CN105817245B - 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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CN105817245B
CN105817245B CN201510701000.9A CN201510701000A CN105817245B CN 105817245 B CN105817245 B CN 105817245B CN 201510701000 A CN201510701000 A CN 201510701000A CN 105817245 B CN105817245 B CN 105817245B
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carbon material
hetero atom
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CN105817245A (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20—Carbon compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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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 4-12 weight %, the N element of 2-6 weight % and 82-94 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 0.5-1, 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 0.8-1.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.
Oxygen atom can be introduced in nano-carbon material by carrying out oxidation processes realization to nano-carbon material, to increase The content of oxygen-containing functional group in nano-carbon material.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or it is strong Oxidizing solution (such as H2O2、KMnO4) in carry out back flow reaction, can also be assisted while back flow reaction carry out microwave heating Or sonic oscillation, to enhance the effect of oxidation reaction.It can but carry out back flow reaction in strong acid and/or strong oxidizing solution Can have an adverse effect to the skeleton structure of nano-carbon material, or even destroy the skeleton structure of nano-carbon material.Such as: it will receive Rice carbon material carries out back flow reaction in nitric acid, although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, Nano-carbon material is easily caused to be cut off and/or obviously increase the defects of graphite network structure position, to reduce nano carbon material The performance of material, such as thermal stability.In addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, to introduce oxygen original The introduction volume of the period of the day from 11 p.m. to 1 a.m, oxygen atom is high to the dependence of operation condition, and fluctuation range is wider.
When introducing nitrogen-atoms in nano-carbon material, according to nitrogen-atoms, locating chemical environment is not in nano-carbon material Together, nitrogen-atoms is usually divided into chemical nitrogen and structure nitrogen.Chemical nitrogen mainly appears in material in the form of surface functional group Surface, such as amino or nitrosyl radical surface nitrogen-containing functional group.Structure nitrogen refer to skeleton structure into nano-carbon material with The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly include graphite mould nitrogen (that is,), pyridine type nitrogen (that is,) and Pyrroles's type nitrogen (that is,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen It is unsaturated nitrogen atom with pyrroles's type nitrogen, while replacing carbon atom, often will cause the missing for closing on carbon atom, form defect Position.
Can by introduced in nano-carbon material synthesis process nitrogenous functional atmosphere (such as ammonia, nitrogen, urea, Melamine), nitrogen is introduced into nano carbon material simultaneously in the synthesis process of nano-carbon material using high temperature and/or high pressure In the skeleton structure of material and/or surface；It can also be by the way that nano-carbon material to be placed in nitrogenous functional atmosphere (such as ammonia, nitrogen Gas, urea, melamine) in, nitrogen is introduced into the surface of nano-carbon material using high temperature and/or high pressure.High temperature and/or For high pressure although can form structure nitrogen in nano-carbon material, the type of nitrogen containing species depends on reaction condition, not easily-controllable System；Also, the different types of nitrogen containing species so generated are unevenly distributed on the surface of nano-carbon material, lead to nitrogenous nanometer The performance of carbon material is unstable.It then can also be reacted with amine, by the way that nano-carbon material is carried out oxidation processes thus in nanometer Carbon material surface introduces nitrogen-atoms, and the nitrogen-atoms so introduced is essentially chemical nitrogen.
Although the research of doping vario-property and its catalytic performance in relation to nano-carbon material achieves many progress, for Some of which basic problem is not built consensus yet, is still needed to doping vario-property nano-carbon material and preparation method thereof and catalysis Performance is furtherd investigate.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of nano-carbon material containing 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 4-12 weight %, and the content of N element is 2-6 weight %, and the content of C element is 82-94 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 element amount be IO c, the amount of the O element determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is IO e, IO c/IO eIn the range of 0.5-1；
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 0.8-1.
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 being dispersed with raw material nano carbon material, at least one nitrogenous compound and at least one peroxide for a kind of Aqueous dispersions are reacted in closed container, and the nitrogenous compound is selected from NH3, hydrazine and urea, in reaction process, the water The temperature of dispersion liquid is maintained in the range of 80-220 DEG C.
According to the third aspect of the present invention, the present invention provides a kind of method systems by the second aspect according to the present invention Standby nano-carbon material containing hetero atom.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing hetero atom, this contains hetero atom Nano-carbon material is to roast the nano-carbon material containing hetero atom in terms of first aspect according to the present invention or third Prepared by.
According to the fifth aspect of the present invention, the present invention provides the nanometers containing hetero atom of first aspect according to the present invention Carbon material, the according to the present invention nano-carbon material containing hetero atom in terms of third or according to the fourth aspect of the present invention Application of the nano-carbon material containing hetero atom as the catalyst of hydrocarbon dehydrogenation reaction.
According to the sixth aspect of the invention, the present invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, is deposited Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with first aspect according to the present invention containing miscellaneous original Sub- nano-carbon material, the according to the present invention nano-carbon material containing hetero atom of third aspect or according to the present invention the 4th side The nano-carbon material containing hetero atom in face contacts.
The preparation method of the nano-carbon material according to the present invention containing hetero atom can not only steadily regulate and control and/or improve to receive Content of heteroatoms in rice carbon material, while small, the nano carbon material containing hetero atom of preparation is influenced on the structure of nano-carbon material itself Material has stable performance.Nano-carbon material containing hetero atom according to the present invention shows good in the dehydrogenation reaction of hydrocarbons Good catalytic performance, can significantly improve feed stock conversion and selectivity of product.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing hetero atom prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo for the raw material nano carbon material that embodiment 1 uses.
Specific embodiment
In the present invention, nano-carbon material refers to that dispersed phase scale at least one dimension is less than the carbon material of 100nm.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing hetero atom, this contains hetero atom Nano-carbon material contains C element, O element and N element.
Nano-carbon material containing hetero atom according to the present invention, on the basis of the total amount of the nano-carbon material containing hetero atom and with Element meter, the content of O element are 4-12 weight %, preferably 4-10 weight %, more preferably 5-9 weight %, further preferably For 5.5-8 weight %；The content of N element be 2-6 weight %, preferably 2.2-5.8 weight %, more preferably 2.5-5 weight %, Further preferably 3-4.5 weight %；The content of C element be 82-94 weight %, preferably 84.2-93.8 weight %, more preferably For 86-92.5 weight %, further preferably 87.5-91.5 weight %.Wherein, the content of each element uses x-ray photoelectron The measurement of power spectrum (XPS) method, the content of element is determined by the corresponding area of 1s electronics spectral peak；Sample is before testing in 150 DEG C of temperature Degree and the pressure of 1 normal atmosphere are 3 hours dry in helium atmosphere.
In the present invention, X-ray photoelectron spectroscopic analysis is in Thermo Scientific company equipped with Thermo It is tested on the ESCALab250 type x-ray photoelectron spectroscopy of Avantage V5.926 software, excitaton source is monochromatization Al K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, base vacuum when analysis test It is 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage software Upper carry out data processing carries out quantitative analysis using sensitivity factor method in analysis module.
