CN105817248B - 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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CN105817248B
CN105817248B CN201510702382.7A CN201510702382A CN105817248B CN 105817248 B CN105817248 B CN 105817248B CN 201510702382 A CN201510702382 A CN 201510702382A CN 105817248 B CN105817248 B CN 105817248B
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carbon material
hetero atom
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CN105817248A (en
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史春风
荣峻峰
于鹏
谢婧新
宗明生
林伟国
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
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    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a kind of nano-carbon materials containing hetero atom and its preparation method and application, the nano-carbon material containing hetero atom contains the C element of the O element of 1-8 weight %, the N element of 2-8 weight % and 84-97 weight %, in x-ray photoelectron spectroscopy, the ratio of the amount of the O element determined by the peak within the scope of 531.0-532.5eV and the amount of the O element determined by the peak within the scope of 532.6-533.5eV is 1.2-2.5, and the ratio of the total amount of the amount and N element of the N element determined by the peak within the scope of 398.5-400.1eV is 0.7-1.The hydrocarbon dehydrogenation reaction method of the nano-carbon material containing hetero atom as catalyst is used the present invention also provides a kind of.The nano-carbon material containing hetero atom shows good catalytic performance in the dehydrogenation reaction of hydrocarbons, can significantly improve feed stock conversion and selectivity of product.

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.It can realize that introducing oxygen is former in nano-carbon material by carrying out oxidation processes to nano-carbon material Son, 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 strong oxidizing solution (such as H2O2、KMnO4) in carry out back flow reaction, can also be assisted while back flow reaction Microwave heating or sonic oscillation are carried out, to enhance the effect of oxidation reaction.But in strong acid and/or strong oxidizing solution into Row back flow reaction may have an adverse effect to the skeleton structure of nano-carbon material, or even destroy the skeleton knot of nano-carbon material Structure.Such as: nano-carbon material is subjected to back flow reaction in nitric acid, although can introduce on nano-carbon material surface a large amount of oxygen-containing Functional group, but nano-carbon material is easily caused to be cut off and/or obviously increase the defects of graphite network structure position, to drop The performance of low nano-carbon material, such as thermal stability.In addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, When introducing oxygen atom, the introduction volume of oxygen atom is high to the dependence of operation condition, and fluctuation range is wider.
When introducing nitrogen-atoms in nano-carbon material, according to nitrogen-atoms, locating chemical environment is not in nano-carbon material Together, nitrogen-atoms is usually divided into chemical nitrogen and structure nitrogen.Chemical nitrogen mainly appears in material in the form of surface functional group Surface, such as amino or nitrosyl radical surface nitrogen-containing functional group.Structure nitrogen refer to skeleton structure into nano-carbon material with The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly include graphite mould nitrogen (that is,), pyridine type nitrogen (that is,) and Pyrroles's type nitrogen (that is,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen It is unsaturated nitrogen atom with pyrroles's type nitrogen, while replacing carbon atom, often will cause the missing for closing on carbon atom, form defect Position.
Can by introduced in nano-carbon material synthesis process nitrogenous functional atmosphere (such as ammonia, nitrogen, urea, Melamine), nitrogen is introduced into nano carbon material simultaneously in the synthesis process of nano-carbon material using high temperature and/or high pressure In the skeleton structure of material and/or surface；It can also be by the way that nano-carbon material to be placed in nitrogenous functional atmosphere (such as ammonia, nitrogen Gas, urea, melamine) in, nitrogen is introduced into the surface of nano-carbon material using high temperature and/or high pressure.High temperature and/or For high pressure although can form structure nitrogen in nano-carbon material, the type of nitrogen containing species depends on reaction condition, not easily-controllable System；Also, the different types of nitrogen containing species so generated are unevenly distributed on the surface of nano-carbon material, lead to nitrogenous nanometer The performance of carbon material is unstable.It then can also be reacted with amine, by the way that nano-carbon material is carried out oxidation processes thus in nanometer Carbon material surface introduces nitrogen-atoms, and the nitrogen-atoms so introduced is essentially chemical nitrogen.
Although the research of doping vario-property and its catalytic performance in relation to nano-carbon material achieves many progress, for Some of which basic problem is not built consensus yet, is still needed to doping vario-property nano-carbon material and preparation method thereof and catalysis Performance is furtherd investigate.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of nano-carbon material containing hetero atom, not using this method It is only capable of in nano-carbon material surface introducing hetero-atoms, and the structure of nano-carbon material itself is influenced little.Of the invention is another One is designed to provide a kind of nano-carbon material containing hetero atom, this contains dehydrogenation of the hetero atom nano-carbon material for hydrocarbons When reaction, higher feed stock conversion can not only be obtained, and higher selectivity of product can be obtained.A further object of the present invention It is to provide a kind of hydrocarbon dehydrogenation reaction method, this method can obtain higher feed stock conversion and selectivity of product.
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 O element are 1-8 weight %, and the content of N element is 2-8 weight %, and the content of C element is 84-97 weight %；
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 1.2-2.5；
This contains in hetero atom nano-carbon material, determines the N in the nano-carbon material containing hetero atom by x-ray photoelectron spectroscopy The total amount of element is IN t, the amount of the N element determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy is IN c, IN c/IN tIn the range of 0.7-1.
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 by a kind of water for being dispersed with raw material nano carbon material, at least one nitrogenous compound and at least one organic base Dispersion liquid is reacted in closed container, and the nitrogenous compound is selected from NH3, hydrazine and urea, the organic base be selected from amine and Quaternary ammonium base, in reaction process, the temperature of the aqueous dispersions is maintained 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 present invention the 4th aspect contain Application of the hetero atom nano-carbon material 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 in the dehydrogenation reaction of hydrocarbons Good catalytic performance, can significantly improve feed stock conversion and selectivity of product.
Detailed description of 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 contains miscellaneous original with this On the basis of the total amount of sub- nano-carbon material and based on the element, the content of O element is 1-8 weight %, preferably 2.5-7.5 weight Measure %, more preferably 3-7 weight %, further preferably 4.5-7 weight %；The content of N element is 2-8 weight %, preferably 2-6 weight %, more preferably 3-5 weight %, further preferably 3.5-4.5 weight %；The content of C element is 84-97 weight Measure %, preferably 86.5-95.5 weight %, more preferably 88-94 weight %, further preferably 88.5-92 weight %.Its In, the content of each element is measured using x-ray photoelectron spectroscopy (XPS) method, determines element by the corresponding area of 1s electronics spectral peak Content；Sample is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before testing.
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, 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 1.3-2.2 in the range of 1.2-2.5 It is selected in the range of 1.4-2.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.In the present invention, when indicating numberical range, " ×-× in the range of " it include two binary values.
