CN105817246B - One kind nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method - Google Patents

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

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CN105817246B
CN105817246B CN201510701423.0A CN201510701423A CN105817246B CN 105817246 B CN105817246 B CN 105817246B CN 201510701423 A CN201510701423 A CN 201510701423A CN 105817246 B CN105817246 B CN 105817246B
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nano
carbon material
hetero atom
containing hetero
material containing
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CN105817246A (en
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史春风
荣峻峰
于鹏
谢婧新
宗明生
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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
    • B01J27/20—Carbon 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
    • 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
    • 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
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • 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
    • C07C2527/20—Carbon compounds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a kind of nano-carbon material containing hetero atom and its application, the C of O the and 78-96 weight % of N, 1-10 weight % containing 3-12 weight %, in XPS spectrum figure, the N element of the peak determination within the scope of 398.5-400.1eV accounts for the 0.8-1 of whole N elements；The ratio of the amount for the O element that the amount for the O element that peak within the scope of 531.0-532.5eV determines and the peak within the scope of 532.6-533.5eV determine is 0.8-1.5.The invention also discloses a kind of preparation methods of nano-carbon material containing hetero atom.The present invention further discloses the hydrocarbon dehydrogenation reaction methods for using the nano-carbon material containing hetero atom.The nano-carbon material containing hetero atom shows good catalytic activity in hydrocarbon dehydrogenation reaction, can significantly improve the conversion ratio and selectivity of product of raw material.

Description

One kind nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon are de- Hydrogen reaction method
Technical field
The present invention relates to a kind of nano-carbon materials containing hetero atom, and the invention further relates to a kind of nano-carbon materials containing hetero atom Preparation method and the nano-carbon material containing hetero atom prepared by this method, the present invention further relate to a kind of by containing miscellaneous original for above-mentioned Sub- nano-carbon material is roasted and the nano-carbon material containing hetero atom for preparing, contains the invention further relates to according to the present invention Application and a kind of hydrocarbon dehydrogenation reaction method of the hetero atom nano-carbon material as the catalyst of hydrocarbon dehydrogenation reaction.
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 pyrrole Cough up type nitrogen (that is,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen and Pyrroles's type nitrogen is unsaturated nitrogen atom, while replacing carbon atom, often will cause the missing for closing on carbon atom, forms defect Position.
It can be utilized by being introduced in nano-carbon material synthesis process nitrogenous functional atmosphere (such as ammonia, nitrogen) Nitrogen is introduced into the skeleton structure of nano-carbon material by high temperature and/or high pressure simultaneously in the synthesis process of nano-carbon material And/or in surface；Height can also be utilized by the way that nano-carbon material to be placed in nitrogenous functional atmosphere (such as ammonia, nitrogen) Nitrogen is introduced into the surface of nano-carbon material by temperature and/or high pressure.High temperature and/or high pressure are although can be in nano-carbon material Structure nitrogen is formed, but the type of nitrogen containing species depends on reaction condition, is difficult to control；Also, the different type so generated Nitrogen containing species be unevenly distributed on the surface of nano-carbon material, cause the performance of nitrogenous nano-carbon material unstable.It can be with By the way that nano-carbon material is carried out oxidation processes, then reacted with amine, to introduce nitrogen-atoms on nano-carbon material surface, so The nitrogen-atoms of introducing 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 hetero atom, using this method energy The content of oxygen atom and nitrogen-atoms in nano-carbon material is steadily improved, and the structure of nano-carbon material itself is influenced not Greatly.
It is another object of the present invention to provide a kind of nano-carbon materials containing hetero atom, this contains hetero atom nano-carbon material There is preferable catalytic effect to the dehydrogenation reaction of hydrocarbons, the conversion ratio of raw material can not only be effectively improved, and to de- Hydroformylation reaction product has preferable selectivity.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing hetero atom, this contains hetero atom Nano-carbon material contains C element, O element and N element, on the basis of the total amount of the nano-carbon material containing hetero atom and with element Meter, the content of N element are that the content of 3-12 weight %, O element is 1-10 weight %, and the content of C element is 78-96 weight %；
The total amount that the N element in the nano-carbon material containing hetero atom is determined by x-ray photoelectron spectroscopy is IN t, by X-ray The amount for the N element that peak in photoelectron spectroscopy within the scope of 398.5-400.1eV determines is IN c, IN c/IN tIn the range of 0.8-1；
This contains in hetero atom nano-carbon material, is determined by the peak within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy O element amount be 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 0.8-1.5.
According to the second aspect of the invention, the present invention provides a kind of preparation method of nano-carbon material containing hetero atom, This method includes reacting a kind of aqueous dispersions for being dispersed with raw material nano carbon material in closed container, the water dispersion Dissolved at least one nitrogenous compound in liquid, the nitrogenous compound is selected from NH3, hydrazine and urea, in reaction process, the water The temperature of dispersion liquid is in the range of 80-250 DEG C.
According to the third aspect of the present invention, the present invention provides a kind of method systems by the second aspect according to the present invention Standby nano-carbon material containing hetero atom.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing hetero atom, this contains hetero atom Nano-carbon material is to roast the nano-carbon material containing hetero atom in terms of first aspect according to the present invention or third Prepared by.
According to the fifth aspect of the present invention, the present invention provides the nanometers containing hetero atom of first aspect according to the present invention Carbon material, the according to the present invention nano-carbon material containing hetero atom in terms of third or according to the fourth aspect of the present invention Application of the nano-carbon material containing hetero atom as the catalyst of hydrocarbon dehydrogenation reaction.
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 miscellaneous original Sub- nano-carbon material, the according to the present invention nano-carbon material containing hetero atom of third aspect or according to the present invention the 4th side The nano-carbon material containing hetero atom in face contacts.
The preparation method of the nano-carbon material according to the present invention containing hetero atom can not only steadily regulate and control and/or improve to receive Content of heteroatoms in rice carbon material, while small, the nano carbon material containing hetero atom of preparation is influenced on the structure of nano-carbon material itself Material has stable performance.
Nano-carbon material containing hetero atom according to the present invention shows good catalysis in the dehydrogenation reaction of hydrocarbons Performance can significantly improve feed stock conversion and selectivity of product.
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 hetero 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 hetero atom, this contains hetero atom Nano-carbon material contains C element, O element and N element.
Nano-carbon material containing hetero atom according to the present invention, on the basis of the total amount of the nano-carbon material containing hetero atom and with Element meter, the content of N element are 3-12 weight %, preferably 3.5-10 weight %, more preferably 3.5-9.5 weight %；O element Content be 1-10 weight %, preferably 3-9 weight %, more preferably 4.5-8 weight %；The content of C element is 78-96 weight Measure %, preferably 81-93.5 weight %, more preferably 82.5-92 weight %.Wherein, the content of each element uses X-ray photoelectricity Sub- power spectrum (XPS) method measurement, the content of element is determined by the corresponding area of 1s electronics spectral peak；Sample is before testing at 150 DEG C Temperature and the pressure of 1 normal atmosphere are 3 hours dry 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 hetero atom according to the present invention determines that this contains hetero atom nano-sized carbon by x-ray photoelectron spectroscopy The total amount of N element in material is IN t, the N element that is determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy Amount be IN c, IN c/IN tIn the range of 0.8-1, preferably in the range of 0.8-0.95, more preferably in the range of 0.85-0.92 It is interior.Nano-carbon material containing hetero atom according to the present invention, by the peak within the scope of 400.6-401.5eV in x-ray photoelectron spectroscopy Determining N element (that is, graphite mould nitrogen) is substantially not present or content is lower.Generally, according to the present invention to be received containing hetero atom In rice 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 tIn the range of 0-0.2, preferably in the range of 0.05-0.2, more preferably in the range of 0.08-0.15.In the present invention, When indicating numberical range, " ×-× in the range of " it include two binary values.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peak in x-ray photoelectron spectroscopyN 1, by X-ray N1s spectral peak in photoelectron spectroscopy is divided into two groups of peaks, i.e., the spectral peak within the scope of 400.6-401.5eV (corresponds to graphite mould nitrogen Species) and 398.5-400.1eV within the scope of spectral peak (nitrogen species in addition to graphite mould nitrogen), determine this respective face in two groups of peaks Product, is denoted as A for the area of the spectral peak within the scope of 400.6-401.5eVN 2, by the spectral peak within the scope of 398.5-400.1eV Area is denoted as AN 3, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, when obtained ratio is 0.01 or less, it is believed that be free of such Species, and the content of such species is denoted as 0.