Nano-carbon material containing hetero atom according to the present invention, 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 eIn the range of 0.5-1, preferably in the range of 0.5-0.95, more preferably In the range of 0.6-0.8.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, the total amount with C element in the nano-carbon material containing hetero atom are Benchmark, the content of the C element determined by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy (that is, graphite mould carbon) It can be 70-92 weight %, preferably 75-85 weight %；By within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The total content for the C element that peak determines can be 8-30 weight %, preferably 15-25 weight %.In the present invention, by X-ray photoelectricity The area A of C1s spectral peak in sub- power spectrumC 1C1s spectral peak in x-ray photoelectron spectroscopy is divided into two groups by the total amount for determining C element Peak, i.e., spectral peak (correspond to graphite mould carbon species) within the scope of 284.7-284.9eV and within the scope of 286.0-288.8eV Spectral peak (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 The area of spectral peak within the scope of 286.0-288.8eV is denoted as AC 3, by within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy Peak determine C element content=AC 2/AC 1, determined by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy C element total content=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 0.3-1, preferably in the model of 0.4-0.95 In enclosing, more preferably in the range of 0.5-0.8.In the present invention, by x-ray photoelectron spectroscopy in 286.0-288.8eV range Interior spectral peak (corresponding to agraphitic carbon species) is further divided into two groups of peaks, i.e., the spectral peak within the scope of 286.0-286.2eV (corresponding to hydroxyl and ether type carbon species) and the spectral peak within the scope of 288.6-288.8eV (correspond to carboxyl, acid anhydride and ester type carbon Species), the area of the spectral peak within the scope of 286.0-286.2eV is denoted as AC 4, by the spectral peak within the scope of 288.6-288.8eV Area be denoted as AC 5, IC c/IC e=AC 5/AC 4。
Nano-carbon material containing hetero atom according to the present invention determines that this contains hetero atom nano-sized carbon by x-ray photoelectron spectroscopy The total amount of N element in material is IN t, the N element that is determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy Amount be IN c, IN c/IN tIn the range of 0.8-1, preferably in the range of 0.8-0.95.It is according to the present invention to be received containing hetero atom Rice carbon material, the N element determined by the peak within the scope of 400.6-401.5eV in x-ray photoelectron spectroscopy (that is, graphite mould nitrogen) contain It measures lower or even is free of.Generally, in nano-carbon material containing hetero atom according to the present invention, by x-ray photoelectron spectroscopy The amount for the N element that peak within the scope of 400.6-401.5eV determines is IN g, IN g/IN tFor not higher than 0.2, generally in the model of 0-0.2 In enclosing, 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 Stating can be for single-walled carbon nanotube containing hetero atom, double-walled carbon nano-tube containing hetero atom and containing hetero atom containing heteroatomic carbon nanotube The combination of one or more of multi-walled carbon nanotube.Nano-carbon material containing hetero atom according to the present invention, preferably contains Hetero atom multi-walled carbon nanotube.
Nano-carbon material containing hetero atom according to the present invention, it is preferable that the ratio table of the multi-walled carbon nanotube containing hetero atom Area is 50-500m2/ g can be further improved the catalytic performance of the nano-carbon material containing hetero atom, especially as hydrocarbon in this way The catalytic performance of the catalyst of substance dehydrogenation reaction.The specific surface area of the multi-walled carbon nanotube containing hetero atom is more preferably 80- 300m2/ g, further preferably 90-200m2/ g is still more preferably 100-150m2/g.In the present invention, specific surface area is by nitrogen The attached BET method measurement of aspiration.
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 in 400 DEG C of the at a temperature of matter that measures Amount loss rate, W800For in 800 DEG C of the at a temperature of mass loss rate that measures, W500For in 500 DEG C of the at a temperature of quality that measures Loss late；The weight-loss ratio is measured in air atmosphere using thermogravimetric analyzer, 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 preferred embodiment of the invention, it is more preferably to contain hetero atom for the nano-carbon material containing hetero atom Wall carbon nano tube, which is 50-500m2/ g, preferably 80-300m2/ g, it is more excellent It is selected as 90-200m2/ g, further preferably 100-150m2/g；Also, w500/w800In the range of 0.01-0.5, preferably exist In the range of 0.02-0.2.
Nano-carbon material containing hetero atom according to the present invention, such as sulphur atom and the other nonmetallic heteroatoms contents of phosphorus atoms It can be customary amount.Generally, in nano-carbon material containing hetero atom according to the present invention, its outside oxygen atom and nitrogen-atoms The total amount of its nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) can be 0.5 weight % hereinafter, preferably 0.2 weight % with Under.Nano-carbon material containing hetero atom according to the present invention can also contain remaining in nano-carbon material preparation process on a small quantity Metallic atom, these remaining metallic atoms are typically derived from the catalyst used when preparing nano-carbon material, these are remaining The content of metallic atom is 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 peroxide 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 peroxide refers to the compound for containing-O-O- key 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 not simultaneously 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 including hexyl), cyclohexyl, octyl (including The various isomers of octyl), nonyl (the various isomers including nonyl), decyl (the various isomers including decyl), 11 Alkyl (the various isomers including undecyl) and dodecyl (the various isomers 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.
Method according to the invention it is possible to be optimized according to type of the type of nitrogenous compound to peroxide.? In a kind of preferred embodiment, the nitrogenous compound is NH3, the peroxide is selected from hydrogen peroxide.Another excellent In the embodiment of choosing, the nitrogenous compound is hydrazine, and the peroxide is selected from tert-butyl hydroperoxide.It is preferred at another Embodiment in, the nitrogenous compound be urea, the peroxide be selected from cumyl hydroperoxide.
According to the method for the present invention, the dosage of the nitrogenous compound and the peroxide can be according to it is contemplated that raw material The content and type of the nitrogen and oxygen element that introduce in nano-carbon material are selected.It is finally preparing containing hetero atom Nano-carbon material is when being used as the catalyst of hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material: nitrogenous compound: peroxidating The weight ratio of object is 1:0.01-10:0.01-10, and the nano-carbon material containing hetero atom thus prepared is being used as hydrocarbon dehydrogenation reaction The catalytic effect further increased can be obtained when catalyst.It is highly preferred that raw material nano carbon material: nitrogenous compound: peroxidating The weight ratio of object is 1:0.05-3:0.02-5.It is further preferred that raw material nano carbon material: nitrogenous compound: peroxide Weight ratio is 1:0.1-0.5:0.1-1.
According to the method for the present invention, the molar ratio of the nitrogenous compound and the peroxide is preferably 1:0.001- 10, hetero atom more uniformly spreading on nano-carbon material surface in the nano-carbon material containing hetero atom thus prepared is being used as Also there is more excellent catalytic activity when the catalyst of hydrocarbon dehydrogenation reaction.The nitrogenous compound rubs with the peroxide You are than being more preferably 1:0.002-5, further preferably 1:0.05-2.