Nano-carbon material containing hetero atom according to the present invention, in the nano-carbon material containing hetero atom by x-ray photoelectron On the basis of the total amount for the C element that power spectrum determines, the C that is determined by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy The content of element (that is, graphite mould carbon) can be 60-98 weight %, preferably 65-95 weight %, more preferably 70-90 weight Measure %；The total content of the C element determined by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy can be 2-40 Weight %, preferably 5-35 weight %, more preferably 10-30 weight %.In the present invention, by the C1s in x-ray photoelectron spectroscopy The area A of spectral peakC 1C1s spectral peak in x-ray photoelectron spectroscopy is divided into two groups of peaks, i.e., in 284.7- by the total amount for determining C element Spectral peak (corresponding to graphite mould carbon species) within the scope of 284.9eV and the spectral peak within the scope of 286.0-288.8eV (correspond to Non-graphite type carbon species), the area of the spectral peak within the scope of 284.7-284.9eV is denoted as AC 2, will be in 286.0-288.8eV model The area of spectral peak in enclosing is denoted as AC 3, the C element that is determined by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy Content=AC 2/AC 1, by the total content for the C element that the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy determines =AC 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 1.5-4, preferably in the model of 1.5-3.5 In enclosing, more preferably in the range of 1.55-3.In the present invention, by x-ray photoelectron spectroscopy within the scope of 286.0-288.8eV Spectral peak (correspond to agraphitic carbon species) be further divided into two groups of peaks, i.e., the spectral peak within the scope of 286.0-286.2eV is (right Should be in hydroxyl and ether type carbon species) and within the scope of 288.6-288.8eV spectral peak (correspond to carboxyl, acid anhydride and ester type carbon object Kind), the area of the spectral peak within the scope of 286.0-286.2eV is denoted as AC 4, by the spectral peak within the scope of 288.6-288.8eV Area is denoted as AC 5, IC c/IC e=AC 5/AC 4。
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 The amount of (that is, nitrogen species in addition to graphite mould nitrogen) is IN c, IN c/IN tIn the range of 0.7-1, preferably in the range of 0.75-0.98 It is interior, more preferably in the range of 0.8-0.95.
Nano-carbon material containing hetero atom according to the present invention, by within the scope of 400.6-401.5eV in x-ray photoelectron spectroscopy Peak determine N element (that is, graphite mould nitrogen) content is lower or even is free of.Generally, nanometer containing hetero atom according to the present invention In 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 t For not higher than 0.3, generally in the range of 0.02-0.25, preferably in the range of 0.05-0.2.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peak in x-ray photoelectron spectroscopyN 1, by X-ray N1s spectral peak in photoelectron spectroscopy is divided into 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.
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 State carbon nanotube containing hetero atom can for single-walled carbon nanotube containing hetero atom, double-walled carbon nano-tube containing hetero atom and contain hetero atom it is more The combination of one or more of wall carbon nano tube.Nano-carbon material containing hetero atom according to the present invention, preferably containing miscellaneous 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 90-150m2/g.Further Preferably, which is 95-140m2/g.In the present invention, specific surface area is inhaled by nitrogen Attached BET method measurement.
Nano-carbon material containing metallic atom according to the present invention, the multi-walled carbon nanotube containing metallic atom is in 400-800 DEG C temperature range in weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that In the range of 0.01-0.5, better catalytic effect, especially urging as hydrocarbons dehydrogenation reaction can be obtained in this way When agent, better catalytic effect can be obtained.It is highly preferred that w500/w800More preferably in the range of 0.02-0.2.The present invention In, w800=W800- W400, w500=W500- W400, W400For in 400 DEG C of the at a temperature of mass loss rate that measures, W800For The mass loss rate measured at a temperature of 800 DEG C, W500For in 500 DEG C of the at a temperature of mass loss rate that measures；The weight-loss ratio It is measured in air atmosphere using thermogravimetric analyzer, test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；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 a preferred embodiment of the invention, the nano-carbon material containing metallic atom preferably contains metal original Sub- multi-walled carbon nanotube, which is 50-500m2/ g, preferably 80-300m2/ G, more preferably 90-150m2/ g, further preferably 95-140m2/g；Also, w500/w800It is excellent in the range of 0.01-0.5 It is selected 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 usual 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 by a kind of water for being dispersed with raw material nano carbon material, at least one nitrogenous compound and at least one organic base Dispersion liquid is reacted in closed container.In the present invention, "at least one" indicates one or more kinds of.
The nitrogenous compound is selected from NH3, hydrazine and urea.
The organic base is selected from amine and quaternary ammonium base.
The quaternary ammonium base is specifically as follows Formulas I compound represented:
In Formulas I, R1、R2、R3And R4It respectively can be C1-C20Alkyl (including C1-C20Straight chained alkyl and C3-C20Branch Alkyl group) or C6-C12Aryl.The C1-C20The specific example of alkyl can include but is not limited to: methyl, ethyl, just Propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, neopentyl, isopentyl, tertiary pentyl, n-hexyl, just Octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, just One of cetyl, n-octadecane base and n-eicosane base are a variety of.The C6-C12The specific example of aryl can wrap Include but be not limited to phenyl, naphthalene, 4- aminomethyl phenyl and 4- ethylphenyl.R1、R2、R3And R4It is preferred that being respectively C1-C10Alkyl (including C1-C10Straight chained alkyl and C3-C10Branched alkyl), more preferably respectively C1-C6Alkyl (including C1-C6Straight chain Alkyl and C3-C6Branched alkyl).
The amine refers to the substance that the one, two or three hydrogen in amino molecule is replaced by organic group and is formed, described Organic group can form cyclic structure with nitrogen atom bonding.The organic group can be to replace (such as hydroxyl substitution) or do not take The aliphatic alkyl in generation and/or substitution (such as hydroxyl substitution) or unsubstituted aromatic hydrocarbyl, the aliphatic alkyl can be Replace (such as hydroxyl substitution) or unsubstituted representative examples of saturated aliphatic chain alkylene, substitution (such as hydroxyl substitution) or unsubstituted unsaturated lipid Fat race chain alkylene replaces (such as hydroxyl substitution) or unsubstituted saturated alicyclic hydrocarbon base and replaces (such as hydroxyl substitution) or do not take One or more of the unsaturated lipid cyclic hydrocarbon radical in generation.Specifically, the amine can be to replace (such as hydroxyl substitution) or not Substituted representative examples of saturated aliphatic amine replaces (such as hydroxyl substitution) or unsubstituted unsaturated aliphatic amine, replaces (such as hydroxyl substitution) Or unsubstituted saturation aliphatic cyclic amine, substitution (such as hydroxyl substitution) or unsubstituted unsaturated lipid cyclammonium, substitution (such as hydroxyl substitution) Or unsubstituted heterocyclic amine and replace one or more of (such as hydroxyl substitution) or unsubstituted arylamine.
The representative examples of saturated aliphatic amine is preferably Formula II compound represented, formula III compound represented and general formula R12 (NH2)2One or more of substance of expression,
In Formula II, R5、R6And R7Respectively H or C1-C6Alkyl, and R5、R6And R7It is not simultaneously H.In the present invention, C1- C6The specific example of alkyl can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl and n-hexyl.
In formula III, R8、R9And R10Respectively-R11OH or hydrogen, and R8、R9And R10At least one of be-R11OH, R11 For C1-C4Alkylidene.In the present invention, C1-C4Alkylidene include C1-C4Straight-chain alkyl-sub and C3-C4Branched alkylidene, Its specific example can include but is not limited to: methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, isobutylidene With sub- tert-butyl.
General formula R12(NH2)2In, R12It can be C1-C6Alkylidene.In the present invention, C1-C6Alkylidene include C1-C6's Straight-chain alkyl-sub and C3-C6Branched alkylidene, specific example can include but is not limited to: methylene, ethylidene, Asia positive third Base, isopropylidene, sub- normal-butyl, isobutylidene, sub- tert-butyl, sub- n-pentyl and sub- n-hexyl.
The unsaturated aliphatic amine refers to the aliphatic streptamine in molecular structure containing unsaturated group, the unsaturation Group is preferably alkenyl (that is,-C=C-).The quantity of the unsaturated group and amino can be one or more, not have It is particularly limited to.
