CN105817247A - Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons - Google Patents

Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons Download PDF

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CN105817247A
CN105817247A CN201510702300.9A CN201510702300A CN105817247A CN 105817247 A CN105817247 A CN 105817247A CN 201510702300 A CN201510702300 A CN 201510702300A CN 105817247 A CN105817247 A CN 105817247A
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nano
hetero atom
range
carbon material
weight
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CN105817247B (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20—Carbon compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a nanometer carbon material containing heteroatoms and a preparation method and application thereof, and a dehydrogenation reaction method for hydrocarbons. The nanometer carbon material containing heteroatoms comprises, by weight, 0.2 to 5% of N, 2 to 10% of O and 85 to 97.8% of C. In an XPS pattern, elemental N determined by peaks in a range of 398.5 to 400.1 eV accounts for 0.6 to 0.95 of the total elemental N while elemental N determined by peaks in a range of 403.5 to 406.5 eV accounts for 0.05 to 0.4 of the total elemental N; a ratio of elemental O determined by peaks in a range of 531.0 to 532.5 eV to elemental O determined by peaks in a range of 532.6 to 533.5 eV is 0.1 to 0.5; and a ratio of elemental C determined by peaks in a range of 288.6 to 288.8 eV to elemental C determined by peaks in a range of 286.0 to 286.2 eV is 0.2 to 0.8. The nanometer carbon material containing heteroatoms shows good catalytic activity in the dehydrogenation reaction of hydrocarbons and can obviously improve the conversion rate of raw materials and olefin selectivity.

Description

One is containing hetero atom nano-carbon material and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
Technical field
The present invention relates to a kind of nano-carbon material Han hetero atom, the invention still further relates to a kind of preparation method containing hetero atom nano-carbon material and by the method prepare containing hetero atom nano-carbon material, the present invention further relate to a kind of by by above-mentioned carry out roasting containing hetero atom nano-carbon material and prepare containing hetero atom nano-carbon material, the invention further relates to according to the present invention containing hetero atom nano-carbon material as the application of the catalyst of hydrocarbon dehydrogenation reaction and a kind of hydrocarbon dehydrogenation reaction method.
Background technology
Nano-carbon material is the inorganic non-metallic catalyst that a class that developed recently gets up is important, the performance of conventional metals catalyst is exhibited improvements in multiple fields such as the hydrocarbon conversion, fine chemistry industry, fuel cell, solar energy conversions, cause the extensive concern of scientific worker, there is huge development potentiality.
Although nano-carbon material itself has certain catalysis activity, but its catalytic performance (such as activity) still awaits improving further.In order to improve the catalytic performance (such as activity) of nano-carbon material further, research worker attempts introducing hetero-atoms in nano-carbon material, so that nano-carbon material is carried out modification, as introduced oxygen atom, nitrogen-atoms in nano-carbon material.
In nano-carbon material, introduce oxygen atom, the oxygen-containing functional groups such as hydroxyl, carbonyl, carboxyl, ester group and anhydride can be formed on nano-carbon material surface.Can realize introducing oxygen atom in nano-carbon material by nano-carbon material being carried out oxidation processes, thus increase the content of oxygen-containing functional group in nano-carbon material.For example, it is possible to by nano-carbon material at strong acid (such as HNO3、H2SO4) and/or strong oxidizing solution (such as H2O2、KMnO4Carry out back flow reaction in), can also assist while back flow reaction and carry out microwave heating or sonic oscillation, to strengthen the effect of oxidation reaction.But, carrying out back flow reaction in strong acid and/or strong oxidizing solution may have a negative impact to the framing structure of nano-carbon material, even destroys the framing structure of nano-carbon material.Such as: nano-carbon material is carried out in nitric acid back flow reaction, although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, but easily cause nano-carbon material cut-off and/or substantially increase the defective bit in graphite network structure, thus reduce the performance of nano-carbon material, such as heat stability.It addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, during to introduce oxygen atom, the introduction volume of oxygen atom is high to the dependency of operation condition, and fluctuation range is wider.
When introducing nitrogen-atoms in nano-carbon material, according to nitrogen-atoms difference of residing chemical environment in nano-carbon material, generally nitrogen-atoms is divided into chemical nitrogen and structure nitrogen.Chemical nitrogen is mainly the surface occurring in material with the form of surface functional group, such as the surface such as amino or nitrosyl radical nitrogen-containing functional group.Structure nitrogen refers to the nitrogen-atoms of framing structure and the carbon atom bonding entering nano-carbon material.Structure nitrogen mainly includes graphite mould nitrogen (i.e.,), pyridine type nitrogen (i.e.,) and pyrroles's type nitrogen is (i.e.,).Carbon atom in graphite mould nitrogen direct substitution graphite lattice, forms saturated nitrogen-atoms；Pyridine type nitrogen and pyrroles's type nitrogen are unsaturated nitrogen atom, while replacing carbon atom, often can cause the disappearance closing on carbon atom, form defective bit.
High temperature and/or high pressure can be utilized to be simultaneously introduced in framing structure and/or the surface of nano-carbon material by nitrogen element in the building-up process of nano-carbon material by introducing nitrogenous functional atmosphere (such as ammonia, nitrogen) in nano-carbon material building-up process；Can also utilize high temperature and/or high pressure that nitrogen element is incorporated into the surface of nano-carbon material by being placed in by nano-carbon material in nitrogenous functional atmosphere (such as ammonia, nitrogen).Although high temperature and/or high pressure can form structure nitrogen in nano-carbon material, but the type of nitrogen containing species depends on reaction condition, wayward；Further, the different types of nitrogen containing species so produced is uneven in the surface distributed of nano-carbon material, causes the unstable properties of nitrogenous nano-carbon material.Then can also react with amine by nano-carbon material is carried out oxidation processes, thus introduce nitrogen-atoms on nano-carbon material surface, the nitrogen-atoms so introduced is essentially chemical nitrogen.
The dehydrogenation reaction of hydrocarbons is the response type that a class is important, and such as major part low carbon chain alkene is to be obtained by the dehydrogenation reaction of low-carbon paraffin.Whether dehydrogenation reaction participates in being divided into direct dehydrogenation reaction (that is, oxygen is not involved in) and oxidative dehydrogenation (that is, oxygen participates in) two classes according to oxygen.Polytype nano-carbon material has been demonstrated that the reaction of the direct dehydrogenation to hydrocarbons and oxidative dehydrogenation are respectively provided with catalytic effect, introduces oxygen atom and/or nitrogen-atoms then can improve its catalysis activity in nano-carbon material.