Method according to the invention it is possible to be selected according to dosage of the amount of raw material carbon nanomaterial to water.Preferably, Raw material nano carbon material: H2The weight ratio of O is 1:2-500, and when within the scope of the dosage of water being in this, nano-carbon material is being located Structural form retentivity during reason is more preferable, such as: when raw material nano carbon material is carbon nanotube, during processing substantially It is not cut off.Raw material nano carbon material: H2The weight ratio of O is more preferably 1:5-250, further preferably 1:15-50.Separately Outside, it can also be adjusted according to dosage of the type of nitrogenous compound and peroxide to water, so that the nitrogenous chemical combination Subject to object and peroxide can be dispersed in water.
It according to the method for the present invention, can also be according to the type of nitrogenous compound and peroxide, to nitrogenous compound And the type of peroxide optimizes, so that the nano-carbon material containing hetero atom of preparation is being used as urging for hydrocarbon dehydrogenation reaction Preferably catalysis reaction effect can be obtained when agent.
In a preferred embodiment, the nitrogenous compound is NH3, the peroxide be selected from hydrogen peroxide, Raw material nano carbon material: nitrogenous compound: the weight ratio of peroxide is 1:0.02-5:0.01-5, preferably 1:0.02-2.5: 0.1-5, more preferably 1:0.1-2:0.4-4.5, further preferably 1:0.2-0.5:0.5-1.In the preferred embodiment In, the molar ratio of nitrogenous compound and peroxide is preferably 1:0.02-2, more preferably 1:0.1-1.8, further preferably 1:1-1.5.In the preferred embodiment, raw material nano carbon material: H2The weight ratio of O is preferably 1:5-300, more preferably 1:10-250, further preferably 1:20-50.
In another preferred embodiment, the nitrogenous compound is hydrazine, and the peroxide is selected from tert-butyl mistake Hydrogen oxide, raw material nano carbon material: nitrogenous compound: the weight ratio of peroxide be 1:0.02-5:0.01-8, more preferably 1: 0.08-3:0.02-5, further preferably 1:0.1-0.5:0.1-1.In the preferred embodiment, nitrogenous compound and mistake The molar ratio of oxide is preferably 1:0.001-8, more preferably 1:0.003-6, further preferably 1:0.1-0.5.It is excellent at this In the embodiment of choosing, raw material nano carbon material: H2The weight ratio of O is preferably 1:5-300, more preferably 1:10-200, into one Step is preferably 1:40-60.
In another preferred embodiment, the nitrogenous compound is urea, and the peroxide is selected from peroxidating Hydrogen isopropylbenzene, raw material nano carbon material: nitrogenous compound: the weight ratio of peroxide be 1:0.02-5:0.01-3, preferably 1: 0.05-2:0.05-2, more preferably 1:0.2-0.5:0.1-1.In the preferred embodiment, nitrogenous compound and peroxidating The molar ratio of object is preferably 1:0.005-4, more preferably 1:0.05-2.In the preferred embodiment, raw material nano carbon materials Material: H2The weight ratio of O is preferably 1:5-300, more preferably 1:10-250, further preferably 1:10-50.
According to the method for the present invention, the condition of the reaction is to be enough to improve oxygen atom and nitrogen in raw material nano carbon material Subject to the content of atom.Preferably, in reaction process, the temperature of the aqueous dispersions is in the range of 80-220 DEG C.Described When the temperature of aqueous dispersions is within above range, the oxygen atom and nitrogen in raw material nano carbon material can not only be effectively improved Atom content, and the structural form of raw material nano carbon material will not be generated and be significantly affected.It is highly preferred that in reaction process, The temperature of the aqueous dispersions is in the range of 100-180 DEG C.The duration of the reaction can according to the temperature of reaction into Row selection, 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 in 20-50 hours models In enclosing.
Method according to the invention it is possible to form the aqueous dispersions using common various methods, such as can incite somebody to action Raw material nano carbon material is dispersed in water (preferably deionized water), and the nitrogenous compound and the peroxidating is then added Object, to obtain the aqueous dispersions.The nitrogenous compound and the peroxide, respectively can be with molten according to specific substance The form of liquid provides, and can also be provided, is not particularly limited in the form of pure material.In order to further increase raw material nano carbon materials The dispersion effect of material, while shortening the time of dispersion, raw material nano carbon material can be dispersed in using the method for sonic oscillation In water.The condition of the sonic oscillation can be conventional selection, and generally, the frequency of the sonic oscillation can be 10- 100kHz, the duration of the sonic oscillation can be 0.1-6 hours, preferably 0.5-2 hours.
According to the method for the present invention, the content of O element and N element is not particularly limited in the raw material nano carbon material, It can be conventional selection.Generally, the content of O element is not higher than 1.2 weight %, preferably in the raw material nano carbon material Not higher than 0.5 weight %；The content of N element is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably not Higher than 0.1 weight %, it is further preferably not higher than 0.05 weight %.According to the method for the present invention, the raw material nano carbon materials The total amount (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 may be used also according to the difference in source To contain some metallic elements, these metallic elements are typically derived from the catalyst used when preparing raw material nano carbon material, Content is generally in 2 weight % hereinafter, it is preferred that in 1 weight % hereinafter, more preferably below 0.5 weight %.
According to the method for the present invention, raw material nano carbon material can be carried out pre- before use using method commonly used in the art Processing (as washed), to remove some impurity of raw material nano carbon material surface；It can also directly be used without pretreatment, In embodiment disclosed by the invention, raw material nano carbon material is not pre-processed using preceding.
Method according to the invention it is possible to handle the nano-carbon material of various existing forms, received to improve this Oxygen atom and nitrogen atom content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon nanotube, graphite The combination of one or more of alkene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene. The carbon nanotube can be one or more of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube Combination.Preferably, the raw material nano carbon material is carbon nanotube, more preferably multi-walled carbon nanotube.
In a preferred embodiment, the raw material nano carbon material is multi-walled carbon nanotube, and the multi wall carbon is received The specific surface area of mitron is 20-500m2/ g, preferably 50-300m2/ g, more preferably 80-250m2/ g, further preferably 90- 150m2/g.When the specific surface area of the multi-walled carbon nanotube is within above range, finally obtained nanometer containing hetero atom Carbon material has better catalytic activity, especially when being used as the catalyst of dehydrogenation reaction of hydrocarbons, can obtain more preferable Catalytic effect.
When the raw material nano carbon material is multi-walled carbon nanotube, temperature of the multi-walled carbon nanotube at 400-800 DEG C The weight-loss ratio spent in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that in 0.01- In the range of 0.5, more preferably in the range of 0.02-0.2.Thus the nano-carbon material containing hetero atom prepared is shown preferably Catalytic effect can obtain better catalytic effect when being especially used as the catalyst of hydrocarbons dehydrogenation reaction.
In a kind of more preferably embodiment of the invention, the raw material nano carbon material is multi-walled carbon nanotube, The specific surface area of the multi-walled carbon nanotube is 20-500m2/ g, preferably 50-300m2/ g, more preferably 80-250m2/ g, into One step is preferably 90-150m2/g；Weight-loss ratio of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that more preferably existing in the range of 0.01-0.5 In the range of 0.02-0.2.