Nano-carbon material containing hetero atom according to the present invention, by within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy Peak determine O element (that is, C=O) amount be IO c, true by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy The amount of fixed O element (that is, C-O) is IO e, IO c/IO eIt is more excellent preferably in the range of 0.85-1.2 in the range of 0.8-1.5 It is selected in the range of 0.9-1.In the present invention, by the area A of the O1s spectral peak in x-ray photoelectron spectroscopyO 1Determine the total of O element Amount, is divided into two groups of peaks for the O1s spectral peak in x-ray photoelectron spectroscopy, i.e., the spectral peak within the scope of 531.0-532.5eV is (corresponding In C=O species) and spectral peak (correspond to C-O species) within the scope of 532.6-533.5eV, it will be in 531.0-532.5eV model The area of spectral peak in enclosing is denoted as AO 2, the area of the spectral peak within the scope of 532.6-533.5eV is denoted as AO 3, IO c/IO e=AO 2/ AO 3。
Nano-carbon material containing hetero atom according to the present invention, the total amount with C element in the nano-carbon material containing hetero atom are Benchmark, the content of the C element determined by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy (that is, graphite mould carbon) It can be 60-98 weight %, preferably 65-95 weight %, more preferably 75-85 weight %；By in x-ray photoelectron spectroscopy The total content for the C element that peak within the scope of 286.0-288.8eV determines can be 2-40 weight %, preferably 5-35 weight %, More preferably 15-25 weight %.In the present invention, by the area A of the C1s spectral peak in x-ray photoelectron spectroscopyC 1Determine C element C1s spectral peak in x-ray photoelectron spectroscopy is divided into two groups of peaks by total amount, i.e., the spectral peak within the scope of 284.7-284.9eV is (right Should be in graphite mould carbon species) and spectral peak (correspond to non-graphite type carbon species) within the scope of 286.0-288.8eV, it will be The area of spectral peak within the scope of 284.7-284.9eV is denoted as AC 2, the area of the spectral peak within the scope of 286.0-288.8eV is denoted as AC 3, by the content=A for the C element that the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy determinesC 2/AC 1, penetrated by X Total content=the A for the C element that peak in photoelectron spectra within the scope of 286.0-288.8eV determinesC 3/AC 1。
Nano-carbon material containing hetero atom according to the present invention, this contains in hetero atom nano-carbon material, by x-ray photoelectron energy The amount for the C element that peak in spectrum within the scope of 288.6-288.8eV determines is IC c, by 286.0- in x-ray photoelectron spectroscopy The amount for the C element that peak within the scope of 286.2eV determines is IC e, IC c/IC eIn the range of 0.5-1.5, preferably 0.6-1.4's In range.In the present invention, the spectral peak in x-ray photoelectron spectroscopy within the scope of 286.0-288.8eV (is corresponded into agraphitic carbon Species) be further divided into two groups of peaks, i.e., the spectral peak (corresponding to hydroxyl and ether type carbon species) within the scope of 286.0-286.2eV And the spectral peak (corresponding to carboxyl, acid anhydride and ester type carbon species) within the scope of 288.6-288.8eV, it will be in 286.0-286.2eV The area of spectral peak in range is denoted as AC 4, the area of the spectral peak within the scope of 288.6-288.8eV is denoted as AC 5, IC c/IC e= AC 5/AC 4。
In the present invention, position combination as corresponding to the summit at the peak at each peak be can determine that, range determines by mentioned earlier Peak refer to combination corresponding to summit can peak within that range, in the range may include a peak, also can wrap Include more than two peaks.Such as: the peak within the scope of 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 hetero atom according to the present invention can exist with common various forms, be specifically as follows but not Be limited to carbon nanotube containing hetero atom, graphene containing hetero atom, thin layer graphite containing hetero atom, nano carbon particle containing hetero atom, containing miscellaneous The combination of one or more of atom carbon nano-fiber, Nano diamond containing hetero atom and doped fullerene.Institute Stating can be for single-walled carbon nanotube containing hetero atom, double-walled carbon nano-tube containing hetero atom and containing hetero atom containing heteroatomic carbon nanotube The combination of one or more of multi-walled carbon nanotube.Nano-carbon material containing hetero atom according to the present invention, preferably contains Hetero atom multi-walled carbon nanotube.
Nano-carbon material containing hetero atom according to the present invention, it is preferable that the ratio table of the multi-walled carbon nanotube containing hetero atom Area is 50-500m2/ g can be further improved the catalytic performance of the nano-carbon material containing hetero atom, especially as hydrocarbon in this way The catalytic performance of the catalyst of substance dehydrogenation reaction.It is highly preferred that the specific surface area for containing hetero atom multi-walled carbon nanotube is 80-300m2/g.It is further preferred that the specific surface area for containing hetero atom multi-walled carbon nanotube is 90-250m2/g.Further Preferably, which is 95-150m2/g.In the present invention, specific surface area is inhaled by nitrogen Attached BET method measurement.
Nano-carbon material containing hetero atom according to the present invention, the multi-walled carbon nanotube containing hetero atom is at 400-800 DEG C Weight-loss ratio in temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that In the range of 0.01-0.5, better catalytic effect can be obtained in this way, is especially used as the catalysis of hydrocarbons dehydrogenation reaction When agent, better catalytic effect can be obtained.It is highly preferred that w500/w800In the range of 0.02-0.2.In the present invention, w800= W800- W400, w500=W500- W400, W400For in 400 DEG C of the at a temperature of mass loss rate that measures, W800For in 800 DEG C of temperature The lower mass loss rate measured of degree, W500For in 500 DEG C of the at a temperature of mass loss rate that measures；The weight-loss ratio uses thermogravimetric Analyzer measures in air atmosphere, and test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample exists before testing 150 DEG C of temperature and the pressure of 1 normal atmosphere are 3 hours dry in helium atmosphere.
In a preferred embodiment of the invention, it is more preferably to contain hetero atom for the nano-carbon material containing hetero atom Wall carbon nano tube, which is 50-500m2/ g, preferably 80-300m2/ g, it is more excellent It is selected as 90-250m2/ g, further preferably 95-150m2/ g, and w500/w800In the range of 0.01-0.5, preferably exist In the range of 0.02-0.2.
Nano-carbon material containing hetero atom according to the present invention, such as sulphur atom and the other nonmetallic heteroatoms contents of phosphorus atoms It can be customary amount.Generally, in nano-carbon material containing hetero atom according to the present invention, its outside oxygen atom and nitrogen-atoms The total amount of its nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) can be 0.5 weight % hereinafter, preferably 0.2 weight % with Under.Nano-carbon material containing hetero atom according to the present invention can also contain a small amount of metallic atom, the general source of these metallic atoms The catalyst used when preparing nano-carbon material, the content of the metallic atom are generally 0.5 weight % hereinafter, preferably 0.2 weight % or less.