Although modified and catalytic performance the research of the Heteroatom doping about nano-carbon material achieves many progress, but some of which basic problem is built consensus not yet, still needs Heteroatom doping nano-carbon material and preparation method thereof and catalytic performance are furtherd investigate.
Summary of the invention
It is an object of the present invention to provide a kind of preparation method containing hetero atom nano-carbon material, use the method can stably improve oxygen atom and the content of nitrogen-atoms in nano-carbon material, and little to the structure influence of nano-carbon material itself.
A kind of nano-carbon material Han hetero atom of offer is provided, this contains hetero atom nano-carbon material and the dehydrogenation reaction of hydrocarbons is had preferable catalytic effect, the conversion ratio of raw material can not only be effectively improved, and alkene is had preferable selectivity.
A further object of the present invention is to provide a kind of hydrocarbon dehydrogenation reaction method, and the method can obtain higher feed stock conversion and olefine selective.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material Han hetero atom, this contains hetero atom nano-carbon material and contains C element, O element and N element, on the basis of this total amount containing hetero atom nano-carbon material and in terms of element, the content of N element is 0.2-5 weight %, the content of O element is 2-10 weight %, and the content of C element is 85-97.8 weight %；
Determined that this total amount containing the N element in hetero atom nano-carbon material is I by x-ray photoelectron power spectrumN t, the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum the amount of the N element determined is IN c, IN c/IN tIn the range of 0.6-0.95, the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum the amount of the N element determined is IN n, IN n/IN tIn the range of 0.05-0.4；
This contains in hetero atom nano-carbon material, the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum the amount of the O element determined is IO c, the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum the amount of the O element determined is IO e, IO c/IO eIn the range of 0.1-0.5；
This contains in hetero atom nano-carbon material, the peak in the range of 288.6-288.8eV in x-ray photoelectron power spectrum the amount of the C element determined is IC c, the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum the amount of the C element determined is IC e, IC c/IC eIn the range of 0.2-0.8.
According to the second aspect of the invention, the invention provides a kind of preparation method containing hetero atom nano-carbon material, the method includes reacting a kind of aqueous dispersions being dispersed with raw material nano material with carbon element in hermetic container, is dissolved with HNO in described aqueous dispersions3, in course of reaction, the temperature of described aqueous dispersions is maintained in the range of 100-250 DEG C.
According to the third aspect of the present invention, the invention provides a kind of by prepare according to the method for second aspect of the present invention containing hetero atom nano-carbon material.
According to the fourth aspect of the present invention, the invention provides a kind of nano-carbon material Han hetero atom, this contains hetero atom nano-carbon material is by prepared according to the carrying out roasting containing hetero atom nano-carbon material of first aspect of the present invention or the 3rd aspect.
According to the fifth aspect of the present invention, the invention provides according to first aspect of the present invention containing hetero atom nano-carbon material, according to third aspect of the present invention containing hetero atom nano-carbon material or according to the fourth aspect of the present invention containing hetero atom nano-carbon material as the application of the catalyst of hydrocarbon dehydrogenation reaction.
According to the sixth aspect of the invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, under conditions of the method is included in presence or absence oxygen, under hydrocarbon dehydrogenation reaction conditions, hydrocarbon is contacted with the nano-carbon material containing hetero atom containing hetero atom nano-carbon material or according to the 4th aspect of the present invention containing hetero atom nano-carbon material, according to third aspect of the present invention according to first aspect of the present invention.
According to the preparation method containing hetero atom nano-carbon material of the present invention, can stably improve oxygen atom and the content of nitrogen-atoms in nano-carbon material, simultaneously little to the structure influence of nano-carbon material itself.The method using the present invention introduces oxygen atom and nitrogen-atoms in nano-carbon material, and good to the selectivity of oxygenated species and nitrogen containing species, the nano-carbon material containing hetero atom of preparation has stable performance.
The nano-carbon material containing hetero atom according to the present invention demonstrates good catalytic performance in the dehydrogenation reaction of hydrocarbons, can significantly improve the conversion ratio of raw material, can also obtain higher selectivity of product simultaneously.Specifically, by according to the present invention containing hetero atom nano-carbon material be used as n butane oxidation dehydrogenation reaction catalyst time, there is higher n-butane conversion, butylene had higher selectivity simultaneously.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.
Fig. 1 is the transmission electron microscope photo containing hetero atom nano-carbon material of embodiment 1 preparation.
Fig. 2 is the transmission electron microscope photo of the raw material nano material with carbon element that embodiment 1 uses.
Detailed description of the invention
In the present invention, nano-carbon material refers to the most one-dimensional material with carbon element less than 100nm of dispersion phase yardstick.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material Han hetero atom, this contains hetero atom nano-carbon material and contains C element, O element and N element.
According to the present invention containing hetero atom nano-carbon material, on the basis of this total amount containing hetero atom nano-carbon material and in terms of element, the content of N element is 0.2-5 weight %, preferably 0.5-4.5 weight %, more preferably 1.5-4 weight %；The content of O element is 2-10 weight %, preferably 3-8 weight %, more preferably 5-8 weight %；The content of C element is 85-97.8 weight %, preferably 87.5-96.5 weight %, more preferably 88-93.5 weight %.Wherein, the content of each element uses x-ray photoelectron power spectrum (XPS) method to measure, the area that 1s electronics spectral peak is corresponding determine the content of element；Sample is depressed in the temperature of 150 DEG C and 1 standard atmosphere before testing and is dried 3 hours in helium atmosphere.
In the present invention, X-ray photoelectron spectroscopic analysis is tested on the ESCALab250 type x-ray photoelectron spectroscopy equipped with ThermoAvantageV5.926 software of ThermoScientific company, excitaton source is monochromatization AlK α X-ray, energy is 1486.6eV, power is 150W, penetrating energy used by narrow scan is 30eV, and base vacuum when analyzing test is 6.5 × 10-10Mbar, C1s peak (284.0eV) correction of electron binding energy simple substance carbon, process in ThermoAvantage software enterprising row data, use sensitivity factor method to carry out quantitative analysis in analyzing module.