According to the method for the present invention, the reaction carries out in closed container.The reaction can self-generated pressure (that is, Do not apply pressure additionally) under carry out, can also carry out under pressure.Preferably, it is described reaction at autogenous pressures into Row.The closed container can be the common reactor for being able to achieve sealing and heating, such as autoclave.
It according to the method for the present invention, can also include solid matter being isolated from the mixture that reaction obtains, and will divide The solid matter separated out is dried, to obtain the nano-carbon material containing hetero atom.
Solid matter can be isolated from the mixture that reaction obtains using common solid-liquid separating method, such as centrifugation, Filtering and decantation one or more of combination.
The condition of the drying can be conventional selection, be can remove the volatile materials in the solid matter isolated It is quasi-.Generally, the drying can 50-200 DEG C at a temperature of carry out, preferably 80-180 DEG C at a temperature of carry out, it is more excellent It is carried out at a temperature of being selected in 120-150 DEG C.The duration of the drying can be selected according to dry temperature and mode. Generally, the duration of the drying can be 0.5-48 hours, preferably 3-24 hours, more preferably 5-12 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 nano-carbon material containing hetero atom are used directly for hydrocarbon dehydrogenation reaction, can also be with Hydrocarbon dehydrogenation reaction is used for after molding.The dehydrogenation reaction can carry out in the presence of oxygen, can not also in the presence of oxygen into Row.Preferably, the dehydrogenation reaction carries out in the presence of oxygen, can obtain better catalytic effect in this way.
According to the sixth aspect of the invention, the present invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, is deposited Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with first aspect according to the present invention containing miscellaneous original Sub- nano-carbon material, the according to the present invention nano-carbon material containing hetero atom of third aspect or according to the present invention the 4th side The nano-carbon material containing hetero atom in face contacts.
Hydrocarbon dehydrogenation reaction method according to the present invention, the nano-carbon material containing hetero atom are used directly for connecing with hydrocarbon Touching is used to contact with hydrocarbon after can also forming the nano-carbon material containing hetero atom.
Hydrocarbon dehydrogenation reaction method according to the present invention can carry out dehydrogenation to a plurality of types of hydrocarbon, to obtain unsaturation Hydrocarbon, such as alkene.According to the method for the present invention particularly suitable for carrying out dehydrogenation to alkane, to obtain alkene.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.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 be with It is carried out under conditions of oxygen is not present.Preferably, hydrocarbon dehydrogenation reaction method according to the present invention, under conditions of there are oxygen It carries out.When method of the invention carries out under conditions of there are oxygen, the dosage of oxygen can be conventional selection.Generally, The molar ratio of hydrocarbon and oxygen can be 0.01-100:1, preferably 0.1-10:1, more preferably 0.2-5:1, most preferably 0.3- 2:1.
Hydrocarbon dehydrogenation reaction method according to the present invention, can by carrier gas by hydrocarbon and optional oxygen be sent into reactor with The haptoreaction of nano-carbon material containing hetero atom.The carrier gas can for it is common at reaction conditions will not with reactant and react The gas that product occurs chemical interaction and will not decompose, such as nitrogen, carbon dioxide, rare gas and vapor One or more of combination.The dosage of the carrier gas can be conventional selection.Generally, the content of carrier gas can be with 30-99.5 volume %, preferably 50-99 volume %, more preferably 70-98 volume %.
The temperature of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be conventional selection, to be enough to send out hydrocarbon Subject to raw dehydrogenation reaction.Generally, the contact can 200-650 DEG C at a temperature of carry out, preferably in 300-600 DEG C of temperature Degree is lower to carry out, more preferably 350-550 DEG C at a temperature of carry out, further preferably 400-450 DEG C at a temperature of carry out.
Hydrocarbon dehydrogenation reaction method according to the present invention, the contact can carry out in fixed bed reactors, can also be It carries out, is not particularly limited in fluidized-bed reactor.Preferably, the contact carries out in fixed bed reactors.
The duration of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be selected according to the temperature of contact It selects, when such as described contact carries out in fixed bed reactors, continuing for contact can be indicated with volume space velocity when the gas of charging Time.Generally, volume space velocity can be 0.1-10000h when the gas of charging-1, preferably 1-6000h-1, more preferably 5- 5000h-1, further preferably 10-4000h-1, such as 600-1200h-1。
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, outfit of the X-ray photoelectron spectroscopic analysis in Thermo Scientific company It is tested on the ESCALab250 type x-ray photoelectron spectroscopy for having Thermo Avantage V5.926 software, excitaton source For monochromatization Al K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, analysis test When base vacuum be 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Data processing is carried out on Avantage software, and quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is being surveyed It is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before examination.
In following embodiment and comparative example, thermogravimetric analysis carries out on TA5000 thermal analyzer, and test condition is air gas Atmosphere, heating rate are 10 DEG C/min, and temperature range is room temperature (25 DEG C) to 1000 DEG C.Sample is before testing in 150 DEG C of temperature It is 3 hours dry in helium atmosphere with the pressure of 1 normal atmosphere.Using the ASAP2000 type N of Micromertrics company, the U.S.2 Physical adsorption appearance measurement the specific area.Raw material nano carbon material is analyzed using the high-resolution-ration transmission electric-lens of FEI Co., U.S. production And the microscopic appearance of the nano-carbon material containing hetero atom.
Embodiment 1-38 is for illustrating nano-carbon material containing hetero atom and preparation method thereof of the invention.
Embodiment 1
(1) using 20g as multi-walled carbon nanotube (the specific surface area 136m of raw material nano carbon material2/ g, oxygen atom content For 0.3 weight %, nitrogen atom content is 0.02 weight %, and (phosphorus is former for remaining nonmetallic heteroatoms in addition to nitrogen-atoms and oxygen atom Son and sulphur atom) total content be 0.01 weight %, metallic atom total content be 0.1 weight %, in 400-800 DEG C of temperature range Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, is purchased from Chinese science Chengdu organic chemistry Co., Ltd, institute) dispersion is in deionized water, wherein it is dispersed under the conditions of sonic oscillation and carries out, ultrasound vibration The condition of swinging includes: that frequency is 14kHz, and the time is 0.5 hour.Then, NH is added into aqueous dispersions3And hydrogen peroxide, stirring Uniformly, to obtain aqueous dispersions, wherein NH3It is provided in the form of 25 weight % aqueous solutions respectively with hydrogen peroxide, by raw material Nano-carbon material: NH3: hydrogen peroxide: H2The weight ratio of O is that the ratio of 1:0.5:1:20 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 130 DEG C of temperature Under, it reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big Air pressure, similarly hereinafter), after 12 hours dry at a temperature of 120 DEG C, nano-carbon material containing 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 130 DEG C of oil bath, back flow reaction 24 hours under normal pressure.After reaction, it is cooled to room temperature to the temperature in three-necked flask, Reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature After the lower drying of degree 6 hours, nano-carbon material containing hetero atom is obtained.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 1.