According to the second aspect of the invention, the present invention provides a kind of preparation method of nano-carbon material containing hetero atom, This method includes reacting a kind of aqueous dispersions for being dispersed with raw material nano carbon material in closed container, the water dispersion Dissolved at least one nitrogenous compound in liquid.In the present invention, "at least one" indicates one or more kinds of.
The nitrogenous compound is selected from NH3, hydrazine and urea.
According to the method for the present invention, the dosage of the nitrogenous compound can be according to it is contemplated that draw in raw material nano carbon material The content and type of the nitrogen and oxygen element that enter are selected.The nano-carbon material containing hetero atom finally prepared with When making the catalyst of hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material: the weight ratio of nitrogenous compound is 1:0.05-50, by The nano-carbon material containing hetero atom of this preparation shows better catalytic activity when being used as the catalyst of hydrocarbon dehydrogenation reaction.It is more excellent Selection of land, raw material nano carbon material: the weight ratio of nitrogenous compound is 1:0.1-20.It is further preferred that raw material nano carbon material: The weight ratio of nitrogenous compound is 1:0.3-10.It is further preferred that raw material nano carbon material: the weight ratio of nitrogenous compound For 1:0.5-5.
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 1:1-200, and when within the scope of the dosage of water being in this, nano-carbon material is being located Structural form retentivity during reason is more preferable, such as: it is carbon nanotube in raw material nano carbon material, during processing substantially It is not cut off.It is highly preferred that raw material nano carbon material: H2The weight ratio of O is 1:2-100.It is further preferred that raw material nano Carbon material: H2The weight ratio of O is 1:10-50.Furthermore it is also possible to be adjusted according to dosage of the type of nitrogenous compound to water It is whole, so that subject to the nitrogenous compound can be dissolved in water.
According to the method for the present invention, nitrogenous compound and water consumption can also be carried out according to the type of nitrogenous compound Optimization.
In a preferred embodiment of the invention, the nitrogenous compound is NH3, raw material nano carbon material: NH3 Weight ratio preferably in the range of 1:0.1-5, more preferably in the range of 1:0.2-2, further preferably 1:0.3-0.8's In range.In the preferred embodiment, raw material nano carbon material: H2The weight ratio of O preferably in the range of 1:2-100, More preferably in the range of 1:5-50, further preferably in the range of 1:8-25.
In another preferred embodiment of the invention, the nitrogenous compound be urea, raw material nano carbon material: The weight ratio of urea is preferably in the range of 1:0.1-25, more preferably in the range of 1:0.5-15, further preferably in 1:1-8 In the range of, still more preferably in the range of 1:1.2-3.In the preferred embodiment, raw material nano carbon material: H2The weight ratio of O is preferably 1:5-100, more preferably 1:10-50, further preferably 1:15-30.
In another preferred embodiment of the invention, the nitrogenous compound is hydrazine, raw material nano carbon material: hydrazine Weight ratio preferably in the range of 1:0.1-15, more preferably in the range of 1:0.2-10, further preferably 1:0.3-6's In range.In the preferred embodiment, raw material nano carbon material: H2The weight ratio of O is preferably 1:2-100, more preferably 1:5-75, further preferably 1:10-50.
According to the method for the present invention, the condition of the reaction is to be enough to improve oxygen atom and nitrogen in raw material nano carbon material Subject to the content of atom.Preferably, in reaction process, the temperature of the aqueous dispersions is in the range of 80-250 DEG C.Described When the temperature of aqueous dispersions is within above range, the oxygen atom and nitrogen in raw material nano carbon material can not only be effectively improved Atom content, and the structural form of raw material nano carbon material will not be generated and be significantly affected.It is highly preferred that in reaction process, The temperature of the aqueous dispersions is in the range of 100-220 DEG C.It is further preferred that in reaction process, the aqueous dispersions Temperature is in the range of 110-200 DEG C.
According to the method for the present invention, the duration of the reaction can be selected according to the temperature of reaction, with can It is introduced in raw material nano carbon material subject to enough oxygen atom and nitrogen-atoms.Generally, the duration of the reaction can be with In the range of 0.5-144 hours, preferably in the range of 2-72 hours, more preferably in the range of 10-60 hours, further It is preferred that in the range of 20-40 hours.
According to the method for the present invention, the temperature of the reaction and duration can be according to nitrogens in the aqueous dispersions The type for closing object is selected.
In a preferred embodiment of the invention, the nitrogenous compound is NH3, the temperature of the aqueous dispersions It is 140-220 DEG C, preferably 150-190 DEG C, the duration of the reaction is 2-72 hours, preferably 6-48 hours, more excellent It is selected as 20-40 hours.
In another preferred embodiment of the invention, the nitrogenous compound is urea, the aqueous dispersions Temperature is 100-160 DEG C, and preferably 105-145 DEG C, duration of the reaction is 8-60 hours, preferably 12-48 hours, More preferably 18-30 hours.
In another preferred embodiment of the invention, the nitrogenous compound is hydrazine, the temperature of the aqueous dispersions Degree is 120-180 DEG C, and preferably 125-165 DEG C, duration of the reaction is 6-96 hours, preferably 12-60 hours, more Preferably 20-40 hours.
Method according to the invention it is possible to form the aqueous dispersions using common various methods, such as can incite somebody to action Raw material nano carbon material is dispersed in water (preferably deionized water), and the nitrogenous compound is then added, to obtain described Aqueous dispersions.The nitrogenous compound can provide as a solution according to specific substance, can also be in the form of pure material It provides, is not particularly limited.In order to further increase the dispersion effect of raw material nano carbon material, while shortening the time of dispersion, Raw material nano carbon material can be dispersed in water using the method for sonic oscillation.The condition of the sonic oscillation can be conventional Selection, generally, the frequency of the sonic oscillation can be 10-100kHz, and the duration of the sonic oscillation can be 0.1-6 hours, preferably 0.5-2 hours.
According to the method for the present invention, the content of O element and N element is not particularly limited in the raw material nano carbon material, It can be conventional selection.Generally, the content of O element is not higher than 1.2 weight %, preferably in the raw material nano carbon material Not higher than 0.5 weight %；The content of N element 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 materials The total amount of oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms can contain in material to be conventional Amount.Generally, in the raw material nano carbon material total amount of oxygen atom and remaining nonmetallic heteroatoms outside nitrogen-atoms (with member Element meter) be not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, it is further excellent It is selected as not higher than 0.05 weight %.According to the method for the present invention, difference of the raw material nano carbon material according to source, Ke Yihan There are some metallic elements, these metallic elements are typically derived from the catalyst used when preparing raw material nano carbon material, content (based on the element) generally in 2 weight % hereinafter, it is preferred that in 1 weight % hereinafter, more preferably below 0.5 weight %.
According to the method for the present invention, raw material nano carbon material can be carried out pre- before use using method commonly used in the art Processing (as washed), to remove some impurity of raw material nano carbon material surface；It can also directly be used without pretreatment, In embodiment disclosed by the invention, raw material nano carbon material is not pre-processed using preceding.
Method according to the invention it is possible to handle the nano-carbon material of various existing forms, received to improve this Oxygen atom and nitrogen atom content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon nanotube, graphite The combination of one or more of alkene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene. The carbon nanotube can be one or more of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube Combination.Preferably, the raw material nano carbon material is carbon nanotube, more preferably multi-walled carbon nanotube.
