CN105817249B

CN105817249B - One kind nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method

Info

Publication number: CN105817249B
Application number: CN201510702385.0A
Authority: CN
Inventors: 史春风; 荣峻峰; 于鹏; 谢婧新; 宗明生; 林伟国
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-01-27
Filing date: 2015-10-26
Publication date: 2018-07-31
Anticipated expiration: 2035-10-26
Also published as: CN105817242B; CN105817245A; CN105820022B; CN105817251A; CN105817248B; CN105817246B; CN105817248A; CN105817251B; CN105817249A; CN105817247B; CN105817245B; CN105817242A; CN105817246A; CN105820022A; CN105817247A

Abstract

The invention discloses a kind of nano-carbon materials containing hetero atom and its preparation method and application, the C of O containing 6 12 weight % and 88 94 weight %, in XPS spectrum figure, the ratio of the amount for the O elements that the amount for the O elements that peak within the scope of 531.0 532.5eV determines is determined with the peak within the scope of 532.6 533.5eV is that the ratio of the amount for the C element that the C element that the peak within the scope of 0.3 1,288.6 288.8eV determines is determined with the peak within the scope of 286.0 286.2eV is 0.4 2.The present invention further discloses the hydrocarbon dehydrogenation reaction methods for using the nano-carbon material containing hetero atom.The nano-carbon material containing hetero atom shows good catalytic activity in hydrocarbon dehydrogenation reaction, can significantly improve the conversion ratio of raw material, while can also obtain preferable olefine selective, especially has higher selectivity to 1 butylene.

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 by 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 technology

Nano-carbon material is a kind of important inorganic non-metallic catalyst that developed recently gets up, in the hydrocarbon conversion, finely The multiple fields such as chemical industry, fuel cell, solar energy conversion exhibit improvements over the performance of conventional metals catalyst, cause section skilled worker The extensive concern of author has huge development potentiality.

Although nano-carbon material itself has certain catalytic activity, catalytic performance (as activity) still up for into One step improves.In order to further increase the catalytic performance (such as activity) of nano-carbon material, researcher attempts in nano-carbon material Middle introducing hetero-atoms introduce oxygen atom, nitrogen-atoms to carry out modification to nano-carbon material such as 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 be introduced 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, residing 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 into nano-carbon material skeleton structure with The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly include graphite mould nitrogen (that is,), pyridine type nitrogen (that is,) and pyrrole Cough up type nitrogen (that is,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen and Pyrroles's type nitrogen is unsaturated nitrogen atom, while replacing carbon atom, can often cause the missing for closing on carbon atom, form defect Position.

Can by introduced in nano-carbon material building-up process nitrogenous functional atmosphere (such as ammonia, nitrogen, urea, Melamine), nitrogen is introduced into nano carbon material simultaneously in the building-up 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 structure nitrogen can be formed 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, in nanometer by the way that nano-carbon material is carried out oxidation processes Carbon material surface introduces nitrogen-atoms, and the nitrogen-atoms so introduced is essentially chemical nitrogen.

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 to hydrocarbon The direct dehydrogenation reaction of matter and oxidative dehydrogenation all have catalytic effect, and oxygen atom and/or nitrogen are introduced in nano-carbon material Atom can then improve its catalytic activity.

Although Heteroatom doping modification and its research of catalytic performance in relation to nano-carbon material achieve many progress, It is not build consensus yet for some of which basic problem, still needs to Heteroatom doping nano-carbon material and its preparation side Method and catalytic performance are furtherd investigate.

Invention content

It is an object of the present invention to provide a kind of preparation methods of nano-carbon material containing hetero atom, using this method energy The content of oxygen atom in nano-carbon material is steadily improved, and the structure of nano-carbon material itself is influenced little.

It is another object of the present invention to provide a kind of nano-carbon materials containing hetero atom, this contains hetero atom nano-carbon material There is preferable catalytic effect to the dehydrogenation reaction of hydrocarbons, the conversion ratio of raw material, and product can not only be effectively improved Selectivity is good.

Another object of the present invention is to provide a kind of hydrocarbon dehydrogenation reaction method, this method can obtain higher raw material conversion Rate and selectivity of product.

According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing hetero atom, this contains hetero atom Nano-carbon material contains C element and O elements, on the basis of the total amount of the nano-carbon material containing hetero atom and based on the element, O elements Content be 6-12 weight %, the content of C element is 88-94 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 elements amount be I_O ^c, the amount of the O elements determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is I_O ^e, I_O ^c/I_O ^eIn the range of 0.3-1；

The amount of the C element determined by the peak within the scope of 288.6-288.8eV in x-ray photoelectron spectroscopy is I_C ^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 I_C ^e, I_C ^c/I_C ^eIn the range of 0.4-2.

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 include by a kind of aqueous dispersions being dispersed with raw material nano carbon material and at least one peroxide in closed container It is reacted, in reaction process, the temperature of the aqueous dispersions is maintained in the range of 100-250 DEG C.

According to the third aspect of the present invention, the present invention provides a kind of method systems by according to the second aspect of 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 will to be roasted according to the nano-carbon material containing hetero atom in terms of the first aspect of 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 according to the first aspect of the present invention Carbon material, according to the nano-carbon material containing hetero atom of third aspect of the present invention or containing according to the 4th aspect of the present invention 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, deposits Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, hydrocarbon is contained into miscellaneous original with according to the first aspect of the present invention Sub- nano-carbon material, according to the nano-carbon material containing hetero atom of third aspect of the present invention or according to the 4th side of the invention 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 Oxygen atom content 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 Expect with stable performance.

Nano-carbon material containing hetero atom according to the present invention shows good catalysis in the dehydrogenation reaction of hydrocarbons Performance can significantly improve feed stock conversion and selectivity of product.Specifically, by nano carbon material containing hetero atom according to the present invention When material is used as the catalyst of n butane oxidation dehydrogenation reaction, there is higher n-butane conversion, and good product selectivity, it is right 1- butylene has higher selectivity.

Description of the drawings

Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

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 implementation mode

In the present invention, nano-carbon material refers to the dispersed phase scale at least one-dimensional carbon material less than 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 and O elements.