According to the method for the present invention, the specific example of the organic base can include but is not limited to methylamine, dimethylamine, front three Amine, ethamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, Tri-n-Propylamine, isopropylamine, diisopropylamine, n-butylamine, two are just Butylamine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, three N-amylamine, neopentyl amine, iso-amylamine, di-iso-amylamine, triisoamylamine, tertiary amylamine, hexylamine, octylame, nonyl amine, decyl amine, undecyl amine, Lauryl amine, dodecyl-dimethyl amine, tridecyl amine, tetradecylamine, pentadecyl amine, hexadecylamine, a second Hydramine, triethanolamine, triisopropanolamine, diethanol amine, dipropanolamine, tripropanol amine, two butanolamines, three butanolamines, dodecane Base dimethyl amine, tetradecyldimethylamine, hexadecyldimethyl benzyl ammonium amine, ethylenediamine, propane diamine, butanediamine, pentanediamine, oneself two It is amine, substituted or unsubstituted pyrroles, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, substituted or unsubstituted Hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substitution or not It is substituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted different Quinoline, substituted or unsubstituted pyrimidine, aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, adjacent methyl Aniline, m-toluidine, open-chain crown ether, 23 dimethyl aniline, 2,4- dimethylaniline, 2,5- dimethylaniline, 2,6- Dimethylaniline, 3,4- dimethylaniline, 3,5- dimethylaniline, 2,4,6- trimethylaniline, o ethyl aniline, N- butyl benzene Amine, 2,6- diethylaniline, cyclohexylamine, cyclopentamine, hexamethylenetetramine, diethylenetriamine, triethylene tetramine, tetramethyl hydrogen-oxygen Change ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide (including its various isomers, such as four n-propyl ammonium hydroxide and four different Propyl ammonium hydroxide), tetrabutylammonium hydroxide (including its various isomers, such as 4-n-butyl ammonium hydroxide, four sec-butyl hydrogen-oxygens Change ammonium, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide (including its various isomers) in One or more.
According to the method for the present invention, the dosage of the nitrogenous compound and the organic base can be according to it is contemplated that raw material be received The content and type of the nitrogen and oxygen element that introduce in rice carbon material are selected.It is received what is finally prepared containing hetero atom Rice carbon material is when being used as the catalyst of hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material: nitrogenous compound: organic base Weight ratio is 1:0.01-20:0.01-20, and the nano-carbon material containing hetero atom thus prepared is in the catalysis for being used as hydrocarbon dehydrogenation reaction Better catalytic effect can be obtained when agent.It is highly preferred that raw material nano carbon material: nitrogenous compound: the weight ratio of organic base is 1:0.02-10:0.02-15.
According to the method for the present invention, the molar ratio of the nitrogenous compound and the organic base is preferably 1:0.05-100, Thus oxygen atom and nitrogen-atoms more uniformly spreading on nano-carbon material surface in the nano-carbon material containing hetero atom prepared, Also there is more excellent catalytic activity when being used as the catalyst of hydrocarbon dehydrogenation reaction.The nitrogenous compound and the organic base Molar ratio be more preferably 1:0.1-90, further preferably 1:0.4-80.
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 1:2-1000, and when within the scope of the dosage of water being in this, nano-carbon material exists Structural form retentivity in treatment process is more preferable, such as: when raw material nano carbon material is carbon nanotube, base during processing This is not cut off.Raw material nano carbon material: H2The weight ratio of O is more preferably 1:5-500, further preferably 1:10-300, It is still more preferably 1:20-200.Furthermore it is also possible to according to the type of nitrogenous compound and organic base to the dosage of water into Row adjustment, so that the nitrogenous compound can be uniformly dispersed in subject in water.
According to the method for the present invention, in a preferred embodiment, the nitrogenous compound is ammonia, the organic base Selected from formula III compound represented, it is preferably selected from ethanol amine, diethanol amine and triethanolamine, what is thus prepared receives containing hetero atom Rice carbon material can obtain preferably catalysis reaction effect when being used as the catalyst of hydrocarbon dehydrogenation reaction.In the preferred embodiment In, raw material nano carbon material: nitrogenous compound: the weight ratio of organic base is preferably in the range of 1:0.02-10:0.05-8, more It is preferred that in the range of 1:0.03-5:0.1-6, further preferably in the range of 1:0.05-2:0.2-5.In the preferred reality Apply in mode, nitrogenous compound: the molar ratio of organic base is preferably in the range of 1:0.05-5, more preferably 1:0.1-2.5's In range, further preferably in the range of 1:0.4-0.8.In the preferred embodiment, raw material nano carbon material: H2O Weight ratio preferably in the range of 1:5-100, more preferably in the range of 1:10-90, further preferably in the model of 1:40-80 In enclosing.
According to the method for the present invention, in another preferred embodiment, the nitrogenous compound is hydrazine, described organic Alkali is selected from quaternary ammonium base shown in Formulas I, and the nano-carbon material containing hetero atom thus prepared is when being used as the catalyst of hydrocarbon dehydrogenation reaction Preferably catalysis reaction effect can be obtained.In the preferred embodiment, raw material nano carbon material: nitrogenous compound: organic The weight ratio of alkali is in the range of 1:0.01-5:0.02-10, preferably in the range of 1:0.02-2.5:1-9, more preferably 1: In the range of 0.02-1.5:4.5-8.In the preferred embodiment, nitrogenous compound: the molar ratio of organic base is preferably 1: 0.5-100, more preferably 1:1-90, further preferably 1:1.1-80.In the preferred embodiment, raw material nano carbon materials Material: H2The weight ratio of O is preferably 1:10-400, more preferably 1:20-250.
According to the method for the present invention, in another preferred embodiment, the nitrogenous compound is urea, described to have Machine alkali is selected from Formula II compound represented and general formula R12(NH2)2The substance of expression is preferably selected from ethylenediamine, n-butylamine and Diamines, it is anti-that the nano-carbon material containing hetero atom thus prepared can obtain preferably catalysis when being used as the catalyst of hydrocarbon dehydrogenation reaction Answer effect.In the preferred embodiment, raw material nano carbon material: nitrogenous compound: the weight ratio of organic base is 1:0.02- 10:0.05-20, preferably 1:0.1-8:0.5-15, more preferably 1:1-5:1-10.It is nitrogenous in the preferred embodiment Compound: the molar ratio of organic base is preferably 1:0.1-5, more preferably 1:0.5-2.In the preferred embodiment, raw material Nano-carbon material: H2The weight ratio of O is preferably 1:5-200, more preferably 1:20-150.
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, can not only effectively improve oxygen atom in raw material nano carbon material and/ Or nitrogen atom content, and the structural form of raw material nano carbon material will not be generated and be significantly affected.It is highly preferred that reaction process In, the temperature of the aqueous dispersions is in the range of 100-180 DEG C.The duration of the reaction can be according to the temperature of reaction It is selected, enough oxygen atom and nitrogen-atoms can be introduced in raw material nano carbon material by being subject to.Generally, the reaction Duration can be in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably at 10-40 hours In range.
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), then mixed with the nitrogenous compound and the organic base It closes, to obtain the aqueous dispersions.In order to further increase the dispersion effect of raw material nano carbon material, while shortening dispersion Raw material nano carbon material can be dispersed in water by the time using the method for sonic oscillation.The condition of the sonic oscillation can be with For conventional selection, generally, the frequency of the sonic oscillation can be 10-100kHz, and the duration of the sonic oscillation can Think 0.1-6 hours, preferably 0.5-2 hours.The nitrogenous compound and the organic base respectively can be with solution (preferably Aqueous solution) form provide, can also be provided, be not particularly limited in the form of pure material.