According to the present invention containing hetero atom nano-carbon material, x-ray photoelectron power spectrum determine that this total amount containing the N element in hetero atom nano-carbon material is IN t, the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum the amount of the N element determined is IN c, IN c/IN tIn the range of 0.6-0.95, preferably in the range of 0.7-0.9, preferably in the range of 0.75-0.85；The amount of the N element determined by the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum is IN n, IN n/IN tIn the range of 0.05-0.4, preferably in the range of 0.1-0.3, more preferably in the range of 0.15-0.25.In the present invention, when representing numerical range, " ×-× in the range of " include two binary values.
According to the present invention containing hetero atom nano-carbon material, the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum content is relatively low does not even contain for the N element determined (that is, graphite mould nitrogen).Usually, according to the present invention containing in hetero atom nano-carbon material, the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum the amount of the N element determined is IN g, IN g/IN tFor not higher than 0.2, typically in the range of 0.02-0.1.
In the present invention, the area of the N1s spectral peak in x-ray photoelectron power spectrum determine total amount A of N elementN 1, the N1s spectral peak in x-ray photoelectron power spectrum is divided into three groups of peaks, i.e. the spectral peak in the range of 403.5-406.5eV is (corresponding to-NO2Species), the spectral peak (corresponding to graphite mould nitrogen species) in the range of 400.6-401.5eV and the spectral peak in the range of 398.5-400.1eV be (corresponding to except graphite mould nitrogen and-NO2Nitrogen species outside type nitrogen), the area of the spectral peak in the range of 400.6-401.5eV is designated as AN 2, the area of the spectral peak in the range of 398.5-400.1eV is designated as AN 3, the area of the spectral peak in the range of 403.5-406.5eV is designated as AN 4, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, IN n/IN t=AN 4/AN 1, when the ratio obtained is less than 0.01, it is believed that without such species, and the content of such species is designated as 0.
According to the present invention containing hetero atom nano-carbon material, the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum the amount of the O element determined (that is, C=O) is IO c, the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum the amount of the O element (that is, C-O) determined is IO e, IO c/IO eIn the range of 0.1-0.5, preferably in the range of 0.15-0.45, more preferably in the range of 0.3-0.45.In the present invention, by the area A of the O1s spectral peak in x-ray photoelectron power spectrumO 1Determine the total amount of O element, O1s spectral peak in x-ray photoelectron power spectrum is divided into two groups of peaks, i.e. the spectral peak (corresponding to C=O species) in the range of 531.0-532.5eV and the spectral peak (corresponding to C-O species) in the range of 532.6-533.5eV, be designated as A by the area of the spectral peak in the range of 531.0-532.5eVO 2, the area of the spectral peak in the range of 532.6-533.5eV is designated as AO 3, IO c/IO e=AO 2/AO 3。
According to the present invention containing hetero atom nano-carbon material, on the basis of this is containing the total amount of C element in hetero atom nano-carbon material, the C element determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum is (i.e., graphite mould carbon) content can be 65-96 weight %, it is preferably 70-95 weight %, more preferably 80-95 weight %, more preferably 85-94 weight %；The total content of the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum can be 4-35 weight %, preferably 5-30 weight %, more preferably 5-20 weight %, more preferably 6-15 weight %.In the present invention, by the area A of the C1s spectral peak in x-ray photoelectron power spectrumC 1Determine the total amount of C element, C1s spectral peak in x-ray photoelectron power spectrum is divided into two groups of peaks, i.e. the spectral peak (corresponding to graphite mould carbon species) in the range of 284.7-284.9eV and the spectral peak (corresponding to non-graphite type carbon species) in the range of 286.0-288.8eV, be designated as A by the area of the spectral peak in the range of 284.7-284.9eVC 2, the area of the spectral peak in the range of 286.0-288.8eV is designated as AC 3, the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum the content=A of the C element determinedC 2/AC 1, the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum the total content=A of the C element determinedC 3/AC 1。
According to the present invention containing hetero atom nano-carbon material, this contains in hetero atom nano-carbon material, the peak in the range of 288.6-288.8eV in x-ray photoelectron power spectrum the amount of the C element determined is IC c, the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum the amount of the C element determined is IC e, IC c/IC eIn the range of 0.2-0.8, preferably in the range of 0.3-0.7, more preferably in the range of 0.4-0.6.In the present invention, spectral peak (corresponding to agraphitic carbon species) in the range of 286.0-288.8eV in x-ray photoelectron power spectrum is further divided into two groups of peaks, i.e. the spectral peak (corresponding to hydroxyl and ether type carbon species) in the range of 286.0-286.2eV and the spectral peak (corresponding to carboxyl, acid anhydride and ester type carbon species) in the range of 288.6-288.8eV, be designated as A by the area of the spectral peak in the range of 286.0-286.2eVC 4, the area of the spectral peak in the range of 288.6-288.8eV is designated as AC 5, IC c/IC e=AC 5/AC 4。
In the present invention, the position at each peak be can determine that by the combination corresponding to the summit at this peak, the peak that scope determines by mentioned earlier refer to the combination corresponding to summit can peak in such range, a peak can be included within the range, it is also possible to include plural peak.Such as: the peak in the range of 398.5-400.1eV refers to that the combination corresponding to summit can be in the whole peaks in the range of 398.5-400.1eV.
Can exist with common various forms containing hetero atom nano-carbon material according to the present invention, it is specifically as follows but is not limited to containing hetero atom CNT, containing hetero atom Graphene, containing hetero atom thin layer graphite, containing hetero atom nano carbon particle, containing hetero atom carbon nano-fiber, containing one or more the combination in hetero atom Nano diamond and doped fullerene.Described can be containing hetero atom SWCN, containing hetero atom double-walled carbon nano-tube with containing one or more the combination in hetero atom multi-walled carbon nano-tubes containing heteroatomic CNT.According to the present invention containing hetero atom nano-carbon material, be preferably the multi-walled carbon nano-tubes Han hetero atom.
According to the present invention containing hetero atom nano-carbon material, it is preferable that the described specific surface area containing hetero atom multi-walled carbon nano-tubes is 50-500m2/ g, so can improve this catalytic performance containing hetero atom nano-carbon material, further especially as the catalytic performance of the catalyst of hydrocarbons dehydrogenation reaction.It is highly preferred that this specific surface area containing hetero atom multi-walled carbon nano-tubes is 80-300m2/g.It is further preferred that this specific surface area containing hetero atom multi-walled carbon nano-tubes is 90-200m2/g.In the present invention, described specific surface area is measured by nitrogen adsorption BET method.