Nano-carbon material containing hetero atom according to the present invention, on the basis of the total amount of the nano-carbon material containing hetero atom and with The content of element meter, O elements is 6-12 weight %, preferably 7-11 weight %；The content of C element is 88-94 weight %, preferably For 89-93 weight %.Wherein, the content of each element is measured using x-ray photoelectron spectroscopy (XPS) method, by 1s electronics spectral peaks pair The area answered determines the content of element；Sample is done in 150 DEG C of temperature and the pressure of 1 normal atmosphere in helium atmosphere before testing Dry 3 hours.

In the present invention, X-ray photoelectron spectroscopic analysis is in Thermo Scientific companies equipped with Thermo It is tested on the ESCALab250 type x-ray photoelectron spectroscopies of Avantage V5.926 softwares, excitaton source is monochromatization Al K α X-rays, 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 peaks C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage softwares Upper carry out data processing carries out quantitative analysis in analysis module using sensitivity factor method.

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 elements (that is, C=O) amount be I_O ^c, true by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy The amount of fixed O elements (that is, C-O) is I_O ^e, I_O ^c/I_O ^eIn the range of 0.3-1, preferably in the range of 0.4-0.95, more preferably In the range of 0.5-0.8, further preferably in the range of 0.6-0.7.In the present invention, by x-ray photoelectron spectroscopy The area A of O1s spectral peaks_O ¹O1s spectral peaks in x-ray photoelectron spectroscopy are divided into two groups of peaks, that is, existed by the total amount for determining O elements Spectral peak (corresponding to C=O species) within the scope of 531.0-532.5eV and the spectral peak within the scope of 532.6-533.5eV are (corresponding In CO species), the area of the spectral peak within the scope of 531.0-532.5eV is denoted as A_O ², will be within the scope of 532.6-533.5eV The area of spectral peak is denoted as A_O ³, I_O ^c/I_O ^e=A_O ²/A_O ³.In the present invention, when indicating numberical range, " ×-× in the range of " packet Include two binary values.

Nano-carbon material containing hetero atom according to the present invention, the total amount with C element in the nano-carbon material containing hetero atom are Benchmark, the content of the C element determined by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy (that is, graphite mould carbon) Can be 60-98 weight %, preferably 70-96 weight %, more preferably 80-95 weight %；By in x-ray photoelectron spectroscopy The total content for the C element that peak within the scope of 286.0-288.8eV determines can be 2-40 weight %, preferably 4-30 weight %, More preferably 5-20 weight %.In the present invention, by the area A of the C1s spectral peaks in x-ray photoelectron spectroscopy_C ¹Determine the total of C element Amount, is divided into two groups of peaks by the C1s spectral peaks in x-ray photoelectron spectroscopy, i.e., the spectral peak within the scope of 284.7-284.9eV is (corresponding In graphite mould carbon species) and spectral peak (correspond to non-graphite type carbon species) within the scope of 286.0-288.8eV, it will be The area of spectral peak within the scope of 284.7-284.9eV is denoted as A_C ², the area of the spectral peak within the scope of 286.0-288.8eV is denoted as A_C ³, by the content=A for the C element that the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy determines_C ²/A_C ¹, penetrated by X Total content=the A for the C element that peak in photoelectron spectra within the scope of 286.0-288.8eV determines_C ³/A_C 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 I_C ^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 I_C ^e, I_C ^c/I_C ^eIn the range of 0.4-2, preferably in the model of 0.5-1.5 In enclosing, more preferably in the range of 0.7-1.2, further preferably in the range of 0.8-1, still more preferably in 0.85- In the range of 0.95.In the present invention, the spectral peak in x-ray photoelectron spectroscopy within the scope of 286.0-288.8eV (is corresponded to non- Graphite carbon species) be further divided into two groups of peaks, i.e., the spectral peak within the scope of 286.0-286.2eV (corresponds to hydroxyl and ether type Carbon species) and spectral peak (correspond to carboxyl, acid anhydride and ester type carbon species) within the scope of 288.6-288.8eV, it will be in 286.0- The area of spectral peak within the scope of 286.2eV is denoted as A_C ⁴, the area of the spectral peak within the scope of 288.6-288.8eV is denoted as A_C ⁵, I_C ^c/I_C ^e=A_C ⁵/A_C ⁴。

In the present invention, the combination corresponding to the summit of the position at each peak by the peak can determine that range determines by mentioned earlier Peak refer to peak that combination corresponding to summit can be within that range, may include a peak in the range, can also wrap Include more than two peaks.Such as：Peak within the scope of 286.0-288.8eV, which refers to the combination corresponding to summit, can be in 286.0- Whole peaks in the range of 288.8eV.

Nano-carbon material containing hetero atom according to the present invention can exist with common various forms, be specifically as follows but not Be limited to carbon nanotube containing hetero atom, graphene containing hetero atom, thin layer graphite containing hetero atom, nano carbon particle containing hetero atom, containing miscellaneous The combination of one or more of atom carbon nano-fiber, Nano diamond containing hetero atom and doped fullerene.Institute Stating can be for single-walled carbon nanotube containing hetero atom, double-walled carbon nano-tube containing hetero atom and containing hetero atom containing heteroatomic carbon nanotube The combination of one or more of multi-walled carbon nanotube.Nano-carbon material containing hetero atom according to the present invention, preferably contains Hetero atom multi-walled carbon nanotube.

Nano-carbon material containing hetero atom according to the present invention, it is preferable that the ratio table of the multi-walled carbon nanotube containing hetero atom Area is 50-500m²/ g can further increase 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 90-200m²/g.In the present invention, The specific surface area is measured by nitrogen adsorption BET method.