In a preferred embodiment, the raw material nano carbon material is multi-walled carbon nanotube, and the multi wall carbon is received The specific surface area of mitron is 20-500m2/ g, preferably 50-300m2/ g, more preferably 80-250m2/ g, further preferably 90- 150m2/g.When the specific surface area of the multi-walled carbon nanotube is within above range, finally obtained nanometer containing hetero atom Carbon material has better catalytic activity, especially when being used as the catalyst of dehydrogenation reaction of hydrocarbons, can obtain more preferable Catalytic effect.
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 is preferred that in 0.01- In the range of 0.5, more preferably in the range of 0.02-0.2.Thus the nano-carbon material containing hetero atom prepared is shown preferably Catalytic effect can obtain better catalytic effect when being especially used as the catalyst of hydrocarbons dehydrogenation reaction.
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 20-500m2/ g, preferably 50-300m2/ g, more preferably 80-250m2/ g, into One step is preferably 90-150m2/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/w800It is preferred that more preferably existing in the range of 0.01-0.5 In the range of 0.02-0.2.
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 hetero 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 100-150 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 3-24 hours, more preferably 5-15 hours.Institute Stating drying can carry out under normal pressure (that is, 1 standard atmospheric pressure), can also carry out at reduced pressure.From further increasing The angle of dry efficiency is set out, and the drying preferably carries out at reduced pressure.
According to the method for the present invention, the oxygen atom and nitrogen atom content in raw material nano carbon material can be effectively improved, together Shi Buhui significantly affects the structural form generation of raw material nano carbon material.
As a result, according to the third aspect of the present invention, the present invention provides one kind by prepared according to the methods of the invention Nano-carbon material containing hetero atom.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing hetero atom, this contains hetero atom Nano-carbon material be by the nano-carbon material containing hetero atom of first aspect according to the present invention or according to the present invention third side Prepared by the nano-carbon material containing hetero atom in face is roasted.
The roasting can carry out under normal conditions.Preferably, it is described roasting 250-500 DEG C at a temperature of carry out. It is highly preferred that it is described roasting 300-450 DEG C at a temperature of carry out.The duration of the roasting can be according to the temperature of roasting It is selected.Generally, the duration of the roasting can be 1-24 hours, and preferably 2-12 hours, more preferably 2-6 was small When.The roasting can carry out in oxygen-containing atmosphere, can also carry out in the atmosphere formed by inert gas.It is described oxygenous Atmosphere can be air atmosphere；It can also be the mixed atmosphere that oxygen and inert gas are mixed to form, in the mixed atmosphere, oxygen Content can be 0.1-22 volume %.The inert gas can include but is not limited to nitrogen and/or rare gas, described dilute Having gas can be argon gas and/or helium.Angularly consider from convenience and cost, it is preferable that the roasting is in oxygen-containing atmosphere It is carried out in (such as air atmosphere).
Nano-carbon material containing hetero atom according to the present invention or the nano-sized carbon containing hetero atom prepared by method of the invention Material has good catalytic performance, and higher catalytic activity is especially shown in hydrocarbons dehydrogenation reaction.
Nano-carbon material containing hetero atom according to the present invention or the nano-sized carbon containing hetero atom prepared by method of the invention Material can be directly used as catalyst, can also be used in the form of preformed catalyst.The preformed catalyst can contain root According to nano-carbon material containing hetero atom of the invention or the nano-carbon material containing hetero atom prepared by method of the invention and glue Tie agent.The binder can be selected according to the specifically used occasion of the preformed catalyst, can satisfy requirement Subject to, such as can be organic binder and/or inorganic binder.The organic binder can be common various polymer Type binder, the inorganic binder can be common various heat-resistant inorganic oxides, such as aluminium oxide and/or silica.? The preformed catalyst is anti-to hydrocarbon dehydrogenation reaction (such as direct dehydrogenation reaction and oxidative dehydrogenation), particularly to oxidative dehydrogenation When should have the preformed catalyst of catalytic action, the binder is preferably inorganic binder.In the preformed catalyst, containing miscellaneous The content of atom nano-carbon material can be selected according to specifically used requirement, be not particularly limited, generally, with it is described at On the basis of the total amount of type catalyst, the content of the nano-carbon material containing hetero atom can be 5-95 weight %.
According to the fifth aspect of the present invention, the present invention provides the nanometers containing hetero atom of first aspect according to the present invention Carbon material, the according to the present invention nano-carbon material containing hetero atom in terms of third or according to the present invention the 4th aspect contain Application of the hetero atom nano-carbon material as the catalyst of hydrocarbon dehydrogenation reaction.
Application according to the present invention, the nano-carbon material containing hetero atom are used directly for hydrocarbon dehydrogenation reaction, can also be with Hydrocarbon dehydrogenation reaction is used for after molding.The dehydrogenation reaction can carry out in the presence of oxygen, can not also in the presence of oxygen into Row.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 miscellaneous original Sub- nano-carbon material, the according to the present invention nano-carbon material containing hetero atom of third aspect or according to the present invention the 4th side The nano-carbon material containing hetero atom in face contacts.
Hydrocarbon dehydrogenation reaction method according to the present invention, the nano-carbon material containing hetero atom are used directly for connecing with hydrocarbon Touching is used to contact with hydrocarbon after can also forming the nano-carbon material containing hetero atom.
Hydrocarbon dehydrogenation reaction method according to the present invention can carry out dehydrogenation to a plurality of types of hydrocarbon, to obtain unsaturation Hydrocarbon, such as alkene.According to the method for the present invention particularly suitable for carrying out dehydrogenation to alkane, to obtain alkene.
According to the method for the present invention, the hydrocarbon is preferably alkane, such as C2-C12Alkane.Specifically, the hydrocarbon can be but Be not limited to ethane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentane, 3- methylpentane, 2,3- dimethylbutane, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- second Base pentane, 3- ethylpentane, 2,3- dimethyl pentane, 2,4- dimethyl pentane, normal octane, 2- methyl heptane, 3- methyl heptane, 4- methyl heptane, 2,3- dimethylhexane, 2,4- dimethylhexane, 2,5- dimethylhexane, 3- ethyl hexane, 2,2,3- front three Base pentane, 2,3,3- trimethylpentane, 2,4,4- trimethylpentane, 2- methyl -3- ethylpentane, n -nonane, 2- methyloctane, 3- methyloctane, 4- methyloctane, 2,3- dimethyl heptane, 2,4- dimethyl heptane, 3- ethyl heptane, 4- ethyl heptane, 2, 3,4- trimethyl cyclohexane, 2,3,5- trimethyl cyclohexane, 2,4,5- trimethyl cyclohexane, 2,2,3- trimethyl cyclohexane, 2,2,4- front three Base hexane, 2,2,5- trimethyl cyclohexane, 2,3,3- trimethyl cyclohexane, 2,4,4- trimethyl cyclohexane, 2- methyl -3- ethyl hexane, 2- methyl -4- ethyl hexane, 3- methyl -3- ethyl hexane, 3- methyl -4- ethyl hexane, 3,3- diethylpentane, 1- methyl - 2- ethyl cyclohexane, 1- methyl -3- ethyl cyclohexane, 1- methyl -4- ethyl cyclohexane, n-propyl hexamethylene, isopropyl hexamethylene Alkane, trimethyl-cyclohexane (the various isomers including trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- front threes Butylcyclohexane, 1,2,5- trimethyl-cyclohexane, 1,3,5- trimethyl-cyclohexane), n-decane, 2- methylnonane, 3- methylnonane, 4- methylnonane, 5- methylnonane, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyl octane, 4- ethyl octane, 2, 3,4- trimethylheptane, 2,3,5- trimethylheptane, 2,3,6- trimethylheptane, 2,4,5- trimethylheptane, 2,4,6- front three Base heptane, 2,2,3- trimethylheptane, 2,2,4- trimethylheptane, 2,2,5- trimethylheptane, 2,2,6- trimethylheptane, 2, 3,3- trimethylheptane, 2,4,4- trimethylheptane, 2- methyl -3- ethyl heptane, 2- methyl -4- ethyl heptane, 2- methyl -5- Ethyl heptane, 3- methyl -3- ethyl heptane, 4- methyl -3- ethyl heptane, 5- methyl -3- ethyl heptane, 4- methyl -4- ethyl Heptane, 4- propyl heptane, 3,3- diethylhexane, 3,4- diethylhexane, 2- methyl -3,3- diethylpentane, vinylbenzene, 1- In phenyl-propane, 2- phenyl-propane, 1- phenyl butane, 2- phenyl butane, 1- phenyl pentane, 2- phenyl pentane and 3- phenyl pentane A combination of one or more.It is highly preferred that the hydrocarbon be one of propane, normal butane, iso-butane and vinylbenzene or It is two or more.It is further preferred that the hydrocarbon is normal butane.