According to the present invention containing hetero atom nano-carbon material, the described multi-walled carbon nano-tubes containing hetero atom weight-loss ratio in the temperature range of 400-800 DEG C is w800, the weight-loss ratio in the temperature range of 400-500 DEG C is w500, w500/w800Preferably in the range of 0.01-0.5, so it is obtained in that more preferable catalytic effect, during in particular as the catalyst of hydrocarbons dehydrogenation reaction, more preferable catalytic effect can be obtained.It is highly preferred that w500/w800More preferably in the range of 0.02-0.2, further preferably in the range of 0.1-0.15.In the present invention, w800=W800-W400, w500=W500-W400, W400For the mass loss rate measured at a temperature of 400 DEG C, W800For the mass loss rate measured at a temperature of 800 DEG C, W500For the mass loss rate measured at a temperature of 500 DEG C；Described weight-loss ratio uses thermogravimetric analyzer to measure in air atmosphere, and test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample is depressed in the temperature of 150 DEG C and 1 standard atmosphere before testing and is dried 3 hours in helium atmosphere.
The present invention one preferred embodiment in, described containing hetero atom nano-carbon material be preferably the multi-walled carbon nano-tubes Han hetero atom, this specific surface area containing hetero atom multi-walled carbon nano-tubes is 50-500m2/ g, preferably 80-300m2/ g, more preferably 90-200m2/g；And w500/w800In the range of 0.01-0.5, preferably in the range of 0.02-0.2, more preferably in the range of 0.1-0.15.
Can be customary amount according to the present invention containing hetero atom nano-carbon material, such as other nonmetallic heteroatoms content such as sulphur atom and phosphorus atoms.Usually, according to the present invention containing in hetero atom nano-carbon material, the total amount of other nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) outside oxygen atom and nitrogen-atoms can be below 0.5 weight %, below preferably 0.2 weight %.According to the present invention containing hetero atom nano-carbon material, a small amount of metallic atom can also be contained, the catalyst that these metallic atom multi-sources use in time preparing nano-carbon material, the content of described metallic atom is generally below 0.5 weight %, below preferably 0.2 weight %.
According to the second aspect of the invention, the invention provides a kind of preparation method containing hetero atom nano-carbon material, the method includes reacting a kind of aqueous dispersions being dispersed with raw material nano material with carbon element in hermetic container, and described aqueous dispersions is dissolved with HNO3。
The method according to the invention, the solids content of described aqueous dispersions is can be as the criterion dispersed for raw material nano material with carbon element.Preferably, raw material nano material with carbon element: HNO3Weight ratio be 1:0.1-10.It is highly preferred that raw material nano material with carbon element: HNO3Weight ratio be 1:0.15-5.It is further preferred that raw material nano material with carbon element: HNO3Weight ratio be 1:0.5-3.It is further preferred that raw material nano material with carbon element: HNO3Weight ratio be 1:1-2.
Method according to the invention it is possible to the consumption of water is selected according to the amount of raw material nano material with carbon element.Preferably, raw material nano material with carbon element: H2The weight ratio of O is 1:1-200, and when the consumption of water is within the scope of this, nano-carbon material configuration retentivity in processing procedure is more preferable, such as: when raw material nano material with carbon element is CNT, substantially without cut-off in processing procedure.It is highly preferred that raw material nano material with carbon element: H2The weight ratio of O is 1:2-100.It is further preferred that raw material nano material with carbon element: H2The weight ratio of O is 1:3-50.It is further preferred that raw material nano material with carbon element: H2The weight ratio of O is 1:3-10.Furthermore it is also possible to according to HNO3Consumption the consumption of water is adjusted, usually, HNO in aqueous dispersions3Mass concentration be preferably not higher than 50 weight %, more preferably not above 40 weight %.
The method according to the invention, the condition of described reaction is as the criterion with the content that be enough to improve oxygen atom and nitrogen-atoms in raw material nano material with carbon element.Preferably, in course of reaction, the temperature of described aqueous dispersions is in the range of 100-250 DEG C.The temperature of described aqueous dispersions be in above-mentioned within the scope of time, the oxygen atom in raw material nano material with carbon element and nitrogen atom content can not only be effectively improved, and the configuration of raw material nano material with carbon element will not be produced and significantly affect.It is highly preferred that in course of reaction, the temperature of described aqueous dispersions is in the range of 120-220 DEG C.
The method according to the invention, the persistent period of described reaction can select according to the temperature of reaction, can introduce enough oxygen atoms in raw material nano material with carbon element and nitrogen-atoms is as the criterion.Usually, the persistent period of described reaction can be in the range of 0.5-144 hour, preferably in the range of 2-72 hour, more preferably in the range of 10-30 hour.
Method according to the invention it is possible to use conventional various methods to form described aqueous dispersions, such as, raw material nano material with carbon element can be dispersed in water (preferably deionized water), be subsequently adding HNO3Mix homogeneously, thus obtain described aqueous dispersions.In order to improve the dispersion effect of raw material nano material with carbon element further, shorten the scattered time simultaneously, the method for sonic oscillation can be used to be dispersed in water by raw material nano material with carbon element.The condition of described sonic oscillation can be conventional selection, and usually, the frequency of described sonic oscillation can be 10-100kHz, preferably 40-60kHz, and the persistent period of described sonic oscillation can be 0.1-12 hour, preferably 0.5-2 hour.HNO3Typically provide in form of an aqueous solutions.
The method according to the invention, in described raw material nano material with carbon element, the content of O element and N element is not particularly limited, and can be conventional selection.Usually, in described raw material nano material with carbon element, the content of O element is not higher than 1.2 weight %, preferably 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 above 0.1 weight %, the most not higher than 0.05 weight %.The method according to the invention, in described raw material nano material with carbon element, the total amount (counting with element) of remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside oxygen atom and nitrogen-atoms can be as customary amount.Usually, in described raw material nano material with carbon element, the total amount of remaining nonmetallic heteroatoms outside oxygen atom and nitrogen-atoms is not higher than 0.5 weight %, it is preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, the most not higher than 0.05 weight %.The method according to the invention, described raw material nano material with carbon element is according to the difference in source, it is also possible to containing some metallic elements, and these metallic elements are typically derived from the catalyst used when preparing raw material nano material with carbon element, its content is typically below 2 weight %, preferably below 0.5 weight %.