Nano-carbon material containing hetero atom according to the present invention, the multi-walled carbon nanotube containing hetero atom is at 400-800 DEG C Weight-loss ratio in temperature range is w₈₀₀, the weight-loss ratio in 400-500 DEG C of temperature range is w₅₀₀, w₅₀₀/w₈₀₀It is preferred that In the range of 0.01-0.5, better catalytic effect can be obtained in this way, is especially used as the catalysis of hydrocarbons dehydrogenation reaction When agent, better catalytic effect can be obtained.It is highly preferred that temperature of the multi-walled carbon nanotube containing hetero atom at 400-800 DEG C Weight-loss ratio in section is w₈₀₀, the weight-loss ratio in 400-500 DEG C of temperature range is w₅₀₀, w₅₀₀/w₈₀₀More preferably in 0.02- In the range of 0.2.In the present invention, w₈₀₀=W₈₀₀- W₄₀₀, w₅₀₀=W₅₀₀- W₄₀₀, W₄₀₀For the matter measured at a temperature of 400 DEG C Amount loss rate, W₈₀₀For the mass loss rate measured at a temperature of 800 DEG C, W₅₀₀For the quality measured at a temperature of 500 DEG C Loss late；The weight-loss ratio is measured using thermogravimetric analyzer in air atmosphere, and test initial temperature is 25 DEG C, and heating rate is 10℃/min；Sample is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before testing.

In a kind of preferred embodiment of the present invention, the nano-carbon material containing hetero atom is preferably more containing hetero atom Wall carbon nano tube, which is 50-500m²/ g, preferably 80-300m²/ g, it is more excellent It is selected as 90-200m²/g；Also, w₅₀₀/w₈₀₀In the range of 0.01-0.5, preferably in the range of 0.02-0.2.

Nano-carbon material containing hetero atom according to the present invention, such as nitrogen-atoms, sulphur atom and phosphorus atoms are other nonmetallic miscellaneous Atom content can be customary amount.Usually, in nano-carbon material containing hetero atom according to the present invention, its outside oxygen atom The total amount of its nonmetallic heteroatoms (such as nitrogen-atoms, sulphur atom and phosphorus atoms) can be 0.5 weight % hereinafter, preferably 0.2 weight Measure % or less.Nano-carbon material containing hetero atom according to the present invention may also contain on a small quantity in nano-carbon material preparation process Remaining metallic atom, for these remaining metallic atoms mostly from the catalyst used when nano-carbon material is prepared, these are residual The content of the metallic atom stayed is generally 2 weight % hereinafter, it is preferred that in 1 weight % hereinafter, more preferably below 0.5 weight %.

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 include by a kind of aqueous dispersions being dispersed with raw material nano carbon material and at least one peroxide in closed container It is reacted.In the present invention, "at least one" indicates one or more kinds of.

The peroxide refers to the compound for containing-O-O- keys in molecular structure.Specifically, the peroxide can be with The organic peroxide shown in the hydrogen peroxide and Formulas I,

In Formulas I, R₁And R₂It each is selected from H, C₄-C₁₂Alkyl, C₆-C₁₂Aryl, C₇-C₁₂Aralkyl andAnd R₁And R₂It is asynchronously H, R₃For C₄-C₁₂Linear or branched alkyl group or C₆-C₁₂Aryl.

In the present invention, C₄-C₁₂The specific example of alkyl can include but is not limited to normal-butyl, sec-butyl, isobutyl group, uncle Butyl, n-pentyl, neopentyl, isopentyl, tertiary pentyl, hexyl (the various isomers for including hexyl), cyclohexyl, octyl (including The various isomers of octyl), nonyl (the various isomers for including nonyl), decyl (the various isomers for including decyl), 11 Alkyl (the various isomers for including undecyl) and dodecyl (the various isomers for including dodecyl).

In the present invention, C₆-C₁₂The specific example of aryl can include but is not limited to phenyl, naphthalene, aminomethyl phenyl and second Base phenyl.

In the present invention, C₇-C₁₂The specific example of aralkyl can include but is not limited to phenyl methyl, phenylethyl, benzene Base n-propyl, phenyl normal-butyl, phenyl t-butyl, propyloxy phenyl base, phenyl n-pentyl and phenyl normal-butyl.

The specific example of the peroxide can include but is not limited to：Hydrogen peroxide, tert-butyl hydroperoxide, peroxidating Hydrogen isopropylbenzene, hydrogen peroxide ethylbenzene, cyclohexyl hydroperoxide, cumyl peroxide, dibenzoyl peroxide, two uncle of peroxidating Butyl and dilauroyl peroxide.

According to the method for the present invention, the dosage of the peroxide can be according to it is contemplated that introduce in raw material nano carbon material Oxygen element content and type selected.In the nano-carbon material containing hetero atom finally prepared as hydrocarbon dehydrogenation reaction Catalyst when, raw material nano carbon material：The weight ratio of peroxide is preferably 1：In the range of 0.5-50.It is highly preferred that former Expect nano-carbon material：The weight ratio of peroxide is 1：In the range of 1-40.When the peroxide is hydrogen peroxide, raw material Nano-carbon material：The weight ratio of peroxide is preferably 1：In the range of 1-5.

Method according to the invention it is possible to be selected the dosage of water according to the amount of raw material nano carbon material.Preferably, Raw material nano carbon material：H₂The weight ratio of O is 1：In the range of 2-50, when within the scope of the dosage of water being in this, nano-sized carbon Structural form retentivity of the material in processing procedure is more preferable, such as：When raw material nano carbon material is carbon nanotube, processed It will not be cut off substantially in journey.It is highly preferred that raw material nano carbon material：H₂The weight ratio of O is 1：In the range of 5-40.Further Preferably, raw material nano carbon material：H₂The weight ratio of O is 1：In the range of 10-30.Furthermore it is also possible to according to peroxide Type is adjusted the dosage of water, so that subject to the peroxide can be dispersed in water.

According to the method for the present invention, the condition of the reaction is to be enough to improve containing for the oxygen atom in raw material nano carbon material Subject to amount.Preferably, in reaction process, the temperature of the aqueous dispersions is in the range of 100-250 DEG C.In the aqueous dispersions Temperature when being within above range, the oxygen atom content in raw material nano carbon material can not only be effectively improved, and not The structural form generation of raw material nano carbon material can be significantly affected.It is highly preferred that in reaction process, the temperature of the aqueous dispersions Degree is in the range of 120-220 DEG C.It is further preferred that in reaction process, the temperature of the aqueous dispersions is at 150-200 DEG C In range.

According to the method for the present invention, the duration of the reaction can be selected according to the temperature of reaction, with can It is introduced in raw material nano carbon material subject to enough oxygen atoms.Usually, the duration of the reaction can be in 0.5-144 In the range of hour, preferably in the range of 2-72 hours, more preferably in the range of 5-40 hours.

