the element, the content of first metallic element is preferably 20-95 weight %, more preferably 65-90 weight %；The content of second metallic element is preferably 5-80 weight %, more preferably 10-35 weight %.According to this The nano-carbon material containing metallic atom of preferred embodiment shows more excellent when being used as the catalyst of hydrocarbon dehydrogenation reaction Catalytic activity.
Nano-carbon material containing metallic atom according to the present invention, on the basis of the total amount of the nano-carbon material containing metallic atom And based on the element, the content of O element is 1-12 weight %, preferably 3-10 weight %, more preferably 6-8 weight %；N element Content is 0.1-6 weight %, preferably 0.5-5.5 weight %, more preferably 0.9-5 weight %；The total amount of metallic element is 0.2-15 weight %, preferably 1.5-8 weight %, more preferably 3-6.5 weight %；The content of C element is 67-98.7 weight Measure %, preferably 76.5-95 weight %, more preferably 80.5-90.1 weight %.Wherein, the content of each element uses X-ray light Electronic spectroscopy measurement.Sample before testing 150 DEG C at a temperature of dry 3 hours in helium atmosphere.
In the present invention, X-ray photoelectron spectroscopic analysis is in Thermo Scientific company equipped with Thermo It is tested on the ESCALab250 type x-ray photoelectron spectroscopy of Avantage V5.926 software, excitaton source is monochromatization Al K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, base vacuum when analysis test It is 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage software Upper carry out data processing carries out quantitative analysis using sensitivity factor method in analysis module.
Nano-carbon material containing metallic atom according to the present invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity The total content for the oxygen element that sub- power spectrum determines is IO t, determined by the peak within the scope of 529.5-530.8eV in x-ray photoelectron spectroscopy O element (that is, the oxygen atom being bonded with metallic atom) content be IO m, IO m/IO tIn the range of 0.05-0.6, preferably exist In the range of 0.1-0.55, more preferably in the range of 0.18-0.3.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 0.4- In the range of 0.95, preferably in the range of 0.6-0.9.In the present invention, when indicating numberical range, " ×-× range It is interior " 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 eIt is more excellent preferably in the range of 0.3-0.95 in the range of 0.2-1 It is selected in the range of 0.6-0.8.In the present invention, by the spectral peak in x-ray photoelectron spectroscopy within the scope of 531.0-533.5eV (corresponding to the oxygen species not being connected with metallic atom) are further separated into two groups of peaks, i.e., the spectrum within the scope of 531.0-532.5eV Peak (corresponding to C=O species) and the spectral peak (corresponding to CO species) within the scope of 532.6-533.5eV, will be in 531.0- The area of spectral peak within the scope of 532.5eV is denoted as AO 4, the area of the spectral peak within the scope of 532.6-533.5eV is denoted as AO 5, IO c/IO e=AO 4/AO 5。
Nano-carbon material containing metallic atom according to the present invention, in the nano-carbon material containing metallic atom by X-ray light It is true by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy on the basis of the total amount for the C element that electron spectrum determines The content of fixed C element (that is, graphite mould carbon) can be 60-95 weight %, preferably 65-85 weight %, more preferably 70-80 Weight %；The total content of the C element determined by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy can be 5- 40 weight %, preferably 15-35 weight %, more preferably 20-30 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 1-5, preferably in the range of 1-3, more It is preferred that in the range of 1.2-2.In the present invention, by the spectral peak in x-ray photoelectron spectroscopy within the scope of 286.0-288.8eV (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 (corresponds to hydroxyl Base and ether type carbon species) and spectral peak (correspond to carboxyl, acid anhydride and ester type carbon species) within the scope of 288.6-288.8eV, it will The area of spectral peak within the scope of 286.0-286.2eV is denoted as AC 4, the area of the spectral peak within the scope of 288.6-288.8eV is remembered For AC 5, IC c/IC e=AC 5/AC 4。
Nano-carbon material containing metallic atom according to the present invention determines that this contains metallic atom and receives by x-ray photoelectron spectroscopy The total amount of N element in rice carbon material is IN t, the N that is determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy The amount of element is IN c, IN c/IN tIn the range of 0-0.5, preferably in the range of 0.01-0.35, more preferably in 0.03-0.15 In the range of.
Nano-carbon material containing metallic atom according to the present invention determines that this contains metallic atom and receives by x-ray photoelectron spectroscopy The total amount of N element in rice carbon material is IN t, the N that is determined by the peak within the scope of 403.5-406.5eV in x-ray photoelectron spectroscopy The content of element is IN n, IN n/IN tIn the range of 0.2-1, preferably in the range of 0.5-0.95, more preferably in 0.65-0.92 In the range of.
Nano-carbon material containing metallic atom according to the present invention, by 400.6-401.5eV range in x-ray photoelectron spectroscopy Content is lower or even is free of for the N element (that is, graphite mould nitrogen) that interior peak determines.Generally, according to the present invention to contain metallic atom In nano-carbon material, the amount of the N element determined by the peak within the scope of 400.6-401.5eV in x-ray photoelectron spectroscopy is IN g, IN g/IN tFor not higher than 0.3, generally in the range of 0.02-0.25, preferably in the range of 0.05-0.2.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peak in x-ray photoelectron spectroscopyN 1, by X-ray N1s spectral peak in photoelectron spectroscopy is divided into three groups of peaks, i.e., the spectral peak within the scope of 403.5-406.5eV (corresponds to-NO2Object Kind), within the scope of spectral peak within the scope of 400.6-401.5eV (corresponding to graphite mould nitrogen species) and 398.5-400.1eV Spectral peak (removes graphite mould nitrogen and-NO2Nitrogen species outside type nitrogen), the area of the spectral peak within the scope of 400.6-401.5eV is remembered For AN 2, the area of the spectral peak within the scope of 398.5-400.1eV is denoted as AN 3, by the spectral peak within the scope of 403.5-406.5eV Area be denoted as AN 4, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, IN n/IN t=AN 4/AN 1, obtained ratio be lower than When 0.01, it is believed that be free of such species, and the content of such species is denoted as 0.