Hydrocarbon dehydrogenation reaction method according to the present invention, the reaction can carry out under conditions of there are oxygen, can also be with It is carried out under conditions of oxygen is not present.Preferably, hydrocarbon dehydrogenation reaction method according to the present invention, under conditions of there are oxygen It carries out.When method of the invention carries out under conditions of there are oxygen, the dosage of oxygen can be conventional selection.Generally, The molar ratio of hydrocarbon and oxygen can be 0.01-100:1, preferably 0.1-10:1, more preferably 0.2-5:1, most preferably 0.3- 2:1, such as 0.4-1:1.
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 hetero atom.The carrier gas can for it is common at reaction conditions will not with reactant and react The gas that product occurs chemical interaction and will not decompose, such as nitrogen, carbon dioxide, rare gas and vapor One or more of combination.The dosage of the carrier gas can be conventional selection.Generally, the content of carrier gas can be with 30-99.5 volume %, preferably 50-99 volume %, more preferably 70-98 volume %.
The temperature of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be conventional selection, to be enough to send out hydrocarbon Subject to raw dehydrogenation reaction.Generally, the contact can 200-650 DEG C at a temperature of carry out, preferably in 300-600 DEG C of temperature Degree is lower to carry out, more preferably 350-550 DEG C at a temperature of carry out, further preferably 400-450 DEG C at a temperature of carry out.
Hydrocarbon dehydrogenation reaction method according to the present invention, the contact can carry out in fixed bed reactors, can also be It carries out, is not particularly limited in fluidized-bed reactor.Preferably, the contact carries out in fixed bed reactors.
The duration of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be selected according to the temperature of contact It selects, when such as described contact carries out in fixed bed reactors, continuing for contact can be indicated with volume space velocity when the gas of charging Time.Generally, volume space velocity can be 0.1-10000h when the gas of charging-1, preferably 1-6000h-1, more preferably 5- 5000h-1, further preferably 10-4000h-1, such as 400-800h-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 hetero atom.
Embodiment 1-29 is for illustrating nano-carbon material containing hetero 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 is in deionized water, wherein it is dispersed under the conditions of sonic oscillation and carries out, ultrasound vibration The condition of swinging includes: that frequency is 14kHz, and the time is 0.5 hour.Then, NH is added into aqueous dispersions3, it stirs evenly, thus To aqueous dispersions, wherein NH3It is provided in the form of 25 weight % aqueous solutions, by raw material nano carbon material: NH3: H2The weight ratio of O It feeds intake for the ratio of 1:0.6:11.8.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 170 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), 6 hours dry at a temperature of 120 DEG C, nano-carbon material containing hetero atom is obtained, this contains hetero atom nano-carbon material Composition, specific surface area and w500/w800It is listed in table 1.
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing hetero atom of preparation, and Fig. 2 is the multi wall as raw material The transmission electron microscope photo of carbon nanotube.It can be seen that the micromorphology of the nano-carbon material containing hetero atom from Fig. 1 and Fig. 2 Well, it is little to show that reaction process influences the structure of the nano-carbon material containing hetero atom.
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 170 DEG C of oil bath, back flow reaction 24 hours under normal pressure.After reaction, it is cooled to room temperature to the temperature in three-necked flask, 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 6 hours, nano-carbon material containing hetero atom is obtained.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 1.
Comparative example 2
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, what step (1) was prepared Aqueous dispersions are free of NH3.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is arranged in table 1 Out.
Comparative example 3
The quartz in roaster is placed in using 20g as the multi-walled carbon nanotube (with embodiment 1) of raw material nano carbon material Middle part (quartz ampoule both ends (i.e. carbon nanotube two sides) are filled with silica wool), is then passed through ammonia by metering pump, wherein stone in pipe Temperature is 170 DEG C, ammonia flow 15mL/min in English pipe, and the time is 24 hours.After reaction, to the temperature in quartz ampoule It is cooled to room temperature, opens roaster, take out carbon nanotube after the processing in quartz ampoule, obtain carbon nanomaterial containing hetero atom.System Composition, specific surface area and the w of the standby nano-carbon material containing hetero atom500/w800It is listed in table 1.
Comparative example 4
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), NH3 With the NH of equimolar amounts4Cl is replaced.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800In table 1 In list.
Embodiment 2
Nitrogenous nano-carbon material is prepared using method same as Example 1, unlike, in step (1), as raw material The specific surface area of the multi-walled carbon nanotube (being purchased from Shandong great Zhan nano material Co., Ltd) of nano-carbon material is 251m2/ g, Weight-loss ratio in 400-800 DEG C of temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/ w800It is 0.33, oxygen atom content is 0.62 weight %, and nitrogen atom content is 0.01 weight %, in addition to nitrogen-atoms and oxygen atom The total content of remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) is 0.01 weight %, and metallic atom total content is 0.08 weight Measure %.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
Embodiment 3
Nitrogenous nano-carbon material is prepared using method same as Example 1, unlike, in step (2), by what is obtained Aqueous dispersions at a temperature of 190 DEG C, react 24 in the autoclave with polytetrafluoroethyllining lining at autogenous pressures Hour.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
Embodiment 4
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), by original Expect nano-carbon material: NH3: H2The weight ratio of O is that the ratio of 1:4:11.8 feeds intake.The group of the nano-carbon material containing hetero atom of preparation At, specific surface area and w500/w800It is listed in table 1.
Embodiment 5
(1) using 20g as multi-walled carbon nanotube (the specific surface area 103m of raw material nano carbon material2/ g, oxygen atom content For 0.2 weight %, nitrogen atom content is 0.01 weight %, and (phosphorus is former for remaining nonmetallic heteroatoms in addition to nitrogen-atoms and oxygen atom Son and sulphur atom) total content be 0.04 weight %, metallic atom total content be 0.3 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 2 hours, and NH is then added3, stir evenly, to obtain aqueous dispersions, wherein NH3It is provided in the form of 20 weight % aqueous solutions, by raw material nano carbon material: NH3: H2The weight ratio of O is the ratio of 1:0.4:19.6 Example feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 150 DEG C of temperature Under, it reacts 36 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, 100 DEG C At a temperature of after dry 12 hours, obtain nano-carbon material containing hetero atom, this contains the composition of hetero atom nano-carbon material, specific surface area And w500/w800It is listed in table 1.