Method according to the invention it is possible to form the aqueous dispersions using common various methods, such as can incite somebody to action Raw material nano carbon material is dispersed in water (preferably deionized water), and peroxide is then added and is uniformly mixed, to obtain State aqueous dispersions.In order to further increase the dispersion effect of raw material nano carbon material, while shortening the time of dispersion, may be used Raw material nano carbon material is dispersed in water by the method for sonic oscillation.The condition of the sonic oscillation can be conventional selection, one As, the frequency of the sonic oscillation can be 10-100kHz, preferably 10-60kHz；The duration of the sonic oscillation It can be 0.1-12 hours, preferably 0.5-1 hours.The peroxide, can be in form of an aqueous solutions according to specific type It provides, can also be provided in the form of pure material.

According to the method for the present invention, the content of O elements is not particularly limited in the raw material nano carbon material, can be normal Rule selection.Usually, the content of O elements is not higher than 1 weight % preferably not higher than 0.5 in the raw material nano carbon material Weight %.According to the method for the present invention, remaining nonmetallic heteroatoms (such as nitrogen in the raw material nano carbon material outside oxygen atom Atom, phosphorus atoms and sulphur atom) total amount (based on the element) can be customary amount.Usually, the raw material nano carbon material The total amount of remaining nonmetallic heteroatoms outside middle oxygen atom be not higher than 0.5 weight %, preferably not higher than 0.2 weight %, More preferably not above 0.1 weight % is further preferably not higher than 0.05 weight %.According to the method for the present invention, the original Expect difference of the nano-carbon material according to source, some metallic elements can also be contained, these metallic elements are typically derived from preparation The catalyst used when raw material nano carbon material, content is generally in 2 weight % hereinafter, it is preferred that in 1 weight % hereinafter, more preferably In 0.5 weight % hereinafter, further preferably below 0.2 weight %.

According to the method for the present invention, method commonly used in the art may be used before use and carry out in advance for raw material nano carbon material Processing (as washed), to remove some impurity of raw material nano carbon material surface；It can not also be pre-processed, directly be used, In embodiment disclosed by the invention, raw material nano carbon material is not pre-processed before.

Method according to the invention it is possible to handle the nano-carbon material of various existing forms, received to improve this Oxygen atom content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon nanotube, graphene, nanogold The combination of one or more of hard rock, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene.The carbon is received Mitron can be the combination of one or more of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube.It is excellent Selection of land, the raw material nano carbon material are 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 100-200m²/g.It is received in the multi wall carbon When the specific surface area of mitron is within above range, there is finally obtained nano-carbon material containing hetero atom preferably catalysis to live Property, especially in the catalyst of the dehydrogenation reaction as hydrocarbons, show higher catalytic activity.

When the raw material nano carbon material is multi-walled carbon nanotube, temperature of the multi-walled carbon nanotube at 400-800 DEG C The weight-loss ratio spent in section is w₈₀₀, the weight-loss ratio in 400-500 DEG C of temperature range is w₅₀₀, w₅₀₀/w₈₀₀It is preferred that in 0.01- In the range of 0.5, more preferably in the range of 0.02-0.2, further preferably 0.15 or less.Thus what is prepared contains hetero atom Nano-carbon material shows that better catalytic effect can obtain more when being especially used as the catalyst of hydrocarbons dehydrogenation reaction Good catalysis reaction effect.

In a kind of more preferably embodiment of the present 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 100-200m²/g；Institute It is w to state weight-loss ratio of the multi-walled carbon nanotube in 400-800 DEG C of temperature range₈₀₀, in 400-500 DEG C of temperature range Weight-loss ratio is w₅₀₀, w₅₀₀/w₈₀₀It is preferred that in the range of 0.01-0.5, more preferably in the range of 0.02-0.2, further preferably It is 0.15 or less.

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 that can realize sealing and heating, such as autoclave.

According to the method for the present invention, can also include solid matter being isolated from mixture obtained by the reaction, and will divide The solid matter separated out is dried, to obtain the nano-carbon material containing hetero atom.

Common solid-liquid separating method may be used and isolate solid matter from mixture obtained by the reaction, such as centrifugation, Filtering and decantation one or more of combination.

The condition of the drying can be conventional selection, be can remove the volatile materials in the solid matter isolated It is accurate.Usually, the drying can carry out at a temperature of 50-200 DEG C, preferably be carried out at a temperature of 80-180 DEG C, 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. Usually, the duration of the drying can be 0.5-48 hours, preferably 3-24 hours, more preferably 4-12 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 content in raw material nano carbon material can be effectively improved, while will not be right The structural form generation of raw material nano carbon material significantly affects.

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 is will be according to the nano-carbon material containing hetero atom of the first aspect of the present invention or according to third of the present invention side Prepared by nano-carbon material containing hetero atom in face is roasted.

The roasting can carry out under normal conditions.Preferably, the roasting carries out at a temperature of 250-500 DEG C. It is highly preferred that the roasting carries out at a temperature of 300-450 DEG C.The duration of the roasting can be according to the temperature of roasting It is selected.Usually, the duration of the roasting can be 1-24 hours, and preferably 2-12 hours, more preferably 3-8 was small When.The roasting can carry out in oxygen-containing atmosphere, can also be carried out in the atmosphere formed by inert gas.It is described oxygenous Atmosphere can be air atmosphere；Can also be the mixed atmosphere that oxygen and inert gas are mixed to form, in the mixed atmosphere, oxygen Content can be 0.1-22 volumes %.The inert gas can include but is not limited to nitrogen and/or rare gas, described dilute It can be argon gas and/or helium to have gas.Angularly consider from convenience and cost, it is preferable that the roasting is in oxygen-containing atmosphere It is carried out in (such as air atmosphere).

Nano-carbon material containing hetero atom according to the present invention or the nano-sized carbon containing hetero atom prepared by the method for the present 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 the method for the present invention Material can be directly used as catalyst, can also be used in the form of preformed catalyst.The preformed catalyst can contain root Nano-carbon material containing hetero atom and glue prepared by the nano-carbon material containing hetero atom according to the present invention or the method by the present invention Tie agent.The binder can be selected according to the specifically used occasion of the preformed catalyst, disclosure satisfy that 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, usually, 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 %.