The method according to the invention, raw material nano material with carbon element can use method commonly used in the art to carry out pretreatment (such as washing), to remove some impurity of raw material nano carbon material surface before use；Can not also carry out pretreatment, directly use, in embodiment disclosed by the invention, raw material nano material with carbon element does not the most all carry out pretreatment.
Method according to the invention it is possible to the nano-carbon material of various existing forms is processed, thus improve the oxygen atom in this nano-carbon material and nitrogen atom content.Described raw material nano material with carbon element can be but be not limited to one or more the combination in CNT, Graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene.Described CNT can be one or more the combination in SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes.Preferably, described raw material nano material with carbon element is CNT, more preferably multi-walled carbon nano-tubes.
In a preferred embodiment, described raw material nano material with carbon element is multi-walled carbon nano-tubes, and the specific surface area of described multi-walled carbon nano-tubes is 20-500m2/ g, preferably 50-300m2/ g, more preferably 100-200m2/g.The specific surface area of described many walls nano-carbon material be in above-mentioned within the scope of time, the nano-carbon material containing hetero atom finally given has and is preferably catalyzed activity, particularly when the catalyst as the dehydrogenation reaction of hydrocarbons, demonstrates higher catalysis activity.
When described raw material nano material with carbon element is multi-walled carbon nano-tubes, described multi-walled carbon nano-tubes weight-loss ratio in the temperature range of 400-800 DEG C is w800, the weight-loss ratio in the temperature range of 400-500 DEG C is w500, w500/w800Preferably in the range of 0.01-0.5, more preferably in the range of 0.02-0.2, more preferably less than 0.15.The nano-carbon material containing hetero atom thus prepared demonstrates more preferable catalytic effect, during in particular as the catalyst of hydrocarbons dehydrogenation reaction, can obtain more preferable catalytic reaction effect.
In a kind of embodiment being more highly preferred to of the present invention, described raw material nano material with carbon element is multi-walled carbon nano-tubes, and the specific surface area of described multi-walled carbon nano-tubes is 20-500m2/ g, preferably 50-300m2/ g, more preferably 100-200m2/g；Described multi-walled carbon nano-tubes weight-loss ratio in the temperature range of 400-800 DEG C is w800, the weight-loss ratio in the temperature range of 400-500 DEG C is w500, w500/w800Preferably in the range of 0.01-0.5, more preferably in the range of 0.02-0.2, more preferably less than 0.15.
The method according to the invention, described reaction is carried out in hermetic container.Described reaction can be carried out under self-generated pressure (i.e., the most additionally applying pressure), it is also possible to carries out under pressure.Preferably, described reaction is carried out at autogenous pressures.Described hermetic container can be the common reactor that can realize sealing and heating, such as autoclave.
The method according to the invention, it is also possible to include isolating solid matter from the mixture that reaction obtains, and isolated solid matter is dried, thus obtain the described nano-carbon material Han hetero atom.
Conventional solid-liquid separating method can be used to isolate solid matter from the mixture that reaction obtains, such as one or more the combination in centrifugal, filtration and decant.
Described dry condition can be conventional selection, is as the criterion with the volatile material that can remove in isolated solid matter.Usually, described being dried can be carried out at a temperature of 50-200 DEG C, preferably carries out at a temperature of 80-180 DEG C, more preferably carries out at a temperature of 100-150 DEG C.The described dry persistent period can select according to dry temperature and mode.Usually, the described dry persistent period can be 0.5-48 hour, preferably 3-24 hour, more preferably 5-12 hour.Described being dried can be carried out under normal pressure (that is, 1 normal atmosphere), it is also possible to carries out at reduced pressure.From the angle improving the efficiency being dried further, described being dried is carried out the most at reduced pressure.
The method according to the invention, can be effectively improved the oxygen atom in raw material nano material with carbon element and nitrogen atom content, will not produce the configuration of raw material nano material with carbon element simultaneously and significantly affect.
Thus, according to the third aspect of the present invention, the invention provides one by prepared according to the methods of the invention nano-carbon material Han hetero atom.
According to the fourth aspect of the present invention, the invention provides a kind of nano-carbon material Han hetero atom, this contain hetero atom nano-carbon material be by according to first aspect of the present invention containing hetero atom nano-carbon material or prepared according to the carrying out roasting containing hetero atom nano-carbon material of third aspect of the present invention.
Described roasting can be carried out under normal conditions.Preferably, described roasting is carried out at a temperature of 250-500 DEG C.It is highly preferred that described roasting is carried out at a temperature of 300-450 DEG C.It is further preferred that described roasting is carried out at a temperature of 350-450 DEG C.The persistent period of described roasting can select according to the temperature of roasting.Usually, the persistent period of described roasting can be 1-24 hour, preferably 2-12 hour, more preferably 2-5 hour.Described roasting can be carried out in oxygen-containing atmosphere, it is also possible to carries out in the atmosphere formed by noble gas.Described oxygen-containing atmosphere can be air atmosphere；The mixed atmosphere can also being mixed to form with noble gas for oxygen, in described mixed atmosphere, the content of oxygen can be 0.1-22 volume %.Described noble gas can include but not limited to nitrogen and/or rare gas, and described rare gas can be argon and/or helium.Angularly consider from convenience and cost, it is preferable that described roasting is carried out in oxygen-containing atmosphere (such as air atmosphere).
Containing hetero atom nano-carbon material or the nano-carbon material containing hetero atom prepared by the method for the present invention, there is good catalytic performance according to the present invention, in hydrocarbons dehydrogenation reaction, particularly demonstrate higher catalysis activity.