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 (based on the element) of oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms can in material Think customary amount.Generally, remaining nonmetallic heteroatoms in the raw material nano carbon material outside oxygen atom and nitrogen-atoms Total amount be not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, further Preferably not higher than 0.05 weight %.According to the method for the present invention, the raw material nano carbon material is according to the difference in source, can be with Containing some metallic elements, these metallic elements are typically derived from the catalyst used when preparing raw material nano carbon material, contain Amount is generally in 2 weight % hereinafter, it is preferred that in 1 weight % hereinafter, more preferably in 0.5 weight % hereinafter, further preferably in 0.2 weight % is measured hereinafter, still more preferably below 0.1 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.It can be separated by solid-liquid separation using common Method isolates solid matter from the mixture that reaction obtains, such as one or more of centrifugation, filtering and decantation 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 4-24 hours, more preferably 6-12 hours.Institute Stating drying can carry out under normal pressure (that is, 1 standard atmospheric pressure), can also carry out at reduced pressure.From further increasing The angle of dry efficiency is set out, and the drying preferably carries out at reduced pressure.
According to the method for the present invention, the oxygen atom and 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, preferably 2-12 hours.The roasting can be with It carries out, can also be carried out in the atmosphere formed by inert gas in oxygen-containing atmosphere.The oxygen-containing atmosphere can be air gas Atmosphere；It can also be the mixed atmosphere that oxygen and inert gas are mixed to form, in the mixed atmosphere, the content of oxygen can be 0.1-22 volume %.The inert gas can include but is not limited to nitrogen and/or rare gas, and the rare gas can be Argon gas and/or helium.Angularly consider from convenience and cost, it is preferable that the roasting is at oxygen-containing atmosphere (such as air atmosphere) Middle progress.
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 carbon nanomaterial 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.Side according to the present invention Method, the hydrocarbon are preferably alkane, such as C2-C12Alkane.Specifically, the hydrocarbon can be but be not limited to ethane, propane, positive fourth Alkane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentane, 3- methylpentane, 2,3- dimethyl Butane, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- ethylpentane, 3- ethylpentane, 2, 3- dimethyl pentane, 2,4- dimethyl pentane, normal octane, 2- methyl heptane, 3- methyl heptane, 4- methyl heptane, 2,3- diformazan Base hexane, 2,4- dimethylhexane, 2,5- dimethylhexane, 3- ethyl hexane, 2,2,3- trimethylpentane, 2,3,3- trimethyl Pentane, 2,4,4- trimethylpentane, 2- methyl -3- ethylpentane, n -nonane, 2- methyloctane, 3- methyloctane, 4- methyl are pungent Alkane, 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- trimethyl cyclohexane, 2,2,5- trimethyl Hexane, 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 cyclohexane, trimethyl-cyclohexane (including The various isomers of trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- trimethyl-cyclohexanes, 1,2,5- trimethyls Hexamethylene, 1,3,5- trimethyl-cyclohexane), n-decane, 2- methylnonane, 3- methylnonane, 4- methylnonane, 5- methyl nonyl Alkane, 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- trimethylheptane, 2,2,3- trimethyl Heptane, 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- phenyl-propane, 2- phenyl third One or more of alkane, 1- phenyl butane, 2- phenyl butane, 1- phenyl pentane, 2- phenyl pentane and 3- phenyl pentane Combination.It is highly preferred that the hydrocarbon is one or more of propane, normal butane, iso-butane and vinylbenzene.It is further excellent Selection of land, the hydrocarbon are 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 0.4- 2:1.
Hydrocarbon and oxygen can be sent into reactor by carrier gas and contain miscellaneous original by hydrocarbon dehydrogenation reaction method according to the present invention Sub- nano-carbon material haptoreaction.The carrier gas can be commonly at reaction conditions will not be with reactant and reaction product The gas that chemical interaction occurs and will not decompose, such as one in nitrogen, carbon dioxide, rare gas and vapor Kind or two or more combinations.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 600-900h-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.
In following embodiment and comparative example, nitrogenous compound and organic base are mentioned in the form of 25 weight % aqueous solutions For.
Embodiment 1-43 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 in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition It include: frequency for 14kHz, the time is 0.5 hour.Then, NH is added3It is uniformly mixed with triethanolamine, to obtain water dispersion Liquid, wherein press raw material nano carbon material: NH3: triethanolamine: H2The weight ratio of O is that the ratio of 1:0.05:0.25:50 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 140 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, in normal pressure, (1 standard is big Air pressure, similarly hereinafter), after 12 hours dry at a temperature of 120 DEG C, nano-carbon material containing hetero atom is obtained, this contains hetero atom nano-sized carbon Composition, specific surface area and the w of material500/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 nano-carbon material.
Comparative example 1
Aqueous dispersions same as Example 1 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 140 DEG C, back flow reaction 36 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 At a temperature of DEG C after drying 12 hours, nano-carbon material containing hetero atom is obtained.The structure of the nano-carbon material containing hetero atom of preparation Parameter is listed in table 1.
Comparative example 2
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), moisture Dispersion liquid is free of triethanolamine, it is, as the dispersion of raw material nano carbon material in deionized water then NH will be added3Mixing Uniformly, wherein press raw material nano carbon material: NH3: triethanolamine: H2The weight ratio of O is that the ratio of 1:0.05:0:50 feeds intake.System The structural parameters of the standby nano-carbon material containing hetero atom are listed in table 1.
Comparative example 3
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), moisture Dispersion liquid is free of NH3, it is, by the multi-walled carbon nanotube as raw material nano carbon material dispersion in deionized water, then plus Enter triethanolamine to be uniformly mixed, wherein NH in the mole and embodiment 1 of triethanolamine3With the integral molar quantity phase of triethanolamine Together.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Comparative example 4
In deionized water, it will be divided using the dispersion of nano-carbon material containing hetero atom of method identical with comparative example 2 preparation It is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes: that frequency is 14kHz, and the time is 0.5 hour.Then three are added Ethanol amine is uniformly mixed, wherein (prepares nanometer containing hetero atom using method identical with comparative example 2 by raw material nano carbon material The raw material nano carbon material used when carbon material): triethanolamine: H2The weight ratio of O is that the ratio of 1:0.25:50 feeds intake.
By obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, at a temperature of 140 DEG C, It is reacted 36 hours under self-generated pressure.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction kettle, it will 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 lower drying 12 hours, nano-carbon material containing hetero atom is obtained, which arranges in table 1 Out.
Embodiment 2
Nano-carbon material containing hetero atom is prepared using method same as Example 1, 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 251m2/ G, the weight-loss ratio in 400-800 DEG C of temperature range are 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 %, 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 0.08 Weight %.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Embodiment 3
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (2), will To aqueous dispersions be placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, at autogenous pressures Reaction 36 hours.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Embodiment 4
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), NH3 With the integral molar quantity of triethanolamine it is same as Example 1 under conditions of, make NH3Molar ratio with triethanolamine is 1:1.Preparation The structural parameters of the nano-carbon material containing hetero atom are 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 0.03 weight %, in 400-800 DEG C of temperature Weight-loss ratio in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.07, is purchased from Chengdu organic chemistry Co., Ltd, the academy of sciences, state) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, ultrasound vibration The condition of swinging includes: that frequency is 90kHz, and the time is 2 hours.Then, NH is added3It is uniformly mixed with diethanol amine, to obtain water Dispersion liquid, wherein press raw material nano carbon material: NH3: diethanol amine: H2The weight ratio of O is that the ratio of 1:2:5:80 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 180 DEG C of temperature Under, it reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into normal pressure, 150 DEG C At a temperature of after dry 6 hours, obtain nano-carbon material containing hetero atom, this contains the structural parameters of hetero atom nano-carbon material in table 1 In list.
Comparative example 5
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, what step (1) was prepared Aqueous dispersions are free of diethanol amine, it is, the multi-walled carbon nanotube as raw material nano carbon material is dispersed in deionized water In, NH is then added3It is uniformly mixed, wherein NH3Mole and embodiment 5 in NH3It is identical with the integral molar quantity of diethanol amine.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Embodiment 6
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 %, is denitrogenated and remaining outside oxygen The total content of nonmetallic heteroatoms (p and s) is 0.01 weight %, and metallic atom total content is 1.6 weight %.Containing for preparation is miscellaneous The structural parameters of atom nano-carbon material are listed in table 1.