Comparative example 2
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, what step (1) was prepared Aqueous dispersions are free of hydrogen peroxide, it is, the multi-walled carbon nanotube as raw material nano carbon material is dispersed in deionized water In, NH is then added3, stir evenly, to obtain aqueous dispersions, wherein press raw material nano carbon material: NH3: hydrogen peroxide: H2The weight ratio of O is that the ratio of 1:0.5:0:20 feeds intake.The composition of the nano-carbon material containing hetero atom of preparation, specific surface area and w500/w800It is listed in table 1.
Comparative example 3
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, what step (1) was prepared Aqueous dispersions are free of NH3, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, so After hydrogen peroxide is added, stir evenly, to obtain aqueous dispersions, wherein press raw material nano carbon material: NH3: hydrogen peroxide: H2The weight ratio of O is that the ratio of 1:0:1:20 feeds intake.The composition of the nano-carbon material containing hetero atom of preparation, specific surface area and w500/w800It is 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 110kHz, and the time is 1 hour.Then, it was added Hydrogen oxide stirs evenly, to obtain aqueous dispersions, wherein presses raw material nano carbon material: hydrogen peroxide: H2The weight ratio of O is 1:0.5:20 ratio feed intake.
Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 130 DEG C, It reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction kettle, Reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature After lower dry 12 hours of degree, obtain nano-carbon material containing hetero atom, this contain the composition of hetero atom nano-carbon material, specific surface area with And w500/w800It is listed in table 1.
Comparative example 5
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.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800? It is listed in table 1.
Comparative example 6
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.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800 It is listed in table 1.
Comparative example 7
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, step does not make in (1) Use hydrogen peroxide；In step (2), it is passed through into autoclave with after the equimolar ozone of hydrogen peroxide, closes reaction under high pressure Kettle is reacted.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
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 %.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
Embodiment 3
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (2), will To aqueous dispersions with polytetrafluoroethyllining lining autoclave in, at a temperature of 80 DEG C, at autogenous pressures instead It answers 24 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
Embodiment 4
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, in step (1), by original Expect nano-carbon material: NH3: hydrogen peroxide: H2The weight ratio of O is that the ratio of 1:0.02:0.04:10 feeds intake.Preparation contains hetero atom Composition, specific surface area and the w of nano-carbon material500/w800It is listed in table 1.
Embodiment 5
(1) using 20g as multi-walled carbon nanotube (the specific surface area 103m of raw material nano carbon material2/ g, oxygen atom content For 0.2 weight %, nitrogen atom content is 0.01 weight %, and (phosphorus is former for remaining nonmetallic heteroatoms in addition to nitrogen-atoms and oxygen atom Son and sulphur atom) total content be 0.04 weight %, metallic atom total content be 0.3 weight %, 400-800 DEG C of humidity province Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.07, purchased from China Chengdu organic chemistry Co., Ltd, the academy of sciences) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation Condition includes: that frequency is 90kHz, and the time is 2 hours, and NH is then added3And hydrogen peroxide, it stirs evenly, to obtain moisture Dispersion liquid, wherein NH3It is provided in the form of 20 weight % aqueous solutions respectively with hydrogen peroxide, by raw material nano carbon material: NH3: mistake Hydrogen oxide: H2The weight ratio of O is that the ratio of 1:0.2:0.5:50 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 160 DEG C of temperature Under, it reacts 36 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into normal pressure, 140 DEG C At a temperature of after dry 8 hours, obtain nano-carbon material containing hetero atom, this contains the composition of hetero atom nano-carbon material, specific surface area And w500/w800It is listed in table 1.
Embodiment 6
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), as The specific surface area of the multi-walled carbon nanotube (being purchased from Shandong great Zhan nano material Co., Ltd) of raw material nano carbon material is 103m2/ G, w500/w800It is 0.23, oxygen atom content is 1.1 weight %, and nitrogen atom content is 0.03 weight %, removes nitrogen-atoms and oxygen atom The total content of remaining outer nonmetallic heteroatoms (phosphorus atoms and sulphur atom) is 0.01 weight %, and metallic atom total content is 1.6 Weight %.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
Embodiment 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 200 DEG C, at autogenous pressures instead It answers 36 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 1.
Embodiment 8
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), by original Expect nano-carbon material: NH3: hydrogen peroxide: H2The weight ratio of O is that the ratio of 1:2:0.1:250 feeds intake.Preparation is received containing hetero atom Composition, specific surface area and the w of rice carbon material500/w800It is listed in table 1.
Embodiment 9
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), peroxide The tert-butyl hydroperoxide for changing hydrogen equimolar amounts replaces.The composition of the nano-carbon material containing hetero atom of preparation, specific surface area with And w500/w800It is listed in table 1.
Embodiment 10
Nano-carbon material containing hetero atom is prepared using method same as Example 5, unlike, in step (1), peroxide The cumyl peroxide for changing hydrogen equimolar amounts replaces.The composition of the nano-carbon material containing hetero atom of preparation, specific surface area with And w500/w800It is listed in table 1.
Comparative example 8
Nano-carbon material containing hetero atom is prepared using method same as in Example 10, 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 After cumyl peroxide is added, stir evenly, to obtain aqueous dispersions, wherein press raw material nano carbon material: NH3: peroxide Change diisopropylbenzene (DIPB): H2The weight ratio of O is that the ratio of 1:0:0.7:50 feeds intake.The composition of the nano-carbon material containing hetero atom of preparation, Specific surface area and w500/w800It is listed in table 1.
Embodiment 11
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 hydrogen peroxide, stirring is then added Uniformly, to obtain aqueous dispersions, wherein hydrazine and hydrogen peroxide are provided in the form of the aqueous solution of 25 weight % respectively, by original Expect nano-carbon material: hydrazine: hydrogen peroxide: H2The weight ratio of O is that the ratio of 1:0.1:0.5:25 feeds intake；
In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 150 At a temperature of DEG C, react 24 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Comparative example 9
Aqueous dispersions identical with embodiment 11 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In 150 DEG C of oil bath, back flow reaction 24 hours under normal pressure.After reaction, it is cooled to room temperature to the temperature in three-necked flask, Reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature After the lower drying of degree 6 hours, nano-carbon material containing hetero atom is obtained.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 2.
Comparative example 10
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 11, unlike, what step (1) was prepared 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 Hydrogen peroxide is added, stirs evenly, to obtain aqueous dispersions, wherein presses raw material nano carbon material: hydrazine: hydrogen peroxide: H2O Weight ratio be 1:0:0.6:25 ratio feed intake.The composition of the nano-carbon material containing hetero atom of preparation, specific surface area and w500/w800It is listed in table 2.
Comparative example 11
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 11, unlike, what step (1) was prepared Aqueous dispersions are free of hydrogen peroxide, it is, the multi-walled carbon nanotube as raw material nano carbon material is dispersed in deionized water In, hydrazine is then added, stirs evenly, to obtain aqueous dispersions, wherein presses raw material nano carbon material: hydrazine: hydrogen peroxide: H2O Weight ratio be 1:0.6:0:25 ratio feed intake.The composition of the nano-carbon material containing hetero atom of preparation, specific surface area and w500/w800It is listed in table 2.