Catalyst can be directly used as containing hetero atom nano-carbon material containing hetero atom nano-carbon material or by prepared by the method for the present invention, it is also possible to use with the form of preformed catalyst according to the present invention.Described preformed catalyst can contain the with good grounds present invention containing hetero atom nano-carbon material or by the method for the present invention prepare containing hetero atom nano-carbon material and binding agent.Described binding agent can select according to the specifically used occasion of this preformed catalyst, disclosure satisfy that use requirement is as the criterion, such as, can be organic binder bond and/or inorganic binder.Described organic binder bond can be common various polymer-type binding agents, and described inorganic binder can be common various heat-resistant inorganic oxides, such as aluminium oxide and/or silicon oxide.Described preformed catalyst be to hydrocarbon dehydrogenation reaction (such as direct dehydrogenation reaction and oxidative dehydrogenation), particularly oxidative dehydrogenation is had the preformed catalyst of catalytic action time, described binding agent is preferably inorganic binder.In described preformed catalyst, content containing hetero atom nano-carbon material can select according to specifically used requirement, is not particularly limited, usually, on the basis of the total amount of described preformed catalyst, the described content containing hetero atom nano-carbon material can be 5-95 weight %.
According to the fifth aspect of the present invention, the invention provides according to first aspect of the present invention containing hetero atom nano-carbon material, according to third aspect of the present invention containing hetero atom nano-carbon material or according to the 4th aspect of the present invention containing hetero atom nano-carbon material as the application of the catalyst of hydrocarbon dehydrogenation reaction.
Application according to the present invention, the described nano-carbon material containing hetero atom is used directly for hydrocarbon dehydrogenation reaction, it is also possible to for hydrocarbon dehydrogenation reaction after molding.Described dehydrogenation reaction can be carried out in the presence of oxygen, it is also possible to carries out the most in the presence of oxygen.Preferably, described dehydrogenation reaction is carried out in the presence of oxygen, so can obtain more preferable catalytic effect.
According to the sixth aspect of the invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, under conditions of the method is included in presence or absence oxygen, under hydrocarbon dehydrogenation reaction conditions, hydrocarbon is contacted with the nano-carbon material containing hetero atom containing hetero atom nano-carbon material or according to the 4th aspect of the present invention containing hetero atom nano-carbon material, according to third aspect of the present invention according to first aspect of the present invention.
Hydrocarbon dehydrogenation reaction method according to the present invention, the described nano-carbon material containing hetero atom is used directly for contacting with hydrocarbon, it is also possible to be used for contacting with hydrocarbon containing after hetero atom nano-carbon material molding by described.
Hydrocarbon dehydrogenation reaction method according to the present invention can carry out dehydrogenation to polytype hydrocarbon, thus obtains unsaturated hydrocarbons, such as alkene.The method according to the invention is particularly suitable for alkane is carried out dehydrogenation, thus obtains alkene.The method according to the invention, described hydrocarbon is preferably alkane, such as C2-C12Alkane.nullSpecifically，Described hydrocarbon can be but be not limited to ethane、Propane、Normal butane、Iso-butane、Pentane、Isopentane、Neopentane、Pentamethylene.、Normal hexane、2-methylpentane、3-methylpentane、2,3-dimethylbutane、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-dimethylhexane、2,4-dimethylhexane、2,5-dimethylhexane、3-ethyl hexane、2,2,3-trimethylpentane、2,3,3-trimethylpentane、2,4,4-trimethylpentane、2-methyl-3-ethylpentane、N-nonane、2-methyloctane、3-methyloctane、4-methyloctane、2,3-dimethyl heptane、2,4-dimethyl heptane、3-ethyl heptane、4-ethyl heptane、2,3,4-trimethyl cyclohexane、2,3,5-trimethyl cyclohexane、2,4,5-trimethyl cyclohexane、2,2,3-trimethyl cyclohexane、2,2,4-trimethyl cyclohexane、2,2,5-trimethyl cyclohexane、2,3,3-trimethyl cyclohexane、2,4,4-trimethyl cyclohexane、2-methyl-3-ethyl hexane、2-methyl-4-ethyl hexane、3-methyl-3-ethyl hexane、3-methyl-4-ethyl hexane、3,3-diethylpentane、1-methyl-2-ethyl cyclohexane、1-methyl-3-ethyl cyclohexane、1-methyl-4-ethyl cyclohexane、N-pro-pyl hexamethylene、Isopropyl cyclohexane、Trimethyl-cyclohexane (includes the various isomers of trimethyl-cyclohexane，Such as 1,2,3-trimethyl-cyclohexane、1,2,4-trimethyl-cyclohexane、1,2,5-trimethyl-cyclohexane、1,3,5-trimethyl-cyclohexane)、N-decane、2-methylnonane、3-methylnonane、4-methylnonane、5-methylnonane、2,3-dimethyl octane、2,4-dimethyl octane、3-ethyl octane、4-ethyl octane、2,3,4-trimethylheptane、2,3,5-trimethylheptane、2,3,6-trimethylheptane、2,4,5-trimethylheptane、2,4,6-trimethylheptane、2,2,3-trimethylheptane、2,2,4-trimethylheptane、2,2,5-trimethylheptane、2,2,6-trimethylheptane、2,3,3-trimethylheptane、2,4,4-trimethylheptane、2-methyl-3-ethyl heptane、2-methyl-4-ethyl heptane、2-methyl-5-ethyl heptane、3-methyl-3-ethyl heptane、4-methyl-3-ethyl heptane、5-methyl-3-ethyl heptane、4-methyl-4-ethyl heptane、4-propyl group heptane、3,3-diethylhexane、3,4-diethylhexane、2-methyl-3,3-diethylpentane、Vinylbenzene、1-phenyl-propane、2-phenyl-propane、1-phenyl butane、2-phenyl butane、1-phenyl pentane、One or more combination in 2-phenyl pentane and 3-phenyl pentane.
It is highly preferred that described hydrocarbon is one or more in propane, normal butane, iso-butane and vinylbenzene.It is further preferred that described hydrocarbon is normal butane.
Hydrocarbon dehydrogenation reaction method according to the present invention, described reaction can be carried out under conditions of there is oxygen, it is also possible to carries out under conditions of there is not oxygen.Preferably, according to the hydrocarbon dehydrogenation reaction method of the present invention, carry out under conditions of there is oxygen.The present invention method exist carry out under conditions of oxygen time, the consumption of oxygen can be conventional selection.Usually, hydrocarbon can be 0.01-100:1, preferably 0.1-10:1, more preferably 0.2-5:1, most preferably 0.5-2:1 with the mol ratio of oxygen.