Embodiment 7
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 230 DEG C, at autogenous pressures instead It answers 24 hours.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Embodiment 8
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), NH3 With the integral molar quantity of diethanol amine it is same as Example 5 under conditions of, make NH3: the molar ratio of diethanol amine is 1:0.1.Preparation The structural parameters of the nano-carbon material containing hetero atom listed in table 1.
Embodiment 9
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), diethyl The n-propylamine of hydramine equimolar amounts replaces.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Embodiment 10
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), diethyl The pyridine of hydramine equimolar amounts replaces.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Comparative example 6
Nano-carbon material containing hetero atom is prepared using method same as in Example 10, unlike, in step (1), water Dispersion liquid is free of NH3, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, then Pyridine is added to be uniformly mixed, wherein NH in the mole and embodiment 10 of pyridine3It is identical with the integral molar quantity of pyridine.Preparation The structural parameters of the nano-carbon material containing hetero atom are listed in table 1.
Embodiment 11
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), diethyl The cyclohexylamine of hydramine equimolar amounts replaces.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Embodiment 12
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), diethyl Hydramine is replaced with ethylenediamine, and the mole of ethylenediamine is 0.5 times of the mole of diethanol amine in embodiment 5.Containing for preparation is miscellaneous The structural parameters of atom nano-carbon material are listed in table 1.
Embodiment 13
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), diethyl The tetraethyl ammonium hydroxide of hydramine equimolar amounts replaces.The structural parameters of the nano-carbon material containing hetero atom of preparation are in table 1 It lists.
Comparative example 7
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 13, unlike, what step (1) was prepared Aqueous dispersions are free of NH3, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, so Tetraethyl ammonium hydroxide is added afterwards to be uniformly mixed, wherein NH in the mole and embodiment 13 of tetraethyl ammonium hydroxide3And tetrem The integral molar quantity of base ammonium hydroxide is identical.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Embodiment 14
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), diethyl Hydramine is replaced with hexamethylenetetramine, and the mole of hexamethylenetetramine is 0.25 of the mole of diethanol amine in embodiment 5 Times.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Comparative example 8
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 14, unlike, what step (1) was prepared Aqueous dispersions are free of NH3, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, so Hexamethylenetetramine is added afterwards to be uniformly mixed, wherein the mole of hexamethylenetetramine is NH in embodiment 143Mole The sum of 0.25 times and the mole of hexamethylenetetramine.The structural parameters of the nano-carbon material containing hetero atom of preparation arrange in table 1 Out.
Embodiment 15
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), diethyl Hydramine is replaced with diethylenetriamine, and the mole of diethylenetriamine is 0.3 times of the mole of diethanol amine in embodiment 5.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Comparative example 9
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 15, unlike, what step (1) was prepared Aqueous dispersions are free of NH3, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, so Diethylenetriamine is added afterwards to be uniformly mixed, wherein the mole of diethylenetriamine is NH in embodiment 153Mole 0.3 Times.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 1.
Embodiment 16
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 and tetramethylammonium hydroxide is then added It is uniformly mixed, wherein press raw material nano carbon material: hydrazine: tetramethylammonium hydroxide: H2The weight ratio of O is 1:0.02:4.5:40's Ratio feeds intake；In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 120 DEG C At a temperature of, it reacts 48 hours at autogenous pressures.The structural parameters of the nano-carbon material containing hetero atom of preparation arrange in table 2 Out.
Comparative example 10
Aqueous dispersions identical with embodiment 16 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 120 DEG C, back flow reaction 48 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 At a temperature of DEG C after drying 12 hours, nano-carbon material containing hetero atom is obtained.The structure of the nano-carbon material containing hetero atom of preparation Parameter is listed in table 2.
Comparative example 11
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 16, unlike, step (1) preparation Aqueous dispersions are free of hydrazine, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, then Tetramethylammonium hydroxide is added to be uniformly mixed, to obtain aqueous dispersions, wherein the mole of tetramethylammonium hydroxide is to implement The sum of 2 times of the mole of hydrazine and the mole of tetramethylammonium hydroxide in example 16.The nano-carbon material containing hetero atom of preparation Structural parameters are listed in table 2.
Comparative example 12
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 16, unlike, step (1) preparation Aqueous dispersions are free of tetramethylammonium hydroxide, it is, the multi-walled carbon nanotube as raw material nano carbon material is dispersed in In ionized water, hydrazine is then added and is uniformly mixed, to obtain aqueous dispersions, wherein the mole of hydrazine is tetramethyl in embodiment 16 The sum of 0.5 times of the mole of base ammonium hydroxide and the mole of hydrazine.The structural parameters of the nano-carbon material containing hetero atom of preparation It is listed in table 2.
Embodiment 17
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 16, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, at autogenous pressures Reaction 48 hours.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 18
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 16, unlike, as raw material nano The multi-walled carbon nanotube of carbon material is same as Example 2.The structural parameters of the nano-carbon material containing hetero atom of preparation arrange in table 2 Out.
Embodiment 19
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 16, unlike, in step (1), hydrazine Under the same conditions with the integral molar quantity of tetramethylammonium hydroxide and embodiment 16, make hydrazine: the molar ratio of tetramethylammonium hydroxide For 1:85.The structural parameters of the nano-carbon material containing hetero atom of preparation are 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 and tetrapropylammonium hydroxide is then added It is uniformly mixed, to obtain aqueous dispersions, wherein raw material nano carbon material: hydrazine: tetrapropylammonium hydroxide: H2The weight ratio of O is 1:1:8:200；In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in At a temperature of 170 DEG C, react 24 hours at autogenous pressures.
The structural parameters of the nano-carbon material containing hetero atom of preparation are 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 6.The structure ginseng of the nano-carbon material containing hetero atom of preparation Number is listed in table 2.
Embodiment 22
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 20, unlike, in step (1), hydrazine Under the same conditions with the integral molar quantity of tetrapropylammonium hydroxide and embodiment 20, make hydrazine: the molar ratio of tetrapropylammonium hydroxide For 1:1.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 23
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 200 DEG C, at autogenous pressures Reaction 24 hours.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 24
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 20, unlike, in step (1), four The diethanol amine of propyl ammonium hydroxide equimolar amounts replaces.The structural parameters of the nano-carbon material containing hetero atom of preparation are in table 2 In list.
Embodiment 25
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 20, unlike, in step (1), four The n-propylamine of propyl ammonium hydroxide equimolar amounts replaces.The structural parameters of the nano-carbon material containing hetero atom of preparation are in table 2 It lists.
Embodiment 26
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 20, unlike, in step (1), four Propyl ammonium hydroxide is replaced with hexamethylene diamine, and the mole of hexamethylene diamine is the mole of tetrapropylammonium hydroxide in embodiment 20 0.5 times.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 27
Nano-carbon material containing hetero atom is prepared using method same as Example 1, difference is as follows:
It in step (1), disperses raw material nano carbon material in deionized water, urea is added and hexamethylene diamine is uniformly mixed, To obtain aqueous dispersions, wherein raw material nano carbon material: urea: hexamethylene diamine: H2The weight ratio of O is 1:1:1:20；
In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 110 At a temperature of DEG C, react 36 hours at autogenous pressures.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Comparative example 13
Aqueous dispersions identical with embodiment 27 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 110 DEG C, back flow reaction 36 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 At a temperature of DEG C after drying 6 hours, nano-carbon material containing hetero atom is obtained.The structure ginseng of the nano-carbon material containing hetero atom of preparation Number is listed in table 2.