Embodiment 12
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 11, 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.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 13
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 11, unlike, in step (1), make For raw material nano carbon material multi-walled carbon nanotube with embodiment 2.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 2.
Embodiment 14
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 11, unlike, in step (1), press Raw material nano carbon material: hydrazine: hydrogen peroxide: H2The weight ratio of O is that the ratio of 1:2:5:200 feeds intake.Preparation is received containing hetero atom Composition, specific surface area and the w of rice carbon material500/w800It is listed in table 2.
Embodiment 15
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 tert-butyl hydroperoxide is then added Hydrogen stirs evenly, to obtain aqueous dispersions, wherein hydrazine is provided in the form of the aqueous solution of 85 weight %, by raw material nano carbon Material: hydrazine: tert-butyl hydroperoxide: H2The weight ratio of O is that the ratio of 1:0.5:0.5:50 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.
Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 16
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 15, unlike, in step (1), make For raw material nano carbon material multi-walled carbon nanotube with embodiment 6.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 2.
Embodiment 17
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 15, unlike, in step (1), press Raw material nano carbon material: hydrazine: tert-butyl hydroperoxide: H2The weight ratio of O is that the ratio of 1:2:0.02:10 feeds intake.Preparation contains Composition, specific surface area and the w of hetero atom nano-carbon material500/w800It is listed in table 2.
Embodiment 18
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 15, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, at autogenous pressures Reaction 48 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 19
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 15, unlike, in step (1), uncle The cyclohexyl hydroperoxide of butylhydroperoxide equimolar amounts replaces.Composition, the ratio of the nano-carbon material containing hetero atom of preparation Surface area and w500/w800It is listed in table 2.
Embodiment 20
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 15, unlike, in step (1), uncle The cumyl peroxide of butylhydroperoxide equimolar amounts replaces.Composition, the ratio of the nano-carbon material containing hetero atom of preparation Surface area and w500/w800It is listed in table 2.
Embodiment 21
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 15, unlike, in step (1), uncle The hydrogen peroxide of butylhydroperoxide equimolar amounts replaces.The composition of the nano-carbon material containing hetero atom of preparation, specific surface area And w500/w800It is listed in table 2.
Embodiment 22
Nano-carbon material containing hetero atom is prepared using method same as Example 1, difference is as follows:
In step (1), in deionized water by the dispersion of raw material nano carbon material, urea and hydrogen peroxide isopropyl is then added Benzene stirs evenly, to obtain aqueous dispersions, wherein presses raw material nano carbon material: urea: cumyl hydroperoxide: H2O's Weight ratio is that the ratio of 1:0.5:0.1:15 feeds intake；
In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 150 At a temperature of DEG C, react 24 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Comparative example 12
Aqueous dispersions identical with embodiment 22 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In 150 DEG C of oil bath, back flow reaction 24 hours under normal pressure.After reaction, it is cooled to room temperature to the temperature in three-necked flask, Reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature After the lower drying of degree 6 hours, nano-carbon material containing hetero atom is obtained.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 2.
Comparative example 13
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 22, unlike, what step (1) was prepared 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 After cumyl hydroperoxide is added, stir evenly, to obtain aqueous dispersions, wherein press raw material nano carbon material: urea: mistake Hydrogen oxide isopropylbenzene: H2The weight ratio of O is that the ratio of 1:0:0.6:15 feeds intake.The group of the nano-carbon material containing hetero atom of preparation At, specific surface area and w500/w800It is listed in table 2.
Comparative example 14
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 22, unlike, what step (1) was prepared Aqueous dispersions are free of cumyl hydroperoxide, it is, the multi-walled carbon nanotube as raw material nano carbon material is dispersed in In ionized water, urea is then added, stirs evenly, to obtain aqueous dispersions, wherein presses raw material nano carbon material: urea: mistake Hydrogen oxide isopropylbenzene: H2The weight ratio of O is that the ratio of 1:0.6:0:15 feeds intake.The group of the nano-carbon material containing hetero atom of preparation At, specific surface area and w500/w800It is listed in table 2.
Embodiment 23
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 22, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 220 DEG C, at autogenous pressures Reaction 24 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 24
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 22, unlike, as raw material nano The multi-walled carbon nanotube of carbon material is the same as embodiment 2.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/ w800It is listed in table 2.
Embodiment 25
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 22, unlike, in step (1), press Raw material nano carbon material: urea: cumyl hydroperoxide: H2The weight ratio of O is that the ratio of 1:0.05:0.1:250 feeds intake.Preparation The nano-carbon material containing hetero atom composition, specific surface area and w500/w800It is listed in table 2.
Embodiment 26
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 and hydrogen peroxide isopropyl is then added Benzene stirs evenly, to obtain aqueous dispersions, wherein presses raw material nano carbon material: urea: cumyl hydroperoxide: H2O's Weight ratio is that the ratio of 1:0.2:1:40 feeds intake；
In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 120 At a temperature of DEG C, react 48 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 27
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 26, unlike, in step (1), make For raw material nano carbon material multi-walled carbon nanotube with embodiment 6.The composition of the nano-carbon material containing hetero atom of preparation, specific surface Long-pending and w500/w800It is listed in table 2.
Embodiment 28
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 26, unlike, in step (1), press Raw material nano carbon material: urea: cumyl hydroperoxide: H2The weight ratio of O is that the ratio of 1:2:0.05:100 feeds intake.Preparation Composition, specific surface area and the w of the nano-carbon material containing hetero atom500/w800It is listed in table 2.
Embodiment 29
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 26, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, at autogenous pressures Reaction 48 hours.Composition, specific surface area and the w of the nano-carbon material containing hetero atom of preparation500/w800It is listed in table 2.
Embodiment 30
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 26, unlike, in step (1), mistake The cyclohexyl hydroperoxide of hydrogen oxide isopropylbenzene equimolar amounts replaces.Composition, the ratio of the nano-carbon material containing hetero atom of preparation Surface area and w500/w800It is listed in table 2.
Embodiment 31
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 26, unlike, in step (1), mistake The dibenzoyl peroxide of hydrogen oxide isopropylbenzene equimolar amounts replaces.Composition, the ratio of the nano-carbon material containing hetero atom of preparation Surface area and w500/w800It is listed in table 2.
Embodiment 32
Nano-carbon material containing hetero atom is prepared using method identical with embodiment 26, unlike, in step (1), mistake The hydrogen peroxide of hydrogen oxide isopropylbenzene equimolar amounts replaces.The composition of the nano-carbon material containing hetero atom of preparation, specific surface area And w500/w800It is listed in table 2.
Embodiment 33
Nano-carbon material containing hetero atom prepared by embodiment 1 roasts 4 hours in air atmosphere at 350 DEG C.
Comparative example 15
Nano-carbon material containing hetero atom prepared by comparative example 1 roasts 4 hours in air atmosphere at 350 DEG C.