Hydrocarbon dehydrogenation reaction method according to the present invention, can be sent into hydrocarbon and optional oxygen in reactor and containing hetero atom nano-carbon material haptoreaction by carrier gas.Described carrier gas can be conventional at reaction conditions will not be with reactant and reaction product generation chemical interaction and the gas that will not decompose, such as one or more the combination in nitrogen, carbon dioxide, rare gas and steam.The consumption of described carrier gas can be conventional selection.Usually, the content of carrier gas can be with 30-99.5 volume %, preferably 50-99 volume %, more preferably 70-98 volume %.
Hydrocarbon dehydrogenation reaction method according to the present invention, the temperature of described contact can be conventional selection, be enough to make hydrocarbon generation dehydrogenation reaction be as the criterion.Usually, described contact can be carried out at a temperature of 200-650 DEG C, preferably carries out at a temperature of 300-600 DEG C, more preferably carries out at a temperature of 350-550 DEG C, as further preferably carried out at a temperature of 400-450 DEG C when hydrocarbon is butane.
Hydrocarbon dehydrogenation reaction method according to the present invention, described contact can be carried out in fixed bed reactors, it is also possible to carries out in a fluidized bed reactor, is not particularly limited.Preferably, described contact is carried out in fixed bed reactors.
Hydrocarbon dehydrogenation reaction method according to the present invention, the persistent period of described contact can select according to the temperature of contact, when carrying out in fixed bed reactors such as described contact, can represent the persistent period of contact with volume space velocity during the gas fed.Usually, during the gas of charging, volume space velocity can be 0.1-10000h-1, preferably 1-6000h-1, more preferably 5-5000h-1, more preferably 10-4000h-1, such as 400-600h-1。
Describe the present invention in detail below in conjunction with embodiment, but and be not so limited the scope of the present invention.
In following example and comparative example, X-ray photoelectron spectroscopic analysis is tested on the ESCALab250 type x-ray photoelectron spectroscopy equipped with ThermoAvantageV5.926 software of ThermoScientific company, excitaton source is monochromatization AlK α X-ray, energy is 1486.6eV, power is 150W, penetrating energy used by narrow scan is 30eV, and base vacuum when analyzing test is 6.5 × 10-10Mbar, C1s peak (284.0eV) correction of electron binding energy simple substance carbon, process in ThermoAvantage software enterprising row data, use sensitivity factor method to carry out quantitative analysis in analyzing module.Sample is depressed in the temperature of 150 DEG C and 1 standard atmosphere before testing and is dried 3 hours in helium atmosphere.
In following example and comparative example, thermogravimetric analysis is carried out on TA5000 thermal analyzer, and test condition is air atmosphere, and programming rate is 10 DEG C/min, and temperature range is that room temperature (25 DEG C) is to 1000 DEG C.Sample is depressed in the temperature of 150 DEG C and 1 standard atmosphere before testing and is dried 3 hours in helium atmosphere.Use ASAP2000 type N of Micromertrics company of the U.S.2Physical adsorption appearance measurement the specific area.The high-resolution-ration transmission electric-lens using FEI Co. of the U.S. to produce analyzes raw material nano material with carbon element and the microscopic appearance containing hetero atom nano-carbon material.
Embodiment 1-15 for illustrate the present invention containing hetero atom nano-carbon material and preparation method thereof.
Embodiment 1
(1) using 20g, as the multi-walled carbon nano-tubes of raw material nano material with carbon element, (specific surface area is 136m2/ g, oxygen atom content is 0.3 weight %, nitrogen atom content is 0.02 weight %, the total content denitrogenating remaining nonmetallic heteroatoms outside atom and oxygen atom (phosphorus atoms and sulphur atom) is 0.01 weight %, metallic atom total content is 0.1 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) disperse in deionized water, carry out under the conditions of being dispersed in sonic oscillation, sonic oscillation condition includes: frequency is 40kHz, and the time is 0.5 hour.It is subsequently adding HNO3Mix homogeneously, thus obtain aqueous dispersions.Wherein, HNO3There is provided, by raw material nano material with carbon element: HNO with the form of 60 weight % aqueous solutions3: H2The weight ratio of O is that the ratio of 1:1:9 feeds intake.
(2) aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 120 DEG C, reaction 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, open reactor, reactant mixture is filtered and washs, and collect solid matter.By the solid matter collected at normal pressure (1 normal atmosphere, lower with), being dried 12 hours at a temperature of 120 DEG C, obtain containing hetero atom nano-carbon material, this contains the composition of hetero atom nano-carbon material, specific surface area and w500/w800List in Table 1.
Fig. 1 is the transmission electron microscope photo containing hetero atom nano-carbon material of preparation, and Fig. 2 is the transmission electron microscope photo of the multi-walled carbon nano-tubes as raw material nano material with carbon element.From Fig. 1 and Fig. 2 it can be seen that the microscopic pattern containing hetero atom nano-carbon material is good, show that course of reaction is little to the structure influence containing hetero atom nano-carbon material.