Embodiment 6
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (2), will To aqueous dispersions with polytetrafluoroethyllining lining autoclave in, at a temperature of 140 DEG C, at autogenous pressures instead It answers 36 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
Embodiment 7
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), as The specific surface area of the multi-walled carbon nanotube (being purchased from Shandong great Zhan nano material Co., Ltd) of raw material nano carbon material is 103m2/ G, w500/w800It is 0.23, oxygen atom content is 1.1 weight %, and nitrogen atom content is 0.03 weight %, removes nitrogen-atoms and oxygen atom The total content of remaining outer nonmetallic heteroatoms (phosphorus atoms and sulphur atom) is 0.01 weight %, and metallic atom total content is 1.6 Weight %.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
Embodiment 8
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), by original Expect nano-carbon material: NH3: H2The weight ratio of O is that the ratio of 1:0.1:19.6 feeds intake.The nano-carbon material containing hetero atom of preparation Composition, specific surface area and w500/w800It is listed in table 1.
Embodiment 9
Nano-carbon material containing hetero 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, urea is then added, stirs evenly, thus Obtain aqueous dispersions, wherein urea is provided in the form of 20 weight % aqueous solutions, by raw material nano carbon material: urea: H2O's Weight ratio is that the ratio of 1:2.5:22.5 feeds intake；
In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 140 DEG C At a temperature of, it reacts 24 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Comparative example 5
Aqueous dispersions same as Example 9 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In 140 DEG C of oil bath, back flow reaction 24 hours under normal pressure.After reaction, it is cooled to room temperature to the temperature in three-necked flask, 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 6 hours, nano-carbon material containing hetero atom is obtained.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 2.
Comparative example 6
Nano-carbon material containing hetero atom is prepared using method same as Example 9, unlike, step does not make in (1) Use urea.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 10
Nano-carbon material containing hetero atom is prepared using method same as Example 9, unlike, in step (2), will To aqueous dispersions with polytetrafluoroethyllining lining autoclave in, at a temperature of 150 DEG C, at autogenous pressures instead It answers 24 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 11
Nano-carbon material containing hetero atom is prepared using method same as Example 9, unlike, in step (1), as The multi-walled carbon nanotube of raw material nano carbon material is same as Example 2.The composition of the nano-carbon material containing hetero atom of preparation compares table Area and w500/w800It is listed in table 2.
Embodiment 12
Nano-carbon material containing hetero atom is prepared using method same as Example 9, unlike, in step (1), by original Expect nano-carbon material: urea: H2The weight ratio of O is that the ratio of 1:0.2:22.5 feeds intake.The nano-carbon material containing hetero atom of preparation Composition, specific surface area and w500/w800It is listed in table 2.
Embodiment 13
Nano-carbon material containing hetero atom is prepared using method same as Example 5, difference is as follows:
In step (1), in deionized water by the dispersion of raw material nano carbon material, urea is then added, stirs evenly, thus Obtain aqueous dispersions, wherein urea is provided in the form of 20 weight % aqueous solutions, by raw material nano carbon material: urea: H2O's Weight ratio is that the ratio of 1:1.5:28.5 feeds intake；
In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 110 DEG C At a temperature of, it reacts 24 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 14
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 13, unlike, in step (1), make Multi-walled carbon nanotube for raw material nano carbon material is same as Example 7.Composition, the ratio of the nano-carbon material containing hetero atom of preparation Surface area and w500/w800It is listed in table 2.
Embodiment 15
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 13, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 100 DEG C, at autogenous pressures Reaction 24 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 16
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 13, unlike, in step (1), press Raw material nano carbon material: urea: H2The weight ratio of O is that the ratio of 1:0.1:28.5 feeds intake.The nano carbon material containing hetero atom of preparation Composition, specific surface area and the w of material500/w800It is listed in table 2.
Embodiment 17
Nano-carbon material containing hetero 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, hydrazine is then added, stirs evenly, thus To aqueous dispersions, wherein hydrazine is provided in the form of 20 weight % aqueous solutions, by raw material nano carbon material: hydrazine: H2The weight ratio of O It feeds intake for the ratio of 1:5:50；
In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 125 DEG C At a temperature of, it reacts 24 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Comparative example 7
Aqueous dispersions identical with embodiment 17 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In 125 DEG C of oil bath, back flow reaction 24 hours under normal pressure.After reaction, it is cooled to room temperature to the temperature in three-necked flask, 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 6 hours, nano-carbon material containing hetero atom is obtained.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 2.
Comparative example 8
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 17, unlike, step does not make in (1) Use hydrazine.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 18
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 17, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 115 DEG C, at autogenous pressures Reaction 24 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 19
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 17, unlike, in step (1), press Raw material nano carbon material: hydrazine: H2The weight ratio of O is that the ratio of 1:15:50 feeds intake.The group of the nano-carbon material containing hetero atom of preparation At, specific surface area and w500/w800It is listed in table 2.
Embodiment 20
Nano-carbon material containing hetero atom is prepared using method same as Example 5, difference is as follows:
In step (1), in deionized water by the dispersion of raw material nano carbon material, hydrazine is then added, stirs evenly, thus To aqueous dispersions, wherein hydrazine is provided in the form of 25 weight % aqueous solutions, by raw material nano carbon material: hydrazine: H2The weight ratio of O It feeds intake for the ratio of 1:0.4:10；
In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 165 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 hetero atom of preparation500/w800It is listed in table 2.
Embodiment 21
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 20, unlike, in step (1), make Multi-walled carbon nanotube for raw material nano carbon material is same as Example 7.Composition, the ratio of the nano-carbon material containing hetero atom of preparation Surface area and w500/w800It is listed in table 2.
Embodiment 22
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 20, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 175 DEG C, at autogenous pressures Reaction 36 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 23
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 20, unlike, in step (1), press Raw material nano carbon material: hydrazine: H2The weight ratio of O is that the ratio of 1:15:10 feeds intake.The group of the nano-carbon material containing hetero atom of preparation At, specific surface area and w500/w800It is listed in table 2.
Embodiment 24
Nano-carbon material containing hetero atom prepared by embodiment 1 350 DEG C at a temperature of air atmosphere in roast 5 hours.
Comparative example 9
Nano-carbon material containing hetero atom prepared by comparative example 1 350 DEG C at a temperature of air atmosphere in roast 5 hours.
Comparative example 10
Nano-carbon material containing hetero atom prepared by comparative example 2 350 DEG C at a temperature of air atmosphere in roast 5 hours.
Comparative example 11
Nano-carbon material containing hetero atom prepared by comparative example 3 350 DEG C at a temperature of air atmosphere in roast 5 hours.
Comparative example 12
Nano-carbon material containing hetero atom prepared by comparative example 4 350 DEG C at a temperature of air atmosphere in roast 5 hours.
Embodiment 25
Nano-carbon material containing hetero atom prepared by embodiment 2 350 DEG C at a temperature of air atmosphere in roast 5 hours.
Embodiment 26
Nano-carbon material containing hetero atom prepared by embodiment 3 350 DEG C at a temperature of air atmosphere in roast 5 hours.
Embodiment 27
Nano-carbon material containing hetero atom prepared by embodiment 4 350 DEG C at a temperature of air atmosphere in roast 5 hours.
Embodiment 28
Nano-carbon material containing hetero atom prepared by embodiment 9 410 DEG C at a temperature of air atmosphere in roast 4 hours.
Embodiment 29
Nano-carbon material containing hetero atom prepared by embodiment 20 450 DEG C at a temperature of air atmosphere in roast 2 hours.
Embodiment 30-58 is used to illustrate the application and hydrocarbon dehydrogenation reaction of the nano-carbon material according to the present invention containing hetero atom Method.