Comparative example 14
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 27, unlike, step (1) preparation Aqueous dispersions are free of urea, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, so Hexamethylene diamine is added afterwards to be uniformly mixed, to obtain aqueous dispersions, wherein the mole of hexamethylene diamine is that urea rubs in embodiment 27 The sum of 0.5 times of that amount and the mole of hexamethylene diamine.The structural parameters of the nano-carbon material containing hetero atom of preparation arrange in table 2 Out.
Comparative example 15
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 27, unlike, step (1) preparation Aqueous dispersions are free of hexamethylene diamine, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, Then urea is added to be uniformly mixed, to obtain aqueous dispersions, wherein the mole of urea is that hexamethylene diamine rubs in embodiment 27 The sum of 2 times of that amount and the mole of urea.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 28
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 27, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, at autogenous pressures Reaction 36 hours.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 29
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 27, unlike, as raw material nano The multi-walled carbon nanotube of carbon material is same as Example 2.The structural parameters of the nano-carbon material containing hetero atom of preparation arrange in table 2 Out.
Embodiment 30
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 27, unlike, in step (1), Under the same conditions, so that urea: the molar ratio of hexamethylene diamine is 1:0.1 for the integral molar quantity of urea and hexamethylene diamine and embodiment 27.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 31
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 and n-butylamine mixing is equal It is even, to obtain aqueous dispersions, wherein press raw material nano carbon material: urea: n-butylamine: H2The weight ratio of O is 1:4:8:150 Ratio feed intake；In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in At a temperature of 160 DEG C, react 24 hours at autogenous pressures.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 32
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 31, unlike, in step (1), make Multi-walled carbon nanotube for raw material nano carbon material is same as Example 6.The structure ginseng of the nano-carbon material containing hetero atom of preparation Number is listed in table 2.
Embodiment 33
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 31, unlike, in step (1), Under the same conditions, so that urea: the molar ratio of n-butylamine is 1:2.5 for the integral molar quantity of urea and n-butylamine and embodiment 31.
The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 34
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 31, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 190 DEG C, at autogenous pressures Reaction 24 hours.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 35
Using method identical with embodiment 31 prepare nano-carbon material containing hetero atom, the difference is that, n-butylamine with etc. rub The diethanol amine of your amount replaces.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 36
Using method identical with embodiment 31 prepare nano-carbon material containing hetero atom, the difference is that, n-butylamine with etc. rub The tetramethylammonium hydroxide of your amount replaces.The structural parameters of the nano-carbon material containing hetero atom of preparation are listed in table 2.
Embodiment 37
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 31, unlike, n-butylamine second two Amine replaces, and the mole of ethylenediamine is 0.5 times of the mole of n-butylamine in embodiment 31.The nano carbon material containing hetero atom of preparation The structural parameters of material are listed in table 2.
Embodiment 38
Nano-carbon material containing hetero atom prepared by embodiment 1 roasts 4 hours in air atmosphere at 350 DEG C.
Comparative example 16-19
The nano-carbon material containing hetero atom that comparative example 16 prepares comparative example 1 350 DEG C in air atmosphere roasting it is 4 small When；
The nano-carbon material containing hetero atom that comparative example 17 prepares comparative example 2 350 DEG C in air atmosphere roasting it is 4 small When；
The nano-carbon material containing hetero atom that comparative example 18 prepares comparative example 3 350 DEG C in air atmosphere roasting it is 4 small When；
The nano-carbon material containing hetero atom that comparative example 19 prepares comparative example 4 350 DEG C in air atmosphere roasting it is 4 small When.
Embodiment 39
Nano-carbon material containing hetero atom prepared by embodiment 2 roasts 4 hours in air atmosphere at 350 DEG C.
Embodiment 40
Nano-carbon material containing hetero atom prepared by embodiment 3 roasts 4 hours in air atmosphere at 350 DEG C.
Embodiment 41
Nano-carbon material containing hetero atom prepared by embodiment 4 roasts 4 hours in air atmosphere at 350 DEG C.
Embodiment 42
Nano-carbon material containing hetero atom prepared by embodiment 16 roasts 2 hours in air atmosphere at 450 DEG C.
Embodiment 43
Nano-carbon material containing hetero atom prepared by embodiment 31 roasts 12 hours in air atmosphere at 300 DEG C.
Embodiment 44-86 is used to illustrate the application and hydrocarbon dehydrogenation reaction method of the nano-carbon material of the invention containing hetero atom.
Embodiment 44-80
Respectively using the nano-carbon material containing hetero atom of 0.2g (admission space 1.5mL) embodiment 1-37 preparation 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 0.98 volume %, normal butane and oxygen Gas molar ratio 2:5, surplus are nitrogen as carrier gas) it with total volume air speed is 800h-1It is passed through in reactor and is reacted, continuously The composition of the reaction mixture exported from reactor is monitored, and calculates n-butane conversion, total olefin selectivity and butadiene Selectivity, the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 20-34
It is reacted using method identical with embodiment 44-80, unlike, it is prepared respectively using comparative example 1-15 Nano-carbon material containing hetero atom is as catalyst.Reaction result is listed in table 3.
Comparative example 35
It is reacted using method identical with embodiment 44-80, unlike, use raw material same as Example 1 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Comparative example 36
It is reacted using method identical with embodiment 44-80, unlike, use raw material same as Example 5 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Embodiment 81-86
It is reacted using method identical with embodiment 44-80, unlike, contained using prepared by embodiment 38-43 Hetero atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 37-40
It is reacted using method identical with embodiment 44-80, unlike, contained using prepared by comparative example 16-19 Hetero atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 41
It is reacted using method identical with embodiment 44-80, unlike, catalyst is will be same as Example 1 Raw material nano carbon material 350 DEG C at a temperature of air atmosphere in roast 4 hours obtained from.Reaction result arranges in table 4 Out.
Comparative example 42
It is reacted using method identical with embodiment 44-80, unlike, catalyst is will be same as Example 5 Raw material nano carbon material 300 DEG C at a temperature of air atmosphere in roast 12 hours obtained from.Reaction result arranges in table 4 Out.
Table 3
Table 4
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (79)

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 On the basis of the total amount of the nano-carbon material containing hetero atom and based on the element, the content of O element is 1-8 weight %, the content of N element For 2-8 weight %, the content of C element is 84-97 weight %；
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 1.2-2.5；
This contains in hetero atom nano-carbon material, determines the N element in the nano-carbon material containing hetero atom by x-ray photoelectron spectroscopy Total amount be IN t, the amount of the N element determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy is IN c, IN c/ IN tIn the range of 0.7-1；
The preparation method of the nano-carbon material containing hetero atom includes that one kind is dispersed with to raw material nano carbon material, at least one nitrogenous The aqueous dispersions of compound and at least one organic base are reacted in closed container, and the nitrogenous compound is selected from NH3、 Hydrazine and urea, for the organic base in amine and quaternary ammonium base, reaction process, the temperature of the aqueous dispersions is maintained at 80-250 DEG C In the range of.
2. nano-carbon material containing hetero atom according to claim 1, wherein IO c/IO eIn the range of 1.3-2.2；IN c/ IN tIn the range of 0.75-0.98.
3. nano-carbon material containing hetero atom according to claim 2, wherein IO c/IO eIn the range of 1.4-2；IN c/IN t In the range of 0.8-0.95.
4. nano-carbon material containing hetero atom described in any one of -3 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 1.5-4.
5. nano-carbon material containing hetero atom according to claim 4, wherein IC c/IC eIn the range of 1.5-3.5.
6. nano-carbon material containing hetero atom according to claim 5, wherein IC c/IC eIn the range of 1.55-3.
7. nano-carbon material containing hetero atom described in any one of -3 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 70-90 weight %, by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The content of determining C element is 10-30 weight %.