In the present invention, position combination as corresponding to the summit at the peak at each peak be can determine that, range determines by mentioned earlier Peak refer to combination corresponding to summit can peak within that range, in the range may include a peak, also can wrap Include more than two peaks.Such as: the peak within the scope of 398.5-400.1eV refers to that combination corresponding to summit can be in 398.5- Whole peaks in the range of 400.1eV.
Nano-carbon material containing metallic atom according to the present invention can exist with common various forms, be specifically as follows but It is not limited to carbon nanotube containing metallic atom, graphene containing metallic atom, thin layer graphite containing metallic atom, nano-sized carbon containing metallic atom One of particle, carbon nano-fiber containing metallic atom, Nano diamond containing metallic atom and fullerene containing metallic atom or two Kind or more combination.The carbon nanotube containing metallic atom can be single-walled carbon nanotube containing metallic atom, contain metallic atom The combination of one or more of double-walled carbon nano-tube and multi-walled carbon nanotube containing metallic atom.It is according to the present invention to contain gold Belong to atom nano-carbon material, preferably multi-walled carbon nanotube containing metallic atom.
Nano-carbon material containing metallic atom according to the present invention, it is preferable that the multi-walled carbon nanotube containing metallic atom Specific surface area is 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 90-250m2/ g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nanotube is 120-180m2/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, better catalytic effect can be obtained.It is highly preferred that w500/w800In the range of 0.02-0.4.It is further preferred that w500/w800In the range of 0.05-0.15.In the present invention, w800=W800- W400, w500=W500- W400, W400For at 400 DEG C At a temperature of the mass loss rate that measures, W800For in 800 DEG C of the at a temperature of mass loss rate that measures, W500For at 500 DEG C At a temperature of the mass loss rate that measures；The weight-loss ratio is measured in air atmosphere using thermogravimetric analyzer, tests initial temperature It is 25 DEG C, heating rate is 10 DEG C/min；Sample is before testing in 150 DEG C of temperature and the pressure of 1 normal atmosphere in helium atmosphere Middle drying 3 hours.
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 90-250m2/ g, further preferably 120-180m2/ g, and w500/w800It is excellent in the range of 0.01-0.5 It is selected in the range of 0.02-0.4, more preferably in the range of 0.05-0.15.
Nano-carbon material containing metallic atom according to the present invention, for oxygen atom and nitrogen-atoms outside it is other nonmetallic miscellaneous Atom, such as sulphur atom and phosphorus atoms, content can be customary amount.Generally, nanometer containing metallic atom according to the present invention In carbon material, the total amount of other nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) outside oxygen atom and nitrogen-atoms can be 0.5 weight % hereinafter, preferably 0.2 weight % hereinafter, more preferably 0.1 weight % hereinafter, further preferably 0.05 weight Measure % or less.Nano-carbon material containing metallic atom according to the present invention can also contain other metals in addition to aforesaid metal elements Atom, other metallic atoms for example can be for from the catalyst used when preparing nano-carbon material.Other gold The content for belonging to atom is generally 2.5 weight % hereinafter, preferably 2 weight % are hereinafter, further preferably 1 weight % is hereinafter, more Further preferably 0.5 weight % is hereinafter, particularly preferably 0.2 weight % or less.
According to the second aspect of the invention, the present invention provides a kind of preparation sides of nano-carbon material containing metallic atom Method, this method include that one kind is dispersed with to raw material nano carbon material, at least one alkaline metal cpds and at least one nitre The aqueous dispersions of acid metal salt are reacted in closed container.
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 alkalinity containing metallic element Salt.It is highly preferred that the alkaline metal cpds are selected from the hydroxide containing metallic element, the oxide containing metallic element, contain The organic metal salt of metallic element, the carbonate containing metallic element and bicarbonate and subcarbonate containing metallic element. The specific example of the alkaline metal cpds can include but is not limited to: lithium hydroxide, sodium hydroxide, potassium hydroxide, hydrogen-oxygen Change beryllium, magnesia, calcium oxide, barium monoxide, basic magnesium carbonate, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, carbonic acid One or both of sodium, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, calcium bicarbonate, saleratus and barium bicarbonate with On.It is highly preferred that the alkaline metal cpds are sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and magnesium hydroxide One or more of.
According to the method for the present invention, the metallic element in the nitric acid metal salt, which is selected from, can form water-soluble nitric acid metal The metallic element of salt, group ia metal element, group iia metallic element, Group IIIB metal member such as in the periodic table of elements Element, group ivb metallic element, Group VB metallic element, vib metals element, V Group IIB metallic element, group VIII gold Belong to element, I B-group metal element, group iib metallic element, group III A metallic element, group IVA metallic element and V A Race's metallic element.The specific example of metallic element in the nitric acid metal salt can include but is not limited to lithium, sodium, potassium, magnesium, Calcium, barium, strontium, scandium, yttrium, thulium (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, Nickel, palladium, platinum, copper, silver, gold, zinc, aluminium, germanium, tin and antimony.Preferably, the metallic element in the nitric acid metal salt is selected from Section VIII Race's metallic element, group IVA metallic element, I B-group metal element and group iib metallic element.It is highly preferred that the nitric acid Metallic element in metal salt is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
According to the method for the present invention, the dosage of the alkaline metal cpds and the nitric acid metal salt can be according to expection The content and type of the nitrogen, oxygen element and the metallic element that introduce in raw material nano carbon material are selected.Most The nano-carbon material containing metallic atom prepared eventually is when being used as the catalyst of hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material: Alkaline metal cpds: for the weight ratio of nitric acid metal salt in the range of 1:0.01-10:0.01-10, what is thus prepared contains metal Atom 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 Raw material nano carbon material: alkaline metal cpds: the weight ratio of nitric acid metal salt is in the range of 1:0.015-8:0.02-5.Into Preferably, raw material nano carbon material: alkaline metal cpds: the weight ratio of nitric acid metal salt is 1:0.1-2:0.05-4's for one step In range.