Application according to the present invention, the nano-carbon material containing hetero atom are used directly for hydrocarbon dehydrogenation reaction, can also 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.

Hydrocarbon dehydrogenation reaction method according to the present invention, the nano-carbon material containing hetero atom are used directly for connecing with hydrocarbon It touches, for being contacted with hydrocarbon after the nano-carbon material containing hetero atom can also being molded.

Hydrocarbon dehydrogenation reaction method according to the present invention can carry out dehydrogenation to a plurality of types of hydrocarbon, to obtain unsaturation Hydrocarbon, such as alkene.According to the method for the present invention particularly suitable for carrying out dehydrogenation to alkane, to obtain alkene.

According to the method for the present invention, the hydrocarbon is preferably alkane, such as C₂-C₁₂Alkane.Specifically, the hydrocarbon can be but Be not limited to ethane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- second Base pentane, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- dimethyl pentanes, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- front threes Base pentane, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4- dimethyl heptanes, 3- ethyl heptanes, 4- ethyl heptanes, 2, 3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- trimethyl cyclohexanes, 2,2,3- trimethyl cyclohexanes, 2,2,4- front threes Base hexane, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyl cyclohexanes, 2,4,4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- methyl -4- ethyl hexanes, 3,3- diethylpentanes, 1- methyl - 2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- ethyl cyclohexanes, n-propyl hexamethylene, isopropyl hexamethylene Alkane, trimethyl-cyclohexane (include the various isomers of trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- front threes Butylcyclohexane, 1,2,5- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes), n-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyls octane, 4- ethyls octane, 2, 3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethylheptanes, 2,4,5- trimethylheptanes, 2,4,6- front threes Base heptane, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- trimethylheptanes, 2,2,6- trimethylheptanes, 2, 3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 2- methyl -4- ethyl heptanes, 2- methyl -5- Ethyl heptane, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyl heptanes, 4- methyl -4- ethyls Heptane, 4- propyl heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- diethylpentanes, vinylbenzene, 1- In phenyl-propane, 2- phenyl-propanes, 1- phenyl butanes, 2- phenyl butanes, 1- phenyl pentanes, 2- phenyl pentanes and 3- phenyl pentanes A combination of one or more.

It is highly preferred that the hydrocarbon is one or more of propane, normal butane, iso-butane and vinylbenzene.Further Preferably, the hydrocarbon is normal butane.

Hydrocarbon dehydrogenation reaction method according to the present invention, the reaction can carry out under conditions of there are oxygen, can also It is carried out under conditions of there is no oxygen.Preferably, hydrocarbon dehydrogenation reaction method according to the present invention, under conditions of there are oxygen It carries out.When the method for the present invention carries out under conditions of there are oxygen, the dosage of oxygen can be conventional selection.Usually, 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 0.5- 2：1.

Hydrocarbon dehydrogenation reaction method according to the present invention, can by carrier gas by hydrocarbon and optional oxygen be sent into reactor with The haptoreaction of nano-carbon material containing hetero atom.The carrier gas can be it is common at reaction conditions will not with reactant and react The gas that product occurs chemical interaction and will not decompose, such as nitrogen, carbon dioxide, rare gas and vapor One or more of combination.The dosage of the carrier gas can be conventional selection.Usually, the content of carrier gas can be with 30-99.5 volume %, preferably 50-99 volumes %, more preferably 70-98 volumes %.

The temperature of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be conventional selection, to be enough that hydrocarbon is made to send out Subject to raw dehydrogenation reaction.Usually, the contact can carry out at a temperature of 200-650 DEG C, preferably in 300-600 DEG C of temperature Degree is lower to carry out, and is more preferably carried out at a temperature of 350-550 DEG C, further preferably in 400-450 DEG C of temperature when such as hydrocarbon being butane Degree is lower to 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, can indicate continuing for contact with volume space velocity when the gas of charging Time.Usually, 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 100-400h^-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 companies It is tested on the ESCALab250 type x-ray photoelectron spectroscopies for having Thermo Avantage V5.926 softwares, excitaton source For monochromatization Al K α X-rays, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, analysis test When base vacuum be 6.5 × 10^-10Mbar, the peaks C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Data processing is carried out on Avantage softwares, 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 analyzers, 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 types N of Micromertrics companies of the U.S.₂ Physical adsorption appearance measurement the specific area.Raw material nano carbon material is analyzed using the high-resolution-ration transmission electric-lens of FEI Co. of U.S. production And the microscopic appearance of the nano-carbon material containing hetero atom.

Embodiment 1-19 is for illustrating nano-carbon material containing hetero atom according to the present invention and preparation method thereof.

Embodiment 1

(1) using 20g as multi-walled carbon nanotube (the specific surface area 136m of raw material nano carbon material²/ g, oxygen atom content For 0.3 weight %, the total content of remaining nonmetallic heteroatoms (nitrogen-atoms, phosphorus atoms and sulphur atom) outside oxygen atom is 0.03 Weight %, metallic atom total content are 0.1 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w₈₀₀, in 400-500 Weight-loss ratio in DEG C temperature range is w₅₀₀, w₅₀₀/w₈₀₀It is 0.12, is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) point It dissipates in deionized water, is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes：Frequency is 40kHz, and the time is 0.5 hour.Then hydrogen peroxide is added, is uniformly mixed, to obtain aqueous dispersions.Wherein, hydrogen peroxide is bis- with 30 weight % The form of oxygen water provides, by raw material nano carbon material：Hydrogen peroxide：H₂The weight ratio of O is 1：5：25 ratio feeds intake.

(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 150 DEG C of temperature Under, it reacts 24 hours at autogenous pressures.After reaction, it waits for that the temperature in autoclave is cooled to room temperature, opens reaction Reaction mixture is filtered and is washed, and collects solid matter by kettle.By the solid matter being collected into, in normal pressure, (1 standard is big Air pressure, similarly hereinafter), 6 hours dry at a temperature of 120 DEG C, nano-carbon material containing hetero atom is obtained, this contains hetero atom nano-carbon material Composition, specific surface area and w₅₀₀/w₈₀₀It is listed in table 1.

Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing hetero atom prepared, and Fig. 2 is the multi wall as raw material The transmission electron microscope photo of carbon nanotube.It can be seen that the microscopic pattern of the nano-carbon material containing hetero atom from Fig. 1 and Fig. 2 Well, it is little to show that reaction process influences the structure of the nano-carbon material containing hetero atom.

Comparative example 1

Aqueous dispersions same as Example 1 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 150 DEG C, back flow reaction 24 hours under normal pressure.After reaction, wait for that the temperature in three-necked flask is down to After room temperature, reaction mixture is filtered and is washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 It is 6 hours dry at a temperature of DEG C, obtain nano-carbon material containing hetero atom.

Composition, specific surface area and the w of the nano-carbon material containing hetero atom prepared₅₀₀/w₈₀₀It is listed in table 1.

Comparative example 2

Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, step (1) obtains Aqueous dispersions are free of hydrogen peroxide.

Comparative example 3

Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), peroxide Change the H of hydrogen equimolar amounts₂SO₄Instead of.

Comparative example 4

Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), peroxide Change the KMnO of hydrogen equimolar amounts₄Instead of.

Comparative example 5

Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, step does not make in (1) With hydrogen peroxide, in step (2), the ozone of equimolar amounts is passed through in the forward direction autoclave for closing autoclave.

Comparative example 6

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 70 DEG C, at autogenous pressures Reaction 24 hours.

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 materials 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-atoms, phosphorus are former for remaining nonmetallic heteroatoms outside oxygen atom Son and sulphur atom) total content be 0.02 weight %, metallic atom total content be 0.08 weight %.

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 110 DEG C, at autogenous pressures Reaction 24 hours.

Embodiment 4

Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), raw material Nano-carbon material：Hydrogen peroxide：H₂The weight ratio of O is 1：0.5：25.

Embodiment 5

Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), peroxide The tert-butyl hydroperoxide for changing hydrogen equimolar amounts replaces.

Embodiment 6

Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), peroxide The cumyl peroxide for changing hydrogen equimolar amounts replaces.

Embodiment 7

(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 %, the total content of remaining nonmetallic heteroatoms (nitrogen-atoms, phosphorus atoms and sulphur atom) outside oxygen atom is 0.05 Weight %, metallic atom total content are 0.1 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w₈₀₀, in 400- Weight-loss ratio in 500 DEG C of temperature range is w₅₀₀, w₅₀₀/w₈₀₀It is 0.07, is purchased from the limited public affairs of Chinese Academy of Sciences's Chengdu organic chemistry Department) it is scattered in deionized water, it is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes：Frequency is 60kHz, when Between be 1 hour.Then hydrogen peroxide is added to be uniformly mixed, to obtain aqueous dispersions.Wherein, hydrogen peroxide and 40 weight % water The form of solution provides, by raw material nano carbon material：Hydrogen peroxide：H₂The weight ratio of O is 1：1.5：10 ratio feeds intake.

(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 200 DEG C of temperature Under, it reacts 8 hours at autogenous pressures.After reaction, it waits for that the temperature in autoclave is cooled to room temperature, opens reaction Reaction mixture is filtered by kettle, and collects solid matter.By the solid matter being collected at a temperature of normal pressure, 140 DEG C It is 6 hours dry, nano-carbon material containing hetero atom is obtained, this contains the composition of hetero atom nano-carbon material, specific surface area and w₅₀₀/ w₈₀₀It is listed in table 1.

Embodiment 8

Nano-carbon material containing hetero atom is prepared using method same as Example 7, unlike, in step (2), will To aqueous dispersions be placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 240 DEG C, at autogenous pressures Reaction 8 hours.

Embodiment 9

Nano-carbon material containing hetero atom is prepared using method same as Example 7, unlike, in step (1), as The specific surface area of the multi-walled carbon nanotube (being purchased from Shandong great Zhan nano materials Co., Ltd) of raw material nano carbon material is 103m²/ G, w₅₀₀/w₈₀₀It is 0.23, oxygen atom content is 1.1 weight %, remaining nonmetallic heteroatoms (nitrogen-atoms, phosphorus outside oxygen atom Atom and sulphur atom) total content be 0.04 weight %, metallic atom total content be 1.6 weight %.

Embodiment 10

Nano-carbon material containing hetero atom is prepared using method same as Example 7, unlike, in step (1), by original Expect nano-carbon material：Hydrogen peroxide：H₂The weight ratio of O is 1：0.8：10 ratio feeds intake.

Comparative example 7

Nano-carbon material containing hetero atom is prepared using method same as Example 7, unlike, it is water-dispersed by what is obtained Liquid is placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 280 DEG C, is reacted 8 hours at autogenous pressures.

Embodiment 11

(1) using 20g as multi-walled carbon nanotube (the specific surface area 175m of raw material nano carbon material²/ g, oxygen atom content For 0.3 weight %, the total content of remaining nonmetallic heteroatoms (nitrogen-atoms, phosphorus atoms and sulphur atom) outside oxygen atom is 0.03 Weight %, metallic atom total content are 0.1 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w₈₀₀, in 400-500 Weight-loss ratio in DEG C temperature range is w₅₀₀, w₅₀₀/w₈₀₀It is 0.15, is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) point It dissipates in deionized water, is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes：Frequency is 14kHz, and the time is 0.5 hour.Then hydrogen peroxide is added to be uniformly mixed, to obtain aqueous dispersions.Wherein, hydrogen peroxide is water-soluble with 35 weight % The form of liquid provides, by raw material nano carbon material：Hydrogen peroxide：H₂The weight ratio of O is 1：7.5：30 ratio feeds intake.

(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 170 DEG C of temperature Under, it reacts 36 hours at autogenous pressures.After reaction, it waits for that the temperature in autoclave is cooled to room temperature, opens reaction Reaction mixture is filtered and is washed, and collects solid matter by kettle.By the solid matter being collected into normal pressure, 120 DEG C At a temperature of after dry 12 hours, obtain nano-carbon material containing hetero atom, this contains the composition of hetero atom nano-carbon material, specific surface area And w₅₀₀/w₈₀₀It is listed in table 1.