10. nano-carbon material containing hetero atom described in any one of -3 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 0.3.
11. nano-carbon material containing hetero atom according to claim 10, wherein IN g/IN tIn the range of 0.02-0.25.
12. nano-carbon material containing hetero atom according to claim 11, wherein IN g/IN tIn the range of 0.05-0.2.
13. nano-carbon material containing hetero atom described in any one of -3 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 O element is 2.5-7.5 weight %, and the content of C element is 86.5- 95.5 weight %, the content of N element are 2-6 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 O element is 3-7 weight %, and the content of C element is 88-94 weight %, and N element contains Amount is 3-5 weight %.
15. nano-carbon material containing hetero atom according to claim 14, 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 O element is 4.5-7 weight %, and the content of C element is 88.5-92 weight %, N element Content be 3.5-4.5 weight %.
16. nano-carbon material containing hetero atom described in any one of -3 according to claim 1, wherein this contains hetero atom nanometer Carbon material is carbon nanotube containing hetero atom.
17. nano-carbon material containing hetero atom according to claim 16, wherein it is containing miscellaneous that this, which contains hetero atom nano-carbon material, Atom multi-walled carbon nanotube.
18. nano-carbon material containing hetero atom according to claim 17, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 50-500m2/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 80-300m2/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 90-150m2/g。
21. nano-carbon material containing hetero atom according to claim 20, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 95-140m2/g。
22. nano-carbon material containing hetero atom according to claim 17, wherein the multi-walled carbon nanotube containing hetero atom exists 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/ w800In the range of 0.01-0.5, the weight-loss ratio measures in air atmosphere.
23. nano-carbon material containing hetero atom according to claim 22, wherein w500/w800In the range of 0.02-0.2.
24. a kind of preparation method of nano-carbon material containing hetero atom, this method include one kind is dispersed with raw material nano carbon material, The aqueous dispersions of at least one nitrogenous compound and at least one organic base are reacted in closed container, the nitrogen It closes object and is selected from NH3, hydrazine and urea, the organic base is selected from amine and quaternary ammonium base, and in reaction process, the temperature of the aqueous dispersions is protected Hold in the range of 80-250 DEG C, raw material nano carbon material: nitrogenous compound: the weight ratio of organic base is 1:0.01-20: 0.01-20。
25. according to the method for claim 24, wherein raw material nano carbon material: H2The weight ratio of O is 1:2-1000.
26. according to the method for claim 25, wherein raw material nano carbon material: nitrogenous compound: the weight ratio of organic base For 1:0.02-10:0.02-15.
27. according to the method for claim 25, wherein raw material nano carbon material: H2The weight ratio of O is 1:5-500.
28. according to the method for claim 27, wherein raw material nano carbon material: H2The weight ratio of O is 1:10-300.
29. according to the method for claim 28, wherein raw material nano carbon material: H2The weight ratio of O is 1:20-200.
30. the method according to any one of claim 24-29, wherein nitrogenous compound: the molar ratio of organic base is 1:0.05-100.
31. according to the method for claim 30, wherein nitrogenous compound: the molar ratio of organic base is 1:0.1-90.
32. according to the method for claim 31, wherein nitrogenous compound: the molar ratio of organic base is 1:0.4-80.
33. the method according to any one of claim 24-29, wherein the organic base is chemical combination shown in Formulas I Object, Formula II compound represented, formula III compound represented and general formula R12(NH2)2One or both of substance of expression More than, R12For C1-C6Alkylidene,
In Formulas I, R1、R2、R3And R4Respectively C1-C20Alkyl or C6-C12Aryl；
In Formula II, R5、R6And R7Respectively H or C1-C6Alkyl, and R5、R6And R7It is not simultaneously H；
In formula III, R8、R9And R10Respectively-R11OH, hydrogen or C1-C6Alkyl, and R8、R9And R10At least one of for- R11OH, R11For C1-C4Alkylidene.
34. according to the method for claim 33, wherein the nitrogenous compound is ammonia, and the organic base is selected from formula III institute The compound shown, raw material nano carbon material: nitrogenous compound: the weight ratio of organic base is 1:0.02-10:0.05-8, nitrogen Close object: the molar ratio of organic base is 1:0.05-5.
35. according to the method for claim 34, wherein the organic base is selected from ethanol amine, diethanol amine and triethanolamine.
36. according to the method for claim 34, wherein raw material nano carbon material: nitrogenous compound: the weight ratio of organic base For 1:0.03-5:0.1-6, nitrogenous compound: the molar ratio of organic base is 1:0.1-2.5.
37. according to the method for claim 36, wherein raw material nano carbon material: nitrogenous compound: the weight ratio of organic base For 1:0.05-2:0.2-5, nitrogenous compound: the molar ratio of organic base is 1:0.4-0.8.
38. according to the method for claim 33, wherein the nitrogenous compound is hydrazine, and the organic base is selected from shown in Formulas I Compound, raw material nano carbon material: nitrogenous compound: the weight ratio of organic base be 1:0.01-5:0.02-10, nitrogenous chemical combination Object: the molar ratio of organic base is 1:0.5-100.
39. according to the method for claim 38, wherein raw material nano carbon material: nitrogenous compound: the weight ratio of organic base For 1:0.02-2.5:1-9, nitrogenous compound: the molar ratio of organic base is 1:1-90.
40. according to the method for claim 39, wherein raw material nano carbon material: nitrogenous compound: the weight ratio of organic base For 1:0.02-1.5:4.5-8, nitrogenous compound: the molar ratio of organic base is 1:1.1-80.
41. according to the method for claim 33, wherein the nitrogenous compound is urea, and the organic base is selected from Formula II Compound represented and general formula R12(NH2)2The substance of expression, raw material nano carbon material: nitrogenous compound: the weight of organic base Than for 1:0.02-10:0.05-20, nitrogenous compound: the molar ratio of organic base is 1:0.1-5.
42. according to the method for claim 41, wherein the organic base is selected from ethylenediamine, n-butylamine and diamines.
43. according to the method for claim 41, wherein raw material nano carbon material: nitrogenous compound: the weight ratio of organic base For 1:0.1-8:0.5-15.
44. according to the method for claim 43, wherein raw material nano carbon material: nitrogenous compound: the weight ratio of organic base For 1:1-5:1-10.
45. according to the method for claim 41, wherein nitrogenous compound: the molar ratio of organic base is 1:0.5-2.
46. the method according to any one of claim 24-29, wherein in reaction process, the temperature of the aqueous dispersions Degree is maintained in the range of 100-180 DEG C.
47. the method according to any one of claim 24-29, wherein the duration of the reaction is in 0.5-96 In the range of hour.
48. according to the method for claim 47, wherein the duration of the reaction is in the range of 2-72 hours.
49. according to the method for claim 48, wherein the duration of the reaction is in the range of 10-40 hours.
50. the method according to any one of claim 24-29, wherein O element in the raw material nano carbon material Content is not higher than 1.2 weight %, and the content of N element is not higher than 0.5 weight %.
51. according to the method for claim 50, wherein in the raw material nano carbon material content of O element be not higher than 0.5 weight %.
52. according to the method for claim 50, wherein the content of N element is not higher than 0.2 weight %.
53. method according to claim 52, wherein the content of N element is not higher than 0.1 weight %.
54. method according to claim 53, wherein the content of N element is not higher than 0.05 weight %.
55. the method according to any one of claim 24-29, wherein the raw material nano carbon material is carbon nanometer Pipe.
56. method according to claim 55, wherein the raw material nano carbon material is multi-walled carbon nanotube.