According to the method for the present invention, according to the method for the present invention, alkaline metal cpds: the molar ratio of nitric acid metal salt is excellent It is selected in the range of 1:0.001-50, the nano-carbon material containing metallic atom thus prepared is in the catalyst for being used as hydrocarbon dehydrogenation reaction When also there is more excellent catalytic activity.It is highly preferred that alkaline metal cpds: the molar ratio of nitric acid metal salt is 1: In the range of 0.002-45.It is further preferred that alkaline metal cpds: the molar ratio of nitric acid metal salt is 1:0.004-40's In range.
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 1:10-500.Further preferably Ground, raw material nano carbon material: H2The weight ratio of O is in the range of 1:50-150.
According to the method for the present invention, in a preferred embodiment, the metallic element of the alkaline metal cpds Selected from magnesium, calcium and barium, the metallic element of the nitric acid metal salt is selected from iron, cobalt and nickel, the nanometer containing metallic atom thus prepared Carbon material can obtain preferably catalysis reaction effect when being used as the catalyst of hydrocarbon dehydrogenation reaction.Raw material nano carbon material: alkalinity Metallic compound: the weight ratio of nitric acid metal salt is preferably in the range of 1:0.05-6:0.04-6, more preferably in 1:0.1-1: In the range of 0.5-4.In the preferred embodiment, alkaline metal cpds: the molar ratio of nitric acid metal salt is preferably 1: In the range of 0.03-45, more preferably in the range of 1:0.4-40.In the preferred embodiment, raw material nano carbon material: H2The weight ratio of O is preferably in the range of 1:20-200, more preferably in the range of 1:100-150.
According to the method for the present invention, in another preferred embodiment, the metal member of the alkaline metal cpds Element is selected from sodium and potassium, and the metallic element of the nitric acid metal salt is selected from ruthenium, rhodium, palladium and platinum, and what is thus prepared receives containing metallic atom Rice carbon material can obtain preferably catalysis reaction effect when being used as the catalyst of hydrocarbon dehydrogenation reaction.Raw material nano carbon material: alkali Property metallic compound: the weight ratio of nitric acid metal salt is preferably in the range of 1:0.01-3:0.02-1, more preferably in 1:0.1-2: In the range of 0.05-0.1.In the preferred embodiment, alkaline metal cpds: the molar ratio of nitric acid metal salt preferably exists In the range of 1:0.002-6, more preferably in the range of 1:0.004-0.4.In the preferred embodiment, raw material nano carbon Material: H2The weight ratio of O is preferably in the range of 1:20-200, more preferably in the range of 1:50-150.
According to the method for the present invention, the condition of the reaction is to be enough to improve oxygen atom, nitrogen in raw material nano carbon material Subject to the content of atom and metallic atom.Preferably, in reaction process, range of the temperature of the aqueous dispersions at 80-300 DEG C It is interior.When the temperature of the aqueous dispersions is within above range, can not only effectively improve in raw material nano carbon material Oxygen atom, nitrogen-atoms and metal atom content, and the structural form of raw material nano carbon material will not be generated and be significantly affected.More Preferably, in reaction process, the temperature of the aqueous dispersions is in the range of 110-220 DEG C.
According to the method for the present invention, the duration of the reaction can be selected according to the temperature of reaction, with can It is introduced in raw material nano carbon material subject to enough oxygen atoms, nitrogen-atoms and metallic atom.Generally, the reaction continues Time can be in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably in 24-36 hours ranges It is interior.
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 alkaline metal cpds and the nitric acid are then added Metal salt, to obtain the aqueous dispersions.In order to further increase the dispersion effect of raw material nano carbon material, while shortening and dividing Raw material nano carbon material can be dispersed in water by the scattered time using the method for sonic oscillation.The condition of the sonic oscillation It can be conventional selection, generally, the frequency of the sonic oscillation can be 10-200kHz, preferably 90-140kHz；It is described The duration of sonic oscillation can be 0.1-6 hours, preferably 1-4 hours.According to the method for the present invention, the alkalinous metal Compound and the nitric acid metal salt can respectively be provided in the form of solution (preferably aqueous solution), can also be with pure material Form provides, and is not particularly limited.
According to the method for the present invention, the content of oxygen element and nitrogen does not limit especially in the raw material nano carbon material It is fixed, it can be conventional selection.Generally, in the raw material nano carbon material content of oxygen element be not higher than 1.5 weight %, it is excellent It is selected as further preferably being not higher than 0.3 weight % not higher than 1.2 weight %, more preferably not above 0.5 weight %；Nitrogen member The content of element is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, into one Step is preferably not higher than 0.05 weight %, still more preferably for not higher than 0.02 weight %.According to the method for the present invention, described The total amount of oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms in raw material nano carbon material It (based on the element) can be customary amount.Generally, remaining in the raw material nano carbon material in addition to oxygen element and nitrogen The total amount (based on the element) of nonmetallic heteroatoms is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably Not higher than 0.1 weight %, it is further preferably not higher than 0.05 weight %.According to the method for the present invention, the raw material nano carbon Material may contain some metallic elements according to the difference in source, such as from using when preparing raw material nano carbon material Metallic atom in catalyst.The content (based on the element) of metallic atom is generally 2.5 weights in the raw material nano carbon material Measure % hereinafter, preferably 1.8 weight % hereinafter, further preferably 0.5 weight % hereinafter, still more preferably be 0.1 weight Measure % or less.
According to the method for the present invention, raw material nano carbon material can be washed before use using method commonly used in the art It washs, to remove some impurity of raw material nano carbon material surface；It can also directly be used without washing.It is disclosed by the invention In embodiment, raw material nano carbon material is not pre-processed using preceding.
Method according to the invention it is possible to handle the nano-carbon material of various existing forms, received to improve this Oxygen atom, nitrogen-atoms and metal element content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon and receive One or both of mitron, graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene with On combination.The carbon nanotube can for one of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube or Two or more combinations.Preferably, the raw material nano carbon material is carbon nanotube, more preferably multi-walled carbon nanotube.