Embodiment 12

Nano-carbon material containing hetero atom prepared by embodiment 1 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Comparative example 8

Nano-carbon material containing hetero atom prepared by comparative example 1 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Comparative example 9

Nano-carbon material containing hetero atom prepared by comparative example 2 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Comparative example 10

Nano-carbon material containing hetero atom prepared by comparative example 3 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Comparative example 11

Nano-carbon material containing hetero atom prepared by comparative example 4 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Comparative example 12

Nano-carbon material containing hetero atom prepared by comparative example 5 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Comparative example 13

Nano-carbon material containing hetero atom prepared by comparative example 6 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Embodiment 13

Nano-carbon material containing hetero atom prepared by embodiment 2 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Embodiment 14

Nano-carbon material containing hetero atom prepared by embodiment 3 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Embodiment 15

Nano-carbon material containing hetero atom prepared by embodiment 4 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Embodiment 16

Nano-carbon material containing hetero atom prepared by embodiment 5 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Embodiment 17

Nano-carbon material containing hetero atom prepared by embodiment 6 roasts 5 hours at a temperature of 380 DEG C in air atmosphere.

Embodiment 18

Nano-carbon material containing hetero atom prepared by embodiment 7 roasts 3 hours at a temperature of 450 DEG C in air atmosphere.

Embodiment 19

Nano-carbon material containing hetero atom prepared by embodiment 11 roasts 4 hours at a temperature of 420 DEG C in air atmosphere.

Embodiment 20-38 is used to illustrate application and the hydrocarbon dehydrogenation reaction of the nano-carbon material according to the present invention containing hetero atom Method.

Embodiment 20-30

The nano-carbon material containing hetero atom that 0.2g (admission space 1.5mL) embodiment 1-11 is obtained respectively is as catalysis Agent is seated in universal fixed bed miniature quartz pipe reactor, and two end seal of miniature quartz pipe reactor has quartz sand, Under the conditions of 0.1MPa and 440 DEG C, by gas (a concentration of 1.98 volume % of normal butane, normal butane and oxygen containing hydrocarbon and oxygen Gas molar ratio 0.5：1, Balance Air is nitrogen, accounts for surplus) with total volume air speed for 200h^-1It is passed through in reactor and is reacted, even The composition for the reaction mixture that continuous monitoring is exported from reactor, and calculate n-butane conversion, total olefin selectivity and 1- fourths Alkene selectivity, the results are shown in Table 2 within 3 hours and 24 hours for reaction.

Comparative example 14-20

It is reacted using method identical with embodiment 20-30, unlike, use comparative example 1-7 to prepare respectively Nano-carbon material containing hetero atom is as catalyst.Reaction result is listed in table 2.

Comparative example 21

It is reacted using method identical with embodiment 20-30, unlike, use raw material same as Example 1 Nano-carbon material is as catalyst.Reaction result is listed in table 2.

Comparative example 22

It is reacted using method identical with embodiment 20-30, unlike, use raw material same as Example 7 Nano-carbon material is as catalyst.Reaction result is listed in table 2.

Embodiment 31-38

It is reacted using method identical with embodiment 20-30, unlike, it is prepared respectively using embodiment 12-19 Nano-carbon material containing hetero atom as catalyst.Reaction result is listed in table 3.

Comparative example 23-28

It is reacted using method identical with embodiment 20-30, unlike, use comparative example 8-13 to prepare respectively Nano-carbon material containing hetero atom is as catalyst.Reaction result is listed in table 3.

Comparative example 29

It is reacted using method identical with embodiment 20-30, unlike, catalyst is will be same as Example 1 Raw material nano carbon material roasted 5 hours in air atmosphere at a temperature of 380 DEG C obtained from.Reaction result is in table 3 It lists.

Comparative example 30

It is reacted using method identical with embodiment 20-30, unlike, catalyst is will be same as Example 7 Raw material nano carbon material roasted 3 hours in air atmosphere at a temperature of 450 DEG C obtained from.Reaction result is in table 3 It lists.

Table 2

Table 3

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 can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, 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 of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

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

1. a kind of nano-carbon material containing hetero atom, this contains hetero atom nano-carbon material and contains C element and O elements, 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 elements is 6-12 weight %, and the content of C element is 88-94 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 I_O ^c, the amount of the O elements determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is I_O ^e, I_O ^c/I_O ^eIn the range of 0.3-1；

The amount of the C element determined by the peak within the scope of 288.6-288.8eV in x-ray photoelectron spectroscopy is I_C ^c, by X-ray photoelectricity The amount for the C element that peak in sub- power spectrum within the scope of 286.0-286.2eV determines is I_C ^e, I_C ^c/I_C ^eIn the range of 0.4-2；

The preparation method of the nano-carbon material containing hetero atom includes that one kind being dispersed with raw material nano carbon material and at least one mistake The aqueous dispersions of oxide are reacted in closed container, and in reaction process, the temperature of the aqueous dispersions is maintained at 100- In the range of 250 DEG C, raw material nano carbon material：The weight ratio of peroxide is 1：In the range of 0.5-50, raw material nano carbon materials Material：H₂The weight ratio of O is 1：In the range of 2-50, the peroxide is selected from organic peroxy shown in hydrogen peroxide and Formulas I Object,

In Formulas I, R₁And R₂It each is selected from H, C₄-C₁₂Alkyl, C₆-C₁₂Aryl, C₇-C₁₂Aralkyl andAnd R₁ And R₂It is asynchronously H, R₃For C₄-C₁₂Linear or branched alkyl group or C₆-C₁₂Aryl.

2. nano-carbon material containing hetero atom according to claim 1, wherein I_O ^c/I_O ^eIn the range of 0.4-0.95；I_C ^c/ I_C ^eIn the range of 0.5-1.5.

3. nano-carbon material containing hetero atom according to claim 2, wherein I_O ^c/I_O ^eIn the range of 0.5-0.8.

4. nano-carbon material containing hetero atom according to claim 3, wherein I_O ^c/I_O ^eIn the range of 0.6-0.7.

5. nano-carbon material containing hetero atom according to claim 2, wherein I_C ^c/I_C ^eIn the range of 0.7-1.2.

6. nano-carbon material containing hetero atom according to claim 5, wherein I_C ^c/I_C ^eIn the range of 0.8-1.