Comparative example 16
Nano-carbon material containing hetero atom prepared by comparative example 2 roasts 4 hours in air atmosphere at 350 DEG C.
Comparative example 17-21
The nano-carbon material containing hetero atom that comparative example 17 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 18 prepares comparative example 4 350 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 5 350 DEG C in air atmosphere roasting it is 4 small When；
The nano-carbon material containing hetero atom that comparative example 20 prepares comparative example 6 350 DEG C in air atmosphere roasting it is 4 small When；
The nano-carbon material containing hetero atom that comparative example 21 prepares comparative example 7 350 DEG C in air atmosphere roasting it is 4 small When.
Embodiment 34
Nano-carbon material containing hetero atom prepared by embodiment 2 roasts 4 hours in air atmosphere at 350 DEG C.
Embodiment 35
Nano-carbon material containing hetero atom prepared by embodiment 3 roasts 4 hours in air atmosphere at 350 DEG C.
Embodiment 36
Nano-carbon material containing hetero atom prepared by embodiment 4 roasts 4 hours in air atmosphere at 350 DEG C.
Embodiment 37
Nano-carbon material containing hetero atom prepared by embodiment 11 roasts 2 hours in air atmosphere at 450 DEG C.
Embodiment 38
Nano-carbon material containing hetero atom prepared by embodiment 26 roasts 12 hours in air atmosphere at 300 DEG C.
Embodiment 39-76 is used to illustrate application and the hydrocarbon dehydrogenation reaction side of the nano-carbon material according to the present invention containing hetero atom Method.
Embodiment 39-70
Respectively using the nano-carbon material containing hetero atom of 0.4g (admission space 3.7mL) embodiment 1-32 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 0.15MPa and 450 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 2.0 volume %, normal butane and oxygen Gas molar ratio 1:3, surplus are nitrogen as carrier gas) it with total volume air speed is 900h-1It is passed through in reactor and is reacted, continuously The composition of the reaction mixture exported from reactor is monitored, and calculates the selective and total butylene of n-butane conversion, total olefin (for 1- butylene and 2- butylene) selectivity, the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 22-35
It is reacted using method identical with embodiment 39-70, unlike, it is prepared respectively using comparative example 1-14 Nano-carbon material containing hetero atom is as catalyst.Reaction result is listed in table 3.
Comparative example 36
It is reacted using method identical with embodiment 39-70, unlike, use raw material same as Example 1 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Comparative example 37
It is reacted using method identical with embodiment 39-70, unlike, use raw material same as Example 5 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Embodiment 71-76
It is reacted using method identical with embodiment 39-70, unlike, contained using prepared by embodiment 33-38 Hetero atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 38-44
It is reacted using method identical with embodiment 39-70, unlike, contained using prepared by comparative example 15-21 Hetero atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 45
It is reacted using method identical with embodiment 39-70, 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 46
It is reacted using method identical with embodiment 39-70, 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 (74)

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 4-12 weight %, and N element contains Amount is 2-6 weight %, and the content of C element is 82-94 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 IO c, the amount of the O element determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is IO e, IO c/IO eIn the range of 0.5-1；
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 0.8-1；
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 peroxide are reacted in closed container, and the nitrogenous compound is selected from NH3, hydrazine and urea, the peroxide is selected from organic peroxide shown in hydrogen peroxide and Formulas I,
In Formulas I, R1And R2It each is selected from H, C4-C12Linear or branched alkyl group, C6-C12Aryl, C7-C12Aralkyl andAnd R1And R2It is not simultaneously H, R3For C4-C12Linear or branched alkyl group or C6-C12Aryl,
In reaction process, the temperature of the aqueous dispersions is maintained in the range of 80-220 DEG C.
2. nano-carbon material containing hetero atom according to claim 1, wherein IO c/IO eIn the range of 0.5-0.95；IN c/ IN tIn the range of 0.8-0.95.
3. nano-carbon material containing hetero atom according to claim 2, wherein IO c/IO eIn the range of 0.6-0.8.
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 0.3-1.
5. nano-carbon material containing hetero atom according to claim 4, wherein IC c/IC eIn the range of 0.4-0.95.
6. nano-carbon material containing hetero atom according to claim 5, wherein IC c/IC eIn the range of 0.5-0.8.
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 70-92 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 8-30 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 75-85 weight %, by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The content of determining C element is 15-25 weight %.
9. 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 0.2.
10. nano-carbon material containing hetero atom according to claim 9, wherein IN g/IN tIn the range of 0-0.2.
11. nano-carbon material containing hetero atom according to claim 10, wherein IN g/IN tIn the range of 0.05-0.2.
12. nano-carbon material containing hetero atom 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 4-10 weight %, and the content of C element is 84.2-93.8 Weight %, the content of N element are 2.2-5.8 weight %.
13. nano-carbon material containing hetero atom according to claim 12, 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 5-9 weight %, and the content of C element is 86-92.5 weight %, N element Content is 2.5-5 weight %.
14. nano-carbon material containing hetero atom according to claim 13, wherein with the total of the nano-carbon material containing hetero atom On the basis of amount and based on the element, the content of O element is 5.5-8 weight %, and the content of C element is 87.5-91.5 weight %, N member The content of element is 3-4.5 weight %.
15. 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.
16. nano-carbon material containing hetero atom according to claim 15, wherein it is containing miscellaneous that this, which contains hetero atom nano-carbon material, Atom multi-walled carbon nanotube.
17. nano-carbon material containing hetero atom according to claim 16, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 50-500m2/g。
18. nano-carbon material containing hetero atom according to claim 17, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 80-300m2/g。
19. nano-carbon material containing hetero atom according to claim 18, wherein the multi-walled carbon nanotube containing hetero atom Specific surface area is 90-200m2/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 100-150m2/g。
21. nano-carbon material containing hetero atom according to claim 16, 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.
22. nano-carbon material containing hetero atom according to claim 21, wherein w500/w800In the range of 0.02-0.2.
23. a kind of preparation method of nano-carbon material containing hetero atom, this method include one kind is dispersed with raw material nano carbon material, The aqueous dispersions of at least one nitrogenous compound and at least one peroxide are reacted in closed container, described nitrogenous Compound is selected from NH3, hydrazine and urea, in reaction process, the temperature of the aqueous dispersions is maintained in the range of 80-220 DEG C, former Expect nano-carbon material: nitrogenous compound: the weight ratio of peroxide is 1:0.01-10:0.01-10, and the peroxide is selected from Organic peroxide shown in hydrogen peroxide and Formulas I,
In Formulas I, R1And R2It each is selected from H, C4-C12Linear or branched alkyl group, C6-C12Aryl, C7-C12Aralkyl andAnd R1And R2It is not simultaneously H, R3For C4-C12Linear or branched alkyl group or C6-C12Aryl.
24. according to the method for claim 23, wherein raw material nano carbon material: H2The weight ratio of O is 1:2-500.
25. according to the method for claim 24, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.05-3:0.02-5；
Raw material nano carbon material: H2The weight ratio of O is 1:5-250.