According to the method for the present invention, in a preferred embodiment, the raw material nano carbon material is that multi wall carbon is received Mitron, the specific surface area of the multi-walled carbon nanotube can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100- 260m2/ g, further preferably 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nanotube, temperature of the multi-walled carbon nanotube at 400-800 DEG C The weight-loss ratio spent in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It can be in 0.01- In the range of 0.5, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably exist In the range of 0.05-0.15.
In a kind of more preferably embodiment of the invention, the raw material nano carbon material is multi-walled carbon nanotube, The specific surface area of the multi-walled carbon nanotube is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, into One step is preferably 120-190m2/g；Weight-loss ratio of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, preferably 0.02-0.4's In range, more preferably in the range of 0.05-0.35, further preferably in the range of 0.05-0.15.
According to the method for the present invention, the reaction carries out in closed container.The reaction can self-generated pressure (that is, Do not apply pressure additionally) under carry out, can also carry out under pressure.Preferably, it is described reaction at autogenous pressures into Row.The closed container can be the common reactor for being able to achieve sealing and heating, such as autoclave.
It according to the method for the present invention, can also include solid matter being isolated from the mixture that reaction obtains, and will divide The solid matter separated out is dried, to obtain the nano-carbon material containing metallic atom.
Solid matter can be isolated from the mixture that reaction obtains using common solid-liquid separating method, such as centrifugation, Filtering and decantation one or more of combination.
The condition of the drying can be conventional selection, be can remove the volatile materials in the solid matter isolated It is quasi-.Generally, the drying can 50-200 DEG C at a temperature of carry out, preferably 80-180 DEG C at a temperature of carry out, it is more excellent It is carried out at a temperature of being selected in 120-160 DEG C.The duration of the drying can be selected according to dry temperature and mode. Generally, the duration of the drying can be 0.5-48 hours, preferably 6-24 hours, more preferably 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, oxygen atom, nitrogen-atoms and the metal that can be effectively improved in raw material nano carbon material are former Sub- content, while the structural form of raw material nano carbon material will not be generated and be significantly affected.
According to the third aspect of the present invention, the present invention provides one kind contains metal by prepared according to the methods of the invention Atom nano-carbon material.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material is by the nano-carbon material containing metallic atom of first aspect according to the present invention or according to the present invention Prepared by the nano-carbon material containing metallic atom of three aspects is roasted.
The roasting can carry out under normal conditions.Preferably, it is described roasting 250-500 DEG C at a temperature of carry out. It is highly preferred that it is described roasting 300-450 DEG C at a temperature of carry out, as carried out at a temperature of 350-450 DEG C.The roasting is held The continuous time can be selected according to the temperature of roasting.Generally, the duration of the roasting can be 1-24 hours, preferably It is 2-12 hours, more preferably 2-4 hours.The roasting can carry out in oxygen-containing atmosphere, can also be by the indifferent gas bodily form At atmosphere in carry out.The oxygen-containing atmosphere can be air atmosphere；It can also be mixed to form for oxygen with inert gas mixed Atmosphere is closed, in the mixed atmosphere, the content of oxygen can be 0.1-22 volume %.The inert gas may include but unlimited In nitrogen and/or rare gas, the rare gas can be argon gas and/or helium.Angularly consider from convenience and cost, Preferably, the roasting carries out in oxygen-containing atmosphere (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 unsaturated hydrocarbons, such as 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, the U.S.2 Physical adsorption appearance measurement the specific area.Raw material nano carbon material is analyzed using the high-resolution-ration transmission electric-lens of FEI Co., U.S. production And the microscopic appearance of the nano-carbon material containing metallic atom.
In following embodiment and comparative example, alkaline metal cpds and nitric acid metal salt are respectively mentioned in the form of solid matter For.
Embodiment 1-35 is for illustrating nano-carbon material containing metallic atom and preparation method thereof of the invention.
Embodiment 1
(1) using 20g as multi-walled carbon nanotube (the specific surface area 136m of raw material nano carbon material2/ g, oxygen atom content For 0.3 weight %, nitrogen atom content is 0.02 weight %, and (phosphorus is former for remaining nonmetallic heteroatoms in addition to nitrogen-atoms and oxygen atom Son and sulphur atom) total content be 0.01 weight %, metallic atom total content be 0.1 weight %, in 400-800 DEG C of temperature range Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, is purchased from Chinese science Chengdu organic chemistry Co., Ltd, institute) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition It include: frequency for 140kHz, the time is 1 hour.Then, it is added as the barium hydroxide of alkaline metal cpds and as nitric acid The nickel nitrate of metal salt, to obtain aqueous dispersions, wherein press raw material nano carbon material: alkaline metal cpds: nitric acid metal Salt: H2The weight ratio of O is that the ratio of 1:1:0.5:100 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 150 DEG C of temperature Under, it reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big Air pressure, similarly hereinafter), after 12 hours dry at a temperature of 120 DEG C, nano-carbon material containing metallic atom is obtained, this contains metallic atom and receives Composition, specific surface area and the w of rice carbon material500/w800It is listed in table 1.
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing metallic atom of preparation, and Fig. 2 is as the more of raw material The transmission electron microscope photo of wall carbon nano tube.It can be seen that the microcosmic of the nano-carbon material containing metallic atom from Fig. 1 and Fig. 2 Form is good, and it is little to show that reaction process influences the structure of nano-carbon material.