Embodiment 30-52
The nano-carbon material containing hetero atom that 0.2g (admission space 1.5mL) embodiment 1-23 is obtained respectively is as catalysis 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 450 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 1.28 volume %, normal butane and oxygen Gas molar ratio 0.5:1, Balance Air are nitrogen, Zhan Yuliang) it with total volume air speed is 600h-1It is passed through in reactor and is reacted, even The composition for the reaction mixture that continuous monitoring is exported from reactor, and calculate n-butane conversion, total olefin selectivity and 2- fourth Alkene selectivity, the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 13-20
It is reacted using method identical with embodiment 30-52, unlike, it is prepared respectively using comparative example 1-8 Nano-carbon material containing hetero atom is as catalyst.Reaction result is listed in table 3.
Comparative example 21
It is reacted using method identical with embodiment 30-52, unlike, use raw material same as Example 1 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Comparative example 22
It is reacted using method identical with embodiment 30-52, unlike, use raw material same as Example 5 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Embodiment 53-58
It is reacted using method identical with embodiment 30-52, unlike, it is prepared respectively using embodiment 24-29 Nano-carbon material containing hetero atom as catalyst.Reaction result is listed in table 4.
Comparative example 23-26
It is reacted using method identical with embodiment 30-52, unlike, it is prepared respectively using comparative example 9-12 Nano-carbon material containing hetero atom is as catalyst.Reaction result is listed in table 4.
Comparative example 27
It is reacted using method identical with embodiment 30-52, 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 5 hours obtained from.Reaction result arranges in table 4 Out.
Comparative example 28
It is reacted using method identical with embodiment 30-52, unlike, catalyst is will be same as Example 5 Raw material nano carbon material 450 DEG C at a temperature of air atmosphere in roast 2 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 (76)

1. a kind of nano-carbon material containing hetero atom, this contains hetero atom nano-carbon material and contains C element, O element and N element, with this On the basis of the total amount of the nano-carbon material containing hetero atom and based on the element, the content of N element is the content of 3-12 weight %, O element For 1-10 weight %, the content of C element is 78-96 weight %；
The total amount that the N element in the nano-carbon material containing hetero atom is determined by x-ray photoelectron spectroscopy is IN t, by X-ray photoelectricity The amount for the N element that peak in sub- power spectrum within the scope of 398.5-400.1eV determines is IN c, IN c/IN tIn the range of 0.8-1；
This contains in hetero atom nano-carbon material, the O determined by the peak within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy The amount of 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 0.8-1.5；
The preparation method of the nano-carbon material containing hetero atom include by a kind of aqueous dispersions for being dispersed with raw material nano carbon material in It is reacted in closed container, dissolved at least one nitrogenous compound in the aqueous dispersions, the nitrogenous compound is selected from NH3, hydrazine and urea, in reaction process, the temperature of the aqueous dispersions is in the range of 80-250 DEG C.
2. nano-carbon material containing hetero atom according to claim 1, wherein IN c/IN tIn the range of 0.8-0.95；IO c/ IO eIn the range of 0.85-1.2.
3. nano-carbon material containing hetero atom according to claim 2, wherein IN c/IN tIn the range of 0.85-0.92.
4. nano-carbon material containing hetero atom according to claim 2, wherein IO c/IO eIn the range of 0.9-1.
5. nano-carbon material containing hetero atom described in any one of -4 according to claim 1, wherein this contains hetero atom nano-sized carbon In material, the amount of the C element determined by the peak within the scope of 288.6-288.8eV in x-ray photoelectron spectroscopy is IC c, by X-ray The amount for the C element that peak in photoelectron spectroscopy within the scope of 286.0-286.2eV determines is IC e, IC c/IC eIn the range of 0.5-1.5 It is interior.
6. nano-carbon material containing hetero atom according to claim 5, wherein IC c/IC eIn the range of 0.6-1.4.
7. nano-carbon material containing hetero atom described in any one of -4 according to claim 1, wherein with the nanometer containing hetero atom On the basis of the total amount of the C element determined in carbon material by x-ray photoelectron spectroscopy, by 284.7- in x-ray photoelectron spectroscopy The content for the C element that peak within the scope of 284.9eV determines is 60-98 weight %；By 286.0- in x-ray photoelectron spectroscopy The content for the C element that peak within the scope of 288.8eV determines is 2-40 weight %.
8. nano-carbon material containing hetero atom according to claim 7, wherein in the nano-carbon material containing hetero atom by X On the basis of the total amount for the C element that X-ray photoelectron spectroscopy X determines, by within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy Peak determine C element content be 65-95 weight %；By the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The content of determining C element is 5-35 weight %.
9. nano-carbon material containing hetero atom according to claim 8, wherein in the nano-carbon material containing hetero atom by X On the basis of the total amount for the C element that X-ray photoelectron spectroscopy X determines, by within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy Peak determine C element content be 75-85 weight %；By the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The content of determining C element is 15-25 weight %.
10. nano-carbon material containing hetero atom described in any one of -4 according to claim 1, wherein by x-ray photoelectron energy It composes and determines that the total amount of the N element in the nano-carbon material containing hetero 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 0.2.
11. nano-carbon material containing hetero atom according to claim 10, wherein IN g/IN tIn the range of 0.05-0.2.
12. nano-carbon material containing hetero atom according to claim 11, wherein IN g/IN tIn the range of 0.08-0.15.
13. nano-carbon material containing hetero atom described in any one of -4 according to claim 1, wherein received with this containing hetero atom On the basis of the total amount of rice carbon material and based on the element, the content of N element is that the content of 3.5-10 weight %, O element is 3-9 weight % is measured, the content of C element is 81-93.5 weight %.
14. nano-carbon material containing hetero atom according to claim 13, wherein with the total of the nano-carbon material containing hetero atom On the basis of amount and based on the element, the content of N element is that the content of 3.5-9.5 weight %, O element is 4.5-8 weight %, C element Content be 82.5-92 weight %.
15. nano-carbon material containing hetero atom described in any one of -4 according to claim 1, wherein this contains hetero atom nanometer Carbon material is carbon nanotube containing hetero atom.
16. nano-carbon material containing hetero atom according to claim 15, wherein it is containing miscellaneous that this, which contains hetero atom nano-carbon material, Atom multi-walled carbon nanotube.
17. nano-carbon material containing hetero atom according to claim 16, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 50-500m2/g。
18. nano-carbon material containing hetero atom according to claim 17, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 80-300m2/g。
19. nano-carbon material containing hetero atom according to claim 18, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 90-250m2/g。
20. nano-carbon material containing hetero atom according to claim 19, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 95-150m2/g。
21. nano-carbon material containing hetero atom according to claim 16, wherein the multi-walled carbon nanotube containing hetero atom exists Total weight loss rate in 400-800 DEG C of temperature range is w800, the total weight loss rate 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.
22. nano-carbon material containing hetero atom according to claim 21, wherein w500/w800In the range of 0.02-0.2.
23. a kind of preparation method of nano-carbon material containing hetero atom, this method includes that one kind is dispersed with to raw material nano carbon material Aqueous dispersions reacted in closed container, it is described to contain dissolved at least one nitrogenous compound in the aqueous dispersions Nitrogen compound is selected from NH3, hydrazine and urea, in reaction process, the temperature of the aqueous dispersions is in the range of 80-250 DEG C, raw material Nano-carbon material: the weight ratio of nitrogenous compound is 1:0.05-50, raw material nano carbon material: H2The weight ratio of O is 1:1-200.