26. according to the method for claim 25, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.1-0.5:0.1-1；
Raw material nano carbon material: H2The weight ratio of O is 1:15-50.
27. according to the method for claim 23, wherein nitrogenous compound: the molar ratio of peroxide is 1:0.001-10.
28. according to the method for claim 27, wherein nitrogenous compound: the molar ratio of peroxide is 1:0.002-5.
29. according to the method for claim 28, wherein nitrogenous compound: the molar ratio of peroxide is 1:0.05-2.
30. according to the method for claim 23, wherein the peroxide be selected from hydrogen peroxide, tert-butyl hydroperoxide, Cyclohexyl hydroperoxide, cumyl peroxide, cumyl hydroperoxide and dibenzoyl peroxide.
31. according to the method for claim 23, wherein the nitrogenous compound is NH3, the peroxide is selected from peroxide Change hydrogen, raw material nano carbon material: nitrogenous compound: the weight ratio of peroxide be 1:0.02-5:0.01-5, nitrogenous compound with The molar ratio of peroxide is 1:0.02-2.
32. according to the method for claim 31, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.02-2.5:0.1-5, the molar ratio of nitrogenous compound and peroxide is 1:0.1-1.8.
33. according to the method for claim 32, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.1-2:0.4-4.5, the molar ratio of nitrogenous compound and peroxide is 1:1-1.5.
34. according to the method for claim 33, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.2-0.5:0.5-1.
35. according to the method for claim 23, wherein the nitrogenous compound is hydrazine, and the peroxide is selected from tertiary fourth Base hydrogen peroxide, raw material nano carbon material: nitrogenous compound: the weight ratio of peroxide is 1:0.02-5:0.01-8, nitrogen The molar ratio for closing object and peroxide is 1:0.001-8.
36. according to the method for claim 35, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.08-3:0.02-5, the molar ratio of nitrogenous compound and peroxide is 1:0.003-6.
37. according to the method for claim 36, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.1-0.5:0.1-1, the molar ratio of nitrogenous compound and peroxide is 1:0.1-0.5.
38. according to the method for claim 23, wherein the nitrogenous compound is urea, and the peroxide was selected from Hydrogen oxide isopropylbenzene, raw material nano carbon material: nitrogenous compound: the weight ratio of peroxide is 1:0.02-5:0.01-3, nitrogenous The molar ratio of compound and peroxide is 1:0.005-4.
39. according to the method for claim 38, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.05-2:0.05-2, the molar ratio of nitrogenous compound and peroxide is 1:0.05-2.
40. according to the method for claim 39, wherein raw material nano carbon material: nitrogenous compound: the weight of peroxide Than for 1:0.2-0.5:0.1-1.
41. the method according to any one of claim 23-40, wherein in reaction process, the temperature of the aqueous dispersions Degree is maintained in the range of 100-180 DEG C.
42. the method according to any one of claim 23-40, wherein the duration of the reaction is in 0.5-96 In the range of hour.
43. according to the method for claim 42, wherein the duration of the reaction is in the range of 2-72 hours.
44. according to the method for claim 43, wherein the duration of the reaction is in the range of 20-50 hours.
45. the method according to any one of claim 23-40, wherein N element in the raw material nano carbon material Content is the content not higher than 0.5 weight %, O element for not higher than 1.2 weight %.
46. according to the method for claim 45, wherein in the raw material nano carbon material content of N element be not higher than 0.2 weight %.
47. according to the method for claim 46, wherein in the raw material nano carbon material content of N element be not higher than 0.1 weight %.
48. according to the method for claim 47, wherein in the raw material nano carbon material content of N element be not higher than 0.05 weight %.
49. according to the method for claim 45, wherein the content of O element is not higher than 0.5 weight %.
50. the method according to any one of claim 23-40, wherein the raw material nano carbon material is carbon nanometer Pipe.
51. according to the method for claim 50, wherein the raw material nano carbon material is multi-walled carbon nanotube.
52. method according to claim 51, wherein the specific surface area of the multi-walled carbon nanotube is 20-500m2/g。
53. method according to claim 52, wherein the specific surface area of the multi-walled carbon nanotube is 50-300m2/g。
54. method according to claim 53, wherein the specific surface area of the multi-walled carbon nanotube is 80-250m2/g。
55. method according to claim 54, wherein the specific surface area of the multi-walled carbon nanotube is 90-150m2/g。
56. according to method described in claim 23-40, wherein temperature range of the multi-walled carbon nanotube at 400-800 DEG C Interior weight-loss ratio 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 Interior, the weight-loss ratio measures in air atmosphere.
57. method according to claim 56, wherein w500/w800In the range of 0.02-0.2.
58. the method according to any one of claim 23-40, 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.
59. method according to claim 58, wherein the drying 50-200 DEG C at a temperature of carry out；The drying Duration be 0.5-48 hours.
60. method according to claim 59, wherein the drying 80-180 DEG C at a temperature of carry out；The drying Duration be 3-24 hours.
61. method according to claim 60, wherein the drying 120-150 DEG C at a temperature of carry out；The drying Duration be 5-12 hours.
62. a kind of nano-carbon material containing hetero atom of the preparation of the method as described in any one of claim 23-61.
63. a kind of nano-carbon material containing hetero atom, it is by any one of claim 1-22 that this, which contains hetero atom nano-carbon material, Nano-carbon material containing hetero atom described in the nano-carbon material containing hetero atom or claim 62 is roasted and is made 's.
64. nano-carbon material containing hetero atom according to claim 63, wherein temperature of the roasting at 250-500 DEG C Lower progress；The duration of the roasting is 1-24 hours.
65. nano-carbon material containing hetero atom according to claim 64, wherein temperature of the roasting at 300-450 DEG C Lower progress；The duration of the roasting is 2-12 hours.
66. in nano-carbon material containing hetero atom described in any one of claim 1-22 and 62 or claim 63-65 Application of the nano-carbon material containing hetero atom described in any one as the catalyst of hydrocarbon dehydrogenation reaction.
67. application according to claim 66, wherein the dehydrogenation reaction carries out in the presence of oxygen.
68. the application according to claim 66 or 67, wherein the hydrocarbon is alkane.
69. application according to claim 68, wherein the hydrocarbon is C2-C12Alkane.
70. application according to claim 69, wherein the hydrocarbon is normal butane.
71. 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 63- described in any one of hydrocarbon and claim 1-22 and 62 The contact of nano-carbon material containing hetero atom described in any one of 65.
72. method according to claim 71, wherein the hydrocarbon is alkane.
73. the method according to claim 72, wherein the hydrocarbon is C2-C12Alkane.
74. the method according to claim 73, wherein the hydrocarbon is normal butane.
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Families Citing this family (20)

* 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
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
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
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
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
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
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
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
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
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
CN112673468B (en) * 2018-09-27 2024-05-03 株式会社村田制作所 Module and method for manufacturing same
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
CN115724807B (en) * 2021-08-31 2024-07-09 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
WO2006008049A1 (en) * 2004-07-16 2006-01-26 Nanoc Sdn. Bhd. 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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