Comparative example 1
Aqueous dispersions same as Example 1 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 150 DEG C, back flow reaction 24 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 At a temperature of DEG C after drying 12 hours, nano-carbon material containing metallic atom is obtained.The nano-carbon material containing metallic atom of preparation 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, step (1) is prepared Aqueous dispersions be free of nitric acid metal salt.Wherein, by raw material nano carbon material: alkaline metal cpds: nitric acid metal salt: H2O Weight ratio be 1:1:0:100 ratio feed intake.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 alkaline metal cpds.Wherein, by raw material nano carbon material: alkaline metal cpds: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:0:0.5:100 feeds intake.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 4
Ultrasound in deionized water, will be dispersed in using the nano-carbon material dispersion of method identical with comparative example 2 preparation It is carried out under oscillating condition, sonic oscillation condition includes: that frequency is 140kHz, and the time is 1 hour.Then, it is added as nitric acid gold The nickel nitrate for belonging to salt, to obtain aqueous dispersions, wherein press raw material nano carbon material (raw material nano carbon used in comparative example 2 The amount of material): nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:0.5:100 feeds intake.
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 150 DEG C, It reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction kettle, Reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature After the lower drying of degree 12 hours, nano-carbon material containing metallic atom is obtained, this contains the composition of metallic atom nano-carbon material, specific surface Long-pending and w500/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/w800Be 0.33, oxygen atom content is 0.62 weight %, and nitrogen atom content is 0.01 weight %, except nitrogen-atoms and The total content of remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) outside oxygen atom is 0.01 weight %, metallic atom total content For 0.08 weight %.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/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 placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in self-generated pressure Lower reaction 24 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: alkaline metal cpds: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:6:0.5:100 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: alkaline metal cpds: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:1:0.04:100 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 6
Nano-carbon material containing metallic atom is prepared using method same as Example 1, the difference is that, nickel nitrate with etc. rub The plumbi nitras of your amount replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800In table 1 It lists.
Embodiment 7
Using 20g as multi-walled carbon nanotube (the specific surface area 183m of raw material nano carbon material2/ g, oxygen atom content are 0.2 weight %, nitrogen atom content are 0.01 weight %, remaining nonmetallic heteroatoms (phosphorus atoms in addition to nitrogen-atoms and oxygen atom And sulphur atom) total content be 0.04 weight %, metallic atom total content be 0.03 weight %, 400-800 DEG C of humidity province Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.07, purchased from China Chengdu organic chemistry Co., Ltd, the academy of sciences) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation Condition includes: that frequency is 90kHz, and the time is 4 hours.Then, sodium hydroxide and the conduct as alkaline metal cpds is added The palladium nitrate of nitric acid metal salt, to obtain aqueous dispersions, wherein press raw material nano carbon material: alkaline metal cpds: nitric acid Metal salt: H2The weight ratio of O is that the ratio of 1:0.5:0.1:150 feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 120 DEG C of temperature Under, it reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into normal pressure, 160 DEG C At a temperature of after dry 6 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.
Embodiment 8
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), make Specific surface area for the multi-walled carbon nanotube (be purchased from Shandong great Zhan nano material Co., Ltd) of raw material nano carbon material is 103m2/ g, w500/w800Be 0.23, oxygen atom content be 1.1 weight %, nitrogen atom content be 0.03 weight %, denitrogenate with outside oxygen Remaining nonmetallic heteroatoms (p and s) total content be 0.01 weight %, metallic atom total content be 1.6 weight %.Preparation The nano-carbon material containing metallic atom composition, specific surface area and w500/w800It is listed in table 1.
Embodiment 9
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, it, will in step (2) Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in self-generated pressure Lower reaction 24 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 10
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), alkali Under conditions of the total weight of property metallic compound and nitric acid metal salt remains unchanged, make alkaline metal cpds: nitric acid metal salt Molar ratio be 1:6.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is arranged in table 1 Out.
Embodiment 11
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre The nickel nitrate 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 12
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre The barium nitrate 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 13
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium potassium nitrate, calcium nitrate and sodium nitrate replace, nitric acid in sodium nitrate, the total weight of potassium nitrate and calcium nitrate and embodiment 7 The weight of palladium is identical, and the molar ratio of potassium nitrate, calcium nitrate and sodium nitrate is 1:1:1.The nano-carbon material containing metallic atom of preparation Composition, specific surface area and w500/w800It is listed in table 1.
Embodiment 14
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre The plumbi nitras 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 7, unlike, in step (1), nitre The cobalt nitrate 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 16
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium is replaced with copper nitrate and zinc nitrate, and the total weight of copper nitrate and zinc nitrate is identical as the weight of palladium nitrate in embodiment 7, nitre The molar ratio of sour copper and zinc nitrate is 2:1.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/ w800It is listed in table 1.
Embodiment 17
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre The platinum nitrate 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 18
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), hydrogen The calcium hydroxide of sodium oxide molybdena 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 19
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), hydrogen The magnesium hydroxide of sodium oxide molybdena 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 20
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 alkaline metal cpds Potassium hydroxide and nitric acid ruthenium as nitric acid metal salt, to obtain aqueous dispersions, wherein press raw material nano carbon material: alkali Property metallic compound: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:2:0.05:50 feeds intake；
In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 220 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 5
Aqueous dispersions identical with embodiment 20 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 220 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.
Embodiment 21
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 260 DEG C, in spontaneous pressure It is reacted 36 hours under power.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is arranged in table 2 Out.
Embodiment 22
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, 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 23
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 20, unlike, in step (1), Under conditions of the total weight of alkaline metal cpds and nitric acid metal salt remains unchanged, make alkaline metal cpds: nitric acid metal The molar ratio of salt is 1:0.1.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800In table 2 It lists.
Embodiment 24
Nano-carbon material containing metallic atom is prepared using method same as Example 7, 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 alkaline metal cpds Barium hydroxide and cobalt nitrate as nitric acid metal salt, to obtain aqueous dispersions, wherein press raw material nano carbon material: alkali Property metallic compound: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:0.1:4:150 feeds intake；
In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 110 At a temperature of DEG C, react 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.
Embodiment 25
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 24, unlike, in step (1), Multi-walled carbon nanotube as raw material nano carbon material is the same as embodiment 8.Composition, the ratio of the nano-carbon material containing metallic atom of preparation Surface area and w500/w800It is listed in table 2.