57. method according to claim 56, wherein the specific surface area of the multi-walled carbon nanotube is 20-500m2/g。
58. method according to claim 57, wherein the specific surface area of the multi-walled carbon nanotube is 50-300m2/g。
59. method according to claim 58, wherein the specific surface area of the multi-walled carbon nanotube is 80-250m2/g。
60. method according to claim 59, wherein the specific surface area of the multi-walled carbon nanotube is 90-150m2/g。
61. method according to claim 56, wherein the multi-walled carbon nanotube is in 400-800 DEG C of temperature range Weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, The weight-loss ratio measures in air atmosphere.
62. method according to claim 61, wherein w500/w800In the range of 0.02-0.2.
63. the method according to any one of claim 24-29, wherein this method further include obtained from reaction it is mixed It closes in object and isolates solid matter, and the solid matter isolated is dried.
64. method according to claim 63, wherein the drying 50-200 DEG C at a temperature of carry out, the drying Duration be 0.5-48 hours.
65. method according to claim 64, wherein the drying 80-180 DEG C at a temperature of carry out, the drying Duration be 4-24 hours.
66. method according to claim 65, wherein the drying 100-150 DEG C at a temperature of carry out, the drying Duration be 6-12 hours.
67. a kind of nano-carbon material containing hetero atom of the preparation of the method as described in any one of claim 24-66.
68. a kind of nano-carbon material containing hetero atom, it is by any one of claim 1-23 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 67 is roasted and is made 's.
69. nano-carbon material containing hetero atom according to claim 68, wherein temperature of the roasting at 250-500 DEG C Lower progress；The duration of the roasting is 1-24 hours.
70. nano-carbon material containing hetero atom according to claim 69, wherein temperature of the roasting at 300-450 DEG C Lower progress；The duration of the roasting is 2-12 hours.
71. in nano-carbon material containing hetero atom described in any one of claim 1-23 and 67 or claim 68-70 Application of the nano-carbon material containing hetero atom described in any one as the catalyst of hydrocarbon dehydrogenation reaction.
72. application according to claim 71, wherein the dehydrogenation reaction carries out in the presence of oxygen.
73. the application according to claim 71 or 72, wherein the hydrocarbon is alkane.
74. the application according to claim 73, wherein the hydrocarbon is C2-C12Alkane.
75. application according to claim 74, wherein the hydrocarbon is normal butane.
76. 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 68- described in any one of hydrocarbon and claim 1-23 and 67 The contact of nano-carbon material containing hetero atom described in any one of 70.
77. the method according to claim 76, wherein the hydrocarbon is alkane.
78. the method according to claim 77, wherein the hydrocarbon is C2-C12Alkane.
79. the method according to claim 78, wherein the hydrocarbon is normal butane.
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Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108155020B (en) * 2016-12-02 2019-10-25 中国石油化工股份有限公司 Graphene composite material and its preparation method and application
CN108218696B (en) * 2016-12-21 2021-03-26 江苏优嘉植物保护有限公司 Production process of bifenthrin
CN109305683B (en) * 2017-07-27 2020-08-18 中国石油化工股份有限公司 Heteroatom-containing carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation method
CN109304196B (en) * 2017-07-27 2021-05-14 中国石油化工股份有限公司 Heteroatom-containing carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation method
CN109305666B (en) * 2017-07-28 2020-08-18 中国石油化工股份有限公司 Heteroatom-containing nano carbon material and preparation method thereof, cyclohexane oxidation method and hydrocarbon oxidation dehydrogenation method
CN109304152B (en) * 2017-07-28 2021-10-08 中国石油化工股份有限公司 Heteroatom-containing nano carbon material and acrolein oxidation method
CN109304189B (en) * 2017-07-28 2022-01-04 中国石油化工股份有限公司 Heteroatom-containing nano carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation reaction method
CN109305665B (en) * 2017-07-28 2020-08-18 中国石油化工股份有限公司 Heteroatom-containing nano carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation reaction method
CN109304198B (en) * 2017-07-28 2022-03-11 中国石油化工股份有限公司 Heteroatom-containing nano carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation reaction method
CN109304200B (en) * 2017-07-28 2021-11-16 中国石油化工股份有限公司 Heteroatom-containing nano carbon material, preparation method thereof and aromatic hydrocarbon oxidation method
CN107445787B (en) * 2017-08-22 2020-07-07 中国科学院金属研究所 Application of graphitized activated carbon material as catalyst for oxidative dehydrogenation reaction of n-butane
CN108409521B (en) * 2018-04-11 2020-10-09 中国科学院金属研究所 Application of two-dimensional metal carbide material as catalyst for ethylbenzene direct dehydrogenation reaction
CN109046421B (en) * 2018-07-24 2019-06-28 山东科技大学 It is a kind of to prepare C, N co-doped nano pipe/stick catalysis material method using quaternary ammonium base
WO2020067299A1 (en) * 2018-09-27 2020-04-02 株式会社村田製作所 Module and production method therefor
CN112439440B (en) * 2019-08-30 2023-06-09 中国石油化工股份有限公司 Nano nitrogen-carbon material, preparation method thereof and catalytic oxidation method of thioether
CN115724809A (en) * 2021-08-31 2023-03-03 中国石油化工股份有限公司 Method for preparing styrene oxide
CN115724810B (en) * 2021-08-31 2024-05-17 中国石油化工股份有限公司 Method for preparing epoxypropane
CN116199650A (en) * 2021-12-01 2023-06-02 中国石油化工股份有限公司 Ethylbenzene oxidation method
CN116199647A (en) * 2021-12-01 2023-06-02 中国石油化工股份有限公司 Method for producing epoxypropane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436871B1 (en) * 1999-02-22 2002-08-20 Symyx Technologies, Inc. Catalysts for oxidative dehydrogenation
CN102060284A (en) * 2010-10-29 2011-05-18 华南理工大学 Method for preparing nitrogen-phosphorus codoped multi-walled carbon nanotube
CN103682380A (en) * 2012-09-07 2014-03-26 中国科学院大连化学物理研究所 Electrocatalyst of negative electrode of fuel cell as well as preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101014412A (en) * 2004-07-16 2007-08-08 那诺克有限公司 Catalyst comprising nanocarbon structures for the production of unsaturated hydrocarbons
CN1911502A (en) * 2006-09-05 2007-02-14 大庆石油管理局 Nanometer grade low carbon paraffin dehydrogen catalyst
CN101718011B (en) * 2009-11-16 2011-11-23 天津工业大学 Method for preparing carbon nanofibers
CN101774573A (en) * 2010-02-08 2010-07-14 哈尔滨工业大学 Method for amination of carbon nano tube
CN102432085B (en) * 2011-12-20 2013-05-29 华北电力大学（保定） Method for removing mercury ions in water and regeneration method of adsorbent used in same
CN103706388B (en) * 2013-12-30 2016-01-06 中国科学院化学研究所 Composite of N doping porous carbon enveloped carbon nanometer tube and its preparation method and application
CN105817250B (en) * 2015-01-27 2019-07-23 中国石油化工股份有限公司 A kind of carbon-based material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436871B1 (en) * 1999-02-22 2002-08-20 Symyx Technologies, Inc. Catalysts for oxidative dehydrogenation
CN102060284A (en) * 2010-10-29 2011-05-18 华南理工大学 Method for preparing nitrogen-phosphorus codoped multi-walled carbon nanotube
CN103682380A (en) * 2012-09-07 2014-03-26 中国科学院大连化学物理研究所 Electrocatalyst of negative electrode of fuel cell as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Nitrogen-Doped Carbon Nanotubes as a Highly Active Metal-Free Catalyst for Selective Oxidation;Kambiz Chizari et al.;《ChemSusChem》;20111201;第5卷;第102-108页
纳米碳材料和高性能催化;齐伟 等;《化学反应工程与工艺》;20131031;第29卷(第5期);第423-429页

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