24. according to the method for claim 23, wherein raw material nano carbon material: the weight ratio of nitrogenous compound is 1: 0.1-20。
25. according to the method for claim 24, wherein raw material nano carbon material: the weight ratio of nitrogenous compound is 1: 0.3-10。
26. according to the method for claim 25, wherein raw material nano carbon material: the weight ratio of nitrogenous compound is 1: 0.5-5。
27. according to the method for claim 23, wherein raw material nano carbon material: H2The weight ratio of O is 1:2-100.
28. according to the method for claim 27, wherein raw material nano carbon material: H2The weight ratio of O is 1:10-50.
29. the method according to any one of claim 23-28, wherein in reaction process, the temperature of the aqueous dispersions Degree is in the range of 100-220 DEG C.
30. according to the method for claim 23, wherein the nitrogenous compound is NH3, raw material nano carbon material: NH3's Weight ratio is 1:0.1-5, raw material nano carbon material: H2The weight ratio of O is 1:2-100, aqueous dispersions described in reaction process Temperature is 140-220 DEG C.
31. according to the method for claim 30, wherein the nitrogenous compound is NH3, raw material nano carbon material: NH3's Weight ratio is 1:0.2-2, raw material nano carbon material: H2The weight ratio of O is 1:5-50.
32. according to the method for claim 31, wherein the nitrogenous compound is NH3, raw material nano carbon material: NH3's Weight ratio is 1:0.3-0.8, raw material nano carbon material: H2The weight ratio of O is 1:8-25.
33. the method according to any one of claim 30-32, wherein the temperature of aqueous dispersions described in reaction process Degree is 150-190 DEG C.
34. according to the method for claim 23, wherein the nitrogenous compound is hydrazine, raw material nano carbon material: the weight of hydrazine Amount is than being 1:0.1-15, raw material nano carbon material: H2The weight ratio of O is 1:2-100, the temperature of aqueous dispersions described in reaction process Degree is 120-180 DEG C.
35. according to the method for claim 34, wherein the nitrogenous compound is hydrazine, raw material nano carbon material: the weight of hydrazine Amount is than being 1:0.2-10, raw material nano carbon material: H2The weight ratio of O is 1:5-75.
36. according to the method for claim 35, wherein the nitrogenous compound is hydrazine, raw material nano carbon material: the weight of hydrazine Amount is than being 1:0.3-6, raw material nano carbon material: H2The weight ratio of O is 1:10-50.
37. the method according to any one of claim 34-36, wherein the temperature of aqueous dispersions described in reaction process Degree is 125-165 DEG C.
38. according to the method for claim 23, wherein the nitrogenous compound is urea, raw material nano carbon material: urea Weight ratio be 1:0.1-25, raw material nano carbon material: H2The weight ratio of O is 1:5-100, and the temperature of the aqueous dispersions is 100-160℃。
39. according to the method for claim 38, wherein the nitrogenous compound is urea, raw material nano carbon material: urea Weight ratio be 1:0.5-15, raw material nano carbon material: H2The weight ratio of O is 1:10-50.
40. according to the method for claim 39, wherein the nitrogenous compound is urea, raw material nano carbon material: urea Weight ratio be 1:1-8, raw material nano carbon material: H2The weight ratio of O is 1:15-30.
41. according to the method for claim 40, wherein the nitrogenous compound is urea, raw material nano carbon material: urea Weight ratio be 1:1.2-3.
42. the method according to any one of claim 38-41, wherein the temperature of the aqueous dispersions is 105-145 ℃。
43. the method according to any one of claim 23-28,30-32,34-36 and 38-41, wherein the reaction Duration in the range of 0.5-144 hours.
44. according to the method for claim 43, wherein the duration of the reaction is in the range of 2-72 hours.
45. according to the method for claim 44, wherein the duration of the reaction is in the range of 10-60 hours.
46. according to the method for claim 45, wherein the duration of the reaction is in the range of 20-40 hours.
47. the method according to any one of claim 23-28,30-32,34-36 and 38-41, wherein the raw material The content of N element is not higher than 0.5 weight % in nano-carbon material；The content of O element is not higher than 1.2 weight %.
48. according to the method for claim 47, wherein in the raw material nano carbon material content of N element be not higher than 0.2 weight %.
49. according to the method for claim 48, wherein in the raw material nano carbon material content of N element be not higher than 0.1 weight %.
50. according to the method for claim 47, wherein the content of O element is not higher than 0.5 weight %.
51. the method according to any one of claim 23-28,30-32,34-36 and 38-41, wherein the raw material Nano-carbon material is carbon nanotube.
52. method according to claim 51, wherein the raw material nano carbon material is multi-walled carbon nanotube.
53. method according to claim 52, wherein the specific surface area of the multi-walled carbon nanotube is 50-500m2/g。
54. method according to claim 53, wherein the specific surface area of the multi-walled carbon nanotube is 50-300m2/g。
55. method according to claim 54, wherein the specific surface area of the multi-walled carbon nanotube is 80-250m2/g。
56. method according to claim 55, wherein the specific surface area of the multi-walled carbon nanotube is 90-150m2/g。
57. method according to claim 51, wherein the multi-walled carbon nanotube is in 400-800 DEG C of temperature range Total weight loss rate be w800, the total weight loss rate in 400-500 DEG C of temperature range is w500, w500/w800In the model of 0.01-0.5 In enclosing, the weight-loss ratio measures in air atmosphere.
58. method according to claim 57, wherein w500/w800In the range of 0.02-0.2.
59. the method according to any one of claim 23-28,30-32,34-36 and 38-41, wherein this method is also Including isolating solid matter from the mixture that reaction obtains, and the solid matter isolated is dried.
60. method according to claim 59, wherein the drying 50-200 DEG C at a temperature of carry out；The drying Duration be 0.5-48 hours.
61. method according to claim 60, wherein the drying 80-180 DEG C at a temperature of carry out；The drying Duration be 3-24 hours.
62. method according to claim 61, wherein the drying 100-150 DEG C at a temperature of carry out；The drying Duration be 5-15 hours.
63. a kind of nano-carbon material containing hetero atom of the preparation of the method as described in any one of claim 23-62.
64. a kind of nano-carbon material containing hetero atom, it is by any one of claim 1-22 that this, which contains hetero atom nano-carbon material, Nano-carbon material containing hetero atom described in the nano-carbon material containing hetero atom or claim 63 is roasted and is made 's.
65. nano-carbon material containing hetero atom according to claim 64, wherein temperature of the roasting at 250-500 DEG C Lower progress；The duration of the roasting is 1-24 hours.
66. nano-carbon material containing hetero atom according to claim 65, wherein temperature of the roasting at 300-450 DEG C Lower progress；The duration of the roasting is 2-12 hours.
67. nano-carbon material containing hetero atom according to claim 66, wherein the duration of the roasting is that 2-6 is small When.
68. in nano-carbon material containing hetero atom described in any one of claim 1-22 and 63 or claim 64-67 Application of the nano-carbon material containing hetero atom described in any one as the catalyst of hydrocarbon dehydrogenation reaction.
69. application according to claim 68, wherein the dehydrogenation reaction carries out in the presence of oxygen.
70. the application according to claim 68 or 69, wherein the hydrocarbon is alkane.
71. application according to claim 70, wherein the hydrocarbon is C2-C12Alkane.
72. application according to claim 71, wherein the hydrocarbon is normal butane.
73. 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 hetero atom or claim 64- described in any one of hydrocarbon and claim 1-22 and 63 The contact of nano-carbon material containing hetero atom described in any one of 67.
74. the method according to claim 73, wherein the hydrocarbon is alkane.
75. method according to claim 74, wherein the hydrocarbon is C2-C12Alkane.
76. the method according to claim 75, wherein the hydrocarbon is normal butane.
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