Embodiment 26
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 24, unlike, in step (1), By raw material nano carbon material: alkaline metal cpds: nitric acid metal salt: H2The weight ratio of O is that the ratio of 1:8:4:150 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 27
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 24, unlike, in step (1), By raw material nano carbon material: alkaline metal cpds: nitric acid metal salt: H2The weight ratio of O is the ratio of 1:0.1:0.02:150 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 2.
Embodiment 28
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 24, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, in spontaneous pressure It is reacted 36 hours under power.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is arranged in table 2 Out.
Embodiment 29
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 6
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 7
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 8
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 9
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 30
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 31
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 32
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 33
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 34
Nano-carbon material containing metallic atom prepared by embodiment 6 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Embodiment 35
Nano-carbon material containing metallic atom prepared by embodiment 24 450 DEG C at a temperature of air atmosphere in roasting it is 2 small When.
Embodiment 36-70 is used to illustrate application and the hydrocarbon dehydrogenation reaction side of the nano-carbon material of the invention containing metallic atom Method.
Embodiment 36-63
Respectively using the nano-carbon material containing metallic atom of 0.2g (admission space 1.9mL) embodiment 1-28 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 440 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 it is selective and total to calculate n-butane conversion, total olefin Butylene selectivity, the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 10-14
It is reacted using method identical with embodiment 36-63, unlike, it is prepared respectively using comparative example 1-5 Nano-carbon material containing metallic atom is as catalyst.Reaction result is listed in table 3.
Comparative example 15
It is reacted using method identical with embodiment 36-63, unlike, use raw material same as Example 1 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Comparative example 16
It is reacted using method identical with embodiment 36-63, unlike, use raw material same as Example 7 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Embodiment 64-70
It is reacted using method identical with embodiment 36-63, unlike, contained using prepared by embodiment 29-35 Metallic atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 17-20
It is reacted using method identical with embodiment 36-63, unlike, contain gold using prepared by comparative example 6-9 Belong to atom carbon nanotube as catalyst.Reaction result is listed in table 4.
Comparative example 21
It is reacted using method identical with embodiment 36-63, unlike, catalyst is will be same as Example 1 Raw material nano carbon material 350 DEG C at a temperature of air atmosphere in roast 4 hours obtained from.Reaction result arranges in table 4 Out.
Comparative example 22
It is reacted using method identical with embodiment 36-63, unlike, catalyst is will be same as Example 7 Raw material nano carbon material 300 DEG C at a temperature of air atmosphere in roast 12 hours obtained from.Reaction result arranges in table 4 Out.
Table 3
Table 4
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (85)

1. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material contain C element, O element, N element and At least one metallic element, on the basis of the total amount of the nano-carbon material containing metallic atom and based on the element, the content of O element is 1-12 weight %, the content of N element are 0.1-6 weight %, and the total amount of the metallic element is 0.2-15 weight %, C element Content be 67-98.7 weight %, at least partly metallic element be group ia metal element and group iia metallic element,
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 t0.05-0.6's In range；
This contains in metallic atom nano-carbon material, is determined by the peak within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy The amount of O element is IO c, the amount of the O element determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is IO e, IO c/IO eIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, determines the N in the nano-carbon material containing metallic atom by x-ray photoelectron spectroscopy The total amount of element is IN t, the amount of the N element determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy is IN c, IN c/IN tIn the range of 0-0.5, the N determined by the peak within the scope of 403.5-406.5eV in x-ray photoelectron spectroscopy is first The content of element is IN n, IN n/IN tIn 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 1-5；
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 alkaline metal cpds and at least one nitric acid metal salt carry out instead in closed container It answers, the metallic element in the alkaline metal cpds is selected from group ia metal element and group iia metallic element, reaction process In, the temperature of the aqueous dispersions is 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 0.1-0.55； IO c/IO eIn the range of 0.3-0.95；IN c/IN tIn the range of 0.01-0.35；IN n/IN tIn the range of 0.5-0.95； IC c/IC eIn the range of 1-3.
3. nano-carbon material containing metallic atom according to claim 2, wherein IO m/IO tIn the range of 0.18-0.3； IO c/IO eIn the range of 0.6-0.8；IN c/IN tIn the range of 0.03-0.15；IN n/IN tIn the range of 0.65-0.92； IC c/IC eIn the range of 1.2-2.
4. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein contain metallic atom with this On the basis of the total amount of the C element determined in nano-carbon material by x-ray photoelectron spectroscopy, by x-ray photoelectron spectroscopy The content for the C element that peak within the scope of 284.7-284.9eV determines is 60-95 weight %, by x-ray photoelectron spectroscopy The content for the C element that peak within the scope of 286.0-288.8eV determines is 5-40 weight %.
5. nano-carbon material containing metallic atom according to claim 4, 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 65-85 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 15-35 weight %.
6. nano-carbon material containing metallic atom according to claim 5, 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 70-80 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 20-30 weight %.
7. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein by x-ray photoelectron Power spectrum determines that the total amount of the N element in the nano-carbon material containing metallic atom is IN t, by 400.6- in x-ray photoelectron spectroscopy The amount for the N element that peak within the scope of 401.5eV determines is IN g, IN g/IN tFor not higher than 0.3.
8. nano-carbon material containing metallic atom according to claim 7, wherein IN g/IN tIn the range of 0.02-0.25.
9. nano-carbon material containing metallic atom according to claim 8, wherein IN g/IN tIn the range of 0.05-0.2.
10. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein former containing metal with this On the basis of the total amount of sub- nano-carbon material and based on the element, the content of O element is 3-10 weight %, and the content of C element is 76.5- 95 weight %, the content of N element are 0.5-5.5 weight %, and the total amount of the metallic element is 1.5-8 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 6-8 weight %, and the content of C element is 80.5-90.1 weight %, N The content of element is 0.9-5 weight %, and the total amount of the metallic element is 3-6.5 weight %.
12. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein this contains metallic atom Nano-carbon material contains the first metallic element and optional second metallic element, and first metallic element is selected from period of element Group ia metal element and group iia metallic element in table；Second metallic element group VIII in the periodic table of elements Metallic element, I B-group metal element, group iib metallic element and group IVA metallic element.
13. nano-carbon material containing metallic atom according to claim 12, wherein first metallic element is selected from Sodium, potassium, magnesium, barium and calcium；Second metallic element is selected from group VIII metallic element.
14. nano-carbon material containing metallic atom according to claim 12, wherein second metallic element be selected from iron, Ruthenium, cobalt, rhodium, nickel, palladium and platinum.
15. nano-carbon material containing metallic atom according to claim 12, 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 20-100 weight %, second metallic element Content be 0-80 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 40-95 weight %, second metallic element Content is 5-60 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 60-90 weight %；Second metallic element Content is 10-40 weight %.
18. nano-carbon material containing metallic atom according to claim 12, wherein first metallic element be selected from magnesium, Calcium and barium, second metallic element is selected from iron, cobalt and nickel, with the total of the metallic element in the nano-carbon material containing metallic atom On the basis of amount and based on the element, the content of first metallic element is 25-85 weight %, the content of second metallic element For 15-75 weight %.
19. nano-carbon material containing metallic atom according to claim 18, wherein with the nano-carbon material containing metallic atom In metallic element total amount on the basis of and based on the element, the content of first metallic element is 60-75 weight %, described the The content of two metallic elements is 25-40 weight %.
20. nano-carbon material containing metallic atom according to claim 12, wherein first metallic element be selected from sodium and Potassium, second metallic element is selected from ruthenium, rhodium, palladium and platinum, with the total of the metallic element in the nano-carbon material containing metallic atom On the basis of amount and based on the element, the content of first metallic element is 20-95 weight %, the content of second metallic element For 5-80 weight %.
21. nano-carbon material containing metallic atom according to claim 20, wherein with the nano-carbon material containing metallic atom In metallic element total amount on the basis of and based on the element, the content of first metallic element is 65-90 weight %, described the The content of two metallic elements is 10-35 weight %.
22. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein this contains metallic atom Nano-carbon material is carbon nanotube containing metallic atom.
23. nano-carbon material containing metallic atom according to claim 22, wherein this contains metallic atom nano-carbon material and is Multi-walled carbon nanotube containing metallic atom.
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 50-500m2/g。
25. nano-carbon material containing metallic atom according to claim 24, wherein the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 80-300m2/g。
26. nano-carbon material containing metallic atom according to claim 25, wherein the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 90-250m2/g。
27. nano-carbon material containing metallic atom according to claim 26, wherein the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 120-180m2/g。
28. nano-carbon material containing metallic atom according to claim 23, 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.
29. nano-carbon material containing metallic atom according to claim 28, wherein w500/w800In the range of 0.02-0.4 It is interior.
30. nano-carbon material containing metallic atom according to claim 29, wherein w500/w800In the range of 0.05-0.15 It is interior.
31. a kind of preparation method of the nano-carbon material containing metallic atom described in claim 1, this method include being dispersed with one kind The aqueous dispersions of raw material nano carbon material, at least one alkaline metal cpds and at least one nitric acid metal salt are in closed appearance It is reacted in device, the metallic element in the alkaline metal cpds is selected from group ia metal element and group iia metal member Element, in reaction process, the temperature of the aqueous dispersions is maintained in the range of 80-300 DEG C.
32. according to the method for claim 31, wherein raw material nano carbon material: alkaline metal cpds: nitric acid metal salt Weight ratio in the range of 1:0.01-10:0.01-10；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:5-1000.
33. according to the method for claim 32, wherein raw material nano carbon material: alkaline metal cpds: nitric acid metal salt Weight ratio in the range of 1:0.015-8:0.02-5；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:10-500.
34. according to the method for claim 33, wherein raw material nano carbon material: alkaline metal cpds: nitric acid metal salt Weight ratio in the range of 1:0.1-2:0.05-4；
Raw material nano carbon material: H2The weight ratio of O is in the range of 1:50-150.
35. the method according to any one of claim 31-34, wherein alkaline metal cpds: nitric acid metal salt Molar ratio is in the range of 1:0.001-50.
36. according to the method for claim 35, wherein alkaline metal cpds: the molar ratio of nitric acid metal salt is 1: In the range of 0.002-45.
37. according to the method for claim 36, wherein alkaline metal cpds: the molar ratio of nitric acid metal salt is 1: In the range of 0.004-40.
38. the method according to any one of claim 31-34, wherein the metallic element in the nitric acid metal salt Group ia metal element, group iia metallic element, group VIII metallic element, I B-group metal member in the periodic table of elements Element, group iib metallic element and group IVA metallic element.
39. according to the method for claim 38, wherein the metallic element in the nitric acid metal salt is selected from group VIII gold Belong to element.
40. according to the method for claim 39, wherein metallic element in the nitric acid metal salt be selected from iron, ruthenium, cobalt, Rhodium, nickel, palladium and platinum.
41. the method according to any one of claim 31-34, wherein the alkaline metal cpds are selected from containing gold Belong to the hydroxide of element and the basic salt containing metallic element.
42. according to the method for claim 41, wherein the alkaline metal cpds are selected from the hydroxide containing metallic element Object.
43. the method according to any one of claim 31-34, wherein the metal in the alkaline metal cpds Element is selected from group ia metal element and group iia metallic element.
44. according to the method for claim 43, wherein metallic element in the alkaline metal cpds be selected from sodium, potassium, Magnesium, barium and calcium.
45. the method according to any one of claim 31-34, wherein the metal member of the alkaline metal cpds Element is selected from magnesium, calcium and barium, and the metallic element of the nitric acid metal salt is selected from iron, cobalt and nickel, raw material nano carbon material: alkalinous metal Compound: the weight ratio of nitric acid metal salt is in the range of 1:0.05-6:0.04-6, alkaline metal cpds: nitric acid metal salt Molar ratio in the range of 1:0.03-45, raw material nano carbon material: H2The weight ratio of O is in the range of 1:20-200.