7. nano-carbon material containing hetero atom according to claim 6, wherein I_C ^c/I_C ^eIn the range of 0.85-0.95.

8. nano-carbon material containing hetero atom according to claim 1, 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 60-98 weight %；By the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The content of determining C element is 2-40 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 70-96 weight %；By the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The content of determining C element is 4-30 weight %.

10. nano-carbon material containing hetero atom according to claim 9, 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 80-95 weight %；By the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The content of determining C element is 5-20 weight %.

11. nano-carbon material containing hetero atom according to claim 1, 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 elements is 7-11 weight %, and the content of C element is 89-93 weight %.

12. according to the nano-carbon material containing hetero atom described in any one of claim 1-11, wherein this contains hetero atom nanometer Carbon material is carbon nanotube containing hetero atom.

13. nano-carbon material containing hetero atom according to claim 12, wherein it is containing miscellaneous that this, which contains hetero atom nano-carbon material, Atom multi-walled carbon nanotube.

14. nano-carbon material containing hetero atom according to claim 13, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 50-500m²/g。

15. nano-carbon material containing hetero atom according to claim 14, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 80-300m²/g。

16. nano-carbon material containing hetero atom according to claim 15, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 90-200m²/g。

17. nano-carbon material containing hetero atom according to claim 12, 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.

18. nano-carbon material containing hetero atom according to claim 17, wherein w₅₀₀/w₈₀₀In the range of 0.02-0.2.

19. a kind of preparation method of nano-carbon material containing hetero atom, this method includes that one kind being dispersed with raw material nano carbon material It is reacted in closed container with the aqueous dispersions of at least one peroxide, in reaction process, the temperature of the aqueous dispersions Degree is maintained in the range of 100-250 DEG C, raw material nano carbon material：The weight ratio of peroxide is 1：In the range of 0.5-50, Raw material nano carbon material：H₂The weight ratio of O is 1：In the range of 2-50, the duration of the reaction was at 0.5-144 hours In range；

The peroxide is selected from organic peroxide shown in hydrogen peroxide and Formulas I,

20. according to the method for claim 19, wherein raw material nano carbon material：The weight ratio of peroxide is 1：1-40 In the range of.

21. according to the method for claim 19, wherein raw material nano carbon material：H₂The weight ratio of O is 1：The range of 5-40 It is interior.

22. according to the method for claim 21, wherein raw material nano carbon material：H₂The weight ratio of O is 1：The range of 10-30 It is interior.

23. according to the method for claim 19, wherein the peroxide is selected from hydrogen peroxide, tert-butyl hydroperoxide And cumyl peroxide.

24. according to the method described in any one of claim 19-23, wherein in reaction process, the temperature of the aqueous dispersions Degree is maintained in the range of 120-220 DEG C.

25. according to the method for claim 24, wherein in reaction process, the temperature of the aqueous dispersions is maintained at 150- In the range of 200 DEG C.

26. according to the method for claim 19, wherein the duration of the reaction is in the range of 2-72 hours.

27. according to the method for claim 26, wherein the duration of the reaction is in the range of 5-40 hours.

28. according to the method described in any one of claim 19-23, wherein O elements in the raw material nano carbon material Content is not higher than 1 weight %.

29. according to the method for claim 28, wherein in the raw material nano carbon material content of O elements be not higher than 0.5 weight %.

30. according to the method described in any one of claim 19-23, wherein the raw material nano carbon material is carbon nanometer Pipe.

31. according to the method for claim 30, wherein the raw material nano carbon material is multi-walled carbon nanotube.

32. according to the method for claim 31, wherein the specific surface area of the multi-walled carbon nanotube is 20-500m²/g。

33. according to the method for claim 32, wherein the specific surface area of the multi-walled carbon nanotube is 50-3000m²/g。

34. according to the method for claim 33, wherein the specific surface area of the multi-walled carbon nanotube is 100-200m²/g。

35. according to the method for claim 31, 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.

36. according to the method for claim 35, wherein w₅₀₀/w₈₀₀In the range of 0.02-0.2.

37. according to the method described in any one of claim 19-23, wherein this method further includes from obtained by the reaction mixed It closes in object and isolates solid matter, and the solid matter isolated is dried.

38. according to the method for claim 37, wherein the drying carries out at a temperature of 50-200 DEG C；The drying Duration be 0.5-48 hours.

39. according to the method for claim 38, wherein the drying carries out at a temperature of 80-180 DEG C.

40. according to the method for claim 39, wherein the drying carries out at a temperature of 100-150 DEG C.

41. according to the method for claim 38, wherein the duration of the drying is 3-24 hours.

42. according to the method for claim 41, wherein the duration of the drying is 4-12 hours.

43. nano-carbon material containing hetero atom prepared by a kind of method by described in any one of claim 19-42.

44. a kind of nano-carbon material containing hetero atom, it is by any one of claim 1-18 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 43 is roasted and is made 's.

45. nano-carbon material containing hetero atom according to claim 44, wherein temperature of the roasting at 250-500 DEG C Lower progress；The duration of the roasting is 1-24 hours.

46. nano-carbon material containing hetero atom according to claim 45, wherein temperature of the roasting at 300-450 DEG C Lower progress.

47. nano-carbon material containing hetero atom according to claim 45, wherein the duration of the roasting is that 2-12 is small When.

48. nano-carbon material containing hetero atom according to claim 47, wherein the duration of the roasting is that 3-8 is small When.

49. catalysis of the nano-carbon material containing hetero atom as hydrocarbon dehydrogenation reaction described in any one of claim 1-18 and 43 The application of agent.

50. application according to claim 49, wherein the dehydrogenation reaction carries out in the presence of oxygen.

51. the application according to claim 49 or 50, wherein the hydrocarbon is alkane.

52. application according to claim 51, wherein the hydrocarbon is C₂-C₁₂Alkane.

53. application according to claim 52, wherein the hydrocarbon is normal butane.

54. 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, the nano-carbon material containing hetero atom described in any one of hydrocarbon and claim 1-18 and 43 is contacted.

55. method according to claim 54, wherein the hydrocarbon is alkane.

56. method according to claim 55, wherein the hydrocarbon is C₂-C₁₂Alkane.

57. method according to claim 56, wherein the hydrocarbon is normal butane.