46. according to the method for claim 45, wherein raw material nano carbon material: alkaline metal cpds: nitric acid metal salt Weight ratio in the range of 1:0.1-1:0.5-4, alkaline metal cpds: the molar ratio of nitric acid metal salt is 1:0.4-40's In range, raw material nano carbon material: H2The weight ratio of O is in the range of 1:100-150.
47. the method according to any one of claim 31-34, wherein the metal member of the alkaline metal cpds Element is selected from sodium and potassium, and the metallic element of the nitric acid metal salt is selected from ruthenium, rhodium, palladium and platinum, raw material nano carbon material: alkalinous metal Compound: the weight ratio of nitric acid metal salt is in the range of 1:0.01-3:0.02-1, alkaline metal cpds: nitric acid metal salt Molar ratio in the range of 1:0.002-6, raw material nano carbon material: H2The weight ratio of O is in the range of 1:20-200.
48. according to the method for claim 47, wherein raw material nano carbon material: alkaline metal cpds: nitric acid metal salt Weight ratio in the range of 1:0.1-2:0.05-0.1, alkaline metal cpds: the molar ratio of nitric acid metal salt is 1: In the range of 0.004-0.4, raw material nano carbon material: H2The weight ratio of O is in the range of 1:50-150.
49. the method according to any one of claim 31-34, wherein in reaction process, the temperature of the aqueous dispersions Degree is maintained in the range of 110-220 DEG C.
50. the method according to any one of claim 31-34, wherein the duration of the reaction is in 0.5-96 In the range of hour.
51. according to the method for claim 50, wherein the duration of the reaction is in the range of 2-72 hours.
52. method according to claim 51, wherein the duration of the reaction is in the range of 24-36 hours.
53. the method according to any one of claim 31-34, wherein in the raw material nano carbon material, N element Content be not higher than the content of 0.5 weight %, O element be not higher than 1.5 weight %, the total amount of metallic element is 2.5 weights Measure % or less.
54. method according to claim 53, wherein in the raw material nano carbon material, the content of N element be not higher than The content of 0.2 weight %, O element is not higher than 1.2 weight %, and the total amount of metallic element is 1.8 weight % or less.
55. method according to claim 54, wherein in the raw material nano carbon material, the content of N element be not higher than The content of 0.1 weight %, O element is not higher than 0.5 weight %, and the total amount of metallic element is 0.5 weight % or less.
56. method according to claim 55, wherein in the raw material nano carbon material, the content of N element be not higher than The content of 0.05 weight %, O element is not higher than 0.3 weight %, and the total amount of metallic element is 0.1 weight % or less.
57. method according to claim 56, wherein in the raw material nano carbon material, the content of N element be not higher than 0.02 weight %.
58. the method according to any one of claim 31-34, wherein the raw material nano carbon material is carbon nanometer Pipe.
59. method according to claim 58, wherein the raw material nano carbon material is multi-walled carbon nanotube.
60. method according to claim 59, wherein the specific surface area of the multi-walled carbon nanotube is 50-500m2/g。
61. method according to claim 60, wherein the specific surface area of the multi-walled carbon nanotube is 80-300m2/g。
62. method according to claim 61, wherein the specific surface area of the multi-walled carbon nanotube is 100-260m2/g。
63. method according to claim 62, wherein the specific surface area of the multi-walled carbon nanotube is 120-190m2/g。
64. method according to claim 59, 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.
65. method according to claim 64, wherein w500/w800In the range of 0.02-0.4.
66. method according to claim 65, wherein w500/w800In the range of 0.05-0.35.
67. method according to claim 66, wherein w500/w800In the range of 0.05-0.15.
68. the method according to any one of claim 31-34, wherein this method further include obtained from reaction it is mixed It closes in object and isolates solid matter, and the solid matter isolated is dried.
69. method according to claim 68, wherein the drying 50-200 DEG C at a temperature of carry out, the drying Duration be 0.5-48 hours.
70. method according to claim 69, wherein the drying 80-180 DEG C at a temperature of carry out, the drying Duration be 6-24 hours.
71. method according to claim 70, wherein the drying 120-160 DEG C at a temperature of carry out, the drying Duration be 6-12 hours.
72. a kind of nano-carbon material containing metallic atom of the preparation of the method as described in any one of claim 31-71.
73. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material be will be in claim 1-30 arbitrarily Nano-carbon material containing metallic atom described in nano-carbon material containing metallic atom described in one or claim 72 is roasted Prepared by burning.
74. the nano-carbon material containing metallic atom according to claim 73, 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.
75. nano-carbon material containing metallic atom according to claim 74, wherein temperature of the roasting at 300-450 DEG C Degree is lower to carry out, and the duration of the roasting is 2-12 hours.
76. the nano-carbon material containing metallic atom according to claim 75, wherein the duration of the roasting is 2-4 Hour.
77. nano-carbon material containing metallic atom described in any one of claim 1-30 and 72 or claim 73-76 Any one of described in nano-carbon material containing metallic atom as hydrocarbon dehydrogenation reaction catalyst application.
78. the application according to claim 77, wherein the dehydrogenation reaction carries out in the presence of oxygen.
79. the application according to claim 77 or 78, wherein the hydrocarbon is alkane.
80. the application according to claim 79, wherein the hydrocarbon is C2-C12Alkane.
81. the application according to claim 80, wherein the hydrocarbon is normal butane.
82. a kind of hydrocarbon dehydrogenation reaction method, this method is included under conditions of existence or non-existence oxygen, in hydrocarbon dehydrogenation reaction item Under part, by nano-carbon material containing metallic atom or claim described in any one of hydrocarbon and claim 1-30 and 72 The contact of nano-carbon material containing metallic atom described in any one of 73-76.
83. the method according to claim 82, wherein the hydrocarbon is alkane.
84. the method according to claim 83, wherein the hydrocarbon is C2-C12Alkane.
85. the method according to claim 84, wherein the hydrocarbon is normal butane.
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