Comparative example 1
Aqueous dispersions same as in Example 1 is placed in the there-necked flask being equipped with condensing tube, this there-necked flask is placed in the oil bath of 120 DEG C, at ambient pressure back flow reaction 24 hours.After reaction terminates, treat that the temperature in there-necked flask is down to room temperature, reactant mixture filtered and washs, and collecting solid matter.By the solid matter collected at normal pressure, it is dried 6 hours at a temperature of 120 DEG C, obtains containing hetero atom nano-carbon material.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Comparative example 2
Using method preparation nano-carbon material Han hetero atom same as in Example 1, except for the difference that, the aqueous dispersions that step (1) is prepared does not contains HNO3。
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Comparative example 3
20g is positioned over the quartz ampoule in roaster Nei middle part (i.e. CNT both sides, quartz ampoule two ends are filled with silica wool) as the multi-walled carbon nano-tubes (with embodiment 1) of raw material nano material with carbon element, then it is passed through concentrated nitric acid (65 weight %) by dosing pump, wherein, in quartz ampoule, temperature is 150 DEG C, concentrated nitric acid flow is 15mL/min, and the time is 24 hours.After reaction terminates, after the temperature in quartz ampoule is down to room temperature, open roaster, take out CNT after the process in quartz ampoule, obtain containing hetero atom nano-carbon material.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Comparative example 4
Use method preparation nano-carbon material Han hetero atom same as in Example 1, except for the difference that, HNO3With the H of equimolar amounts2SO4Replace.Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Comparative example 5
Use method preparation nano-carbon material Han hetero atom same as in Example 1, except for the difference that, HNO3Replace with the HCl of equimolar amounts.Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Comparative example 6
Use method preparation nano-carbon material Han hetero atom same as in Example 1, except for the difference that, HNO3With the KMnO of equimolar amounts4Replace.Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Embodiment 2
Use method preparation nano-carbon material Han hetero atom same as in Example 1, except for the difference that, in step (1), the specific surface area as the multi-walled carbon nano-tubes (purchased from Shandong great Zhan nano material company limited) of raw material nano material with carbon element is 251m2/ g, the weight-loss ratio in the temperature range of 400-800 DEG C is w800, the weight-loss ratio in the temperature range of 400-500 DEG C is w500, w500/w800It is 0.33, oxygen atom content is 0.62 weight %, nitrogen atom content is 0.01 weight %, and the total content denitrogenating remaining nonmetallic heteroatoms outside atom and oxygen atom (phosphorus atoms and sulphur atom) is 0.01 weight %, and metallic atom total content is 0.08 weight %.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Embodiment 3
Use method preparation nano-carbon material Han hetero atom same as in Example 1, except for the difference that, in step (2), the aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 100 DEG C, reaction 24 hours at autogenous pressures.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Embodiment 4
Use method preparation nano-carbon material Han hetero atom same as in Example 1, except for the difference that, in step (1), by raw material nano material with carbon element: HNO3: H2The weight ratio of O is that the ratio of 1:0.15:9.85 feeds intake.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Embodiment 5
(1) using 20g, as the multi-walled carbon nano-tubes of raw material nano material with carbon element, (specific surface area is 103m2/ g, oxygen atom content is 0.2 weight %, nitrogen atom content is 0.01 weight %, the total content denitrogenating remaining nonmetallic heteroatoms outside atom and oxygen atom (phosphorus atoms and sulphur atom) is 0.04 weight %, metallic atom total content is 0.3 weight %, and the weight-loss ratio in the temperature range of 400-800 DEG C is w800, the weight-loss ratio in the temperature range of 400-500 DEG C is w500, w500/w800It is 0.07, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) it is scattered in deionized water, carry out under the conditions of being dispersed in sonic oscillation, sonic oscillation condition includes: frequency is 60kHz, and the time is 1 hour.It is subsequently adding HNO3Mix homogeneously, thus obtain aqueous dispersions.Wherein, HNO3There is provided with the form of 60 weight % aqueous solutions, raw material nano material with carbon element: HNO3: H2The weight ratio of O is 1:2:3.
(2) aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 180 DEG C, reaction 12 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, open reactor, reactant mixture is filtered, and collect solid matter.By the solid matter collected at normal pressure, being dried 6 hours at a temperature of 140 DEG C, obtain containing hetero atom nano-carbon material, this contains the composition of hetero atom nano-carbon material, specific surface area and w500/w800List in Table 1.
Comparative example 7
Aqueous dispersions same as in Example 5 is placed in the there-necked flask being equipped with condensing tube, this there-necked flask is placed in the oil bath of 180 DEG C, at ambient pressure back flow reaction 12 hours.After reaction terminates, treat that the temperature in there-necked flask is down to room temperature, reactant mixture filtered and washs, and collecting solid matter.By the solid matter collected at normal pressure, it is dried 6 hours at a temperature of 120 DEG C, obtains containing hetero atom nano-carbon material.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Embodiment 6
Use method preparation nano-carbon material Han hetero atom same as in Example 5, except for the difference that, in step (2), the aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 250 DEG C, reaction 12 hours at autogenous pressures.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Embodiment 7
Use method preparation nano-carbon material Han hetero atom same as in Example 5, except for the difference that, in step (1), the specific surface area as the multi-walled carbon nano-tubes (purchased from Shandong great Zhan nano material company limited) of raw material nano material with carbon element is 103m2/ g, w500/w800Being 0.23, oxygen atom content is 1.1 weight %, and nitrogen atom content is 0.03 weight %, and the total content denitrogenating remaining nonmetallic heteroatoms outside atom and oxygen atom (phosphorus atoms and sulphur atom) is 0.01 weight %, and metallic atom total content is 1.6 weight %.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Embodiment 8
Use method preparation nano-carbon material Han hetero atom same as in Example 5, except for the difference that, in step (1), by raw material nano material with carbon element: HNO3: H2The weight ratio of O is that the ratio of 1:3.25:5.75 feeds intake.
Composition containing hetero atom nano-carbon material, specific surface area and the w of preparation500/w800List in Table 1.
Embodiment 9
(1) using 20g, as the multi-walled carbon nano-tubes of raw material nano material with carbon element, (specific surface area is 175m2/ g, oxygen atom content is 0.3 weight %, nitrogen atom content is 0.02 weight %, the total content denitrogenating remaining nonmetallic heteroatoms outside atom and oxygen atom (phosphorus atoms and sulphur atom) is 0.01 weight %, metallic atom total content is 0.1 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.15, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) it is scattered in deionized water, wherein, carry out under the conditions of being dispersed in sonic oscillation, sonic oscillation condition includes: frequency is 60kHz, and the time is 1 hour.It is subsequently adding HNO3Mix homogeneously, thus obtain aqueous dispersions.Wherein, HNO3There is provided, by raw material nano material with carbon element: HNO with the form of 40 weight % aqueous solutions3: H2The weight ratio of O is that the ratio of 1:2:8 feeds intake.
(2) aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 220 DEG C, reaction 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, open reactor, reactant mixture is filtered, and collect solid matter.By the solid matter collected at normal pressure, being dried 8 hours at a temperature of 120 DEG C, obtain containing hetero atom nano-carbon material, this contains the composition of hetero atom nano-carbon material, specific surface area and w500/w800List in Table 1.
Embodiment 10
Prepared by embodiment 1 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Comparative example 8
Prepared by comparative example 1 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Comparative example 9
Prepared by comparative example 2 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Comparative example 10
Prepared by comparative example 3 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Comparative example 11
Prepared by comparative example 4 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Comparative example 12
Prepared by comparative example 5 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Comparative example 13
Prepared by comparative example 6 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Embodiment 11
Prepared by embodiment 2 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Embodiment 12
Prepared by embodiment 3 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Embodiment 13
Prepared by embodiment 4 containing hetero atom nano-carbon material roasting 4 hours in air atmosphere at a temperature of 380 DEG C.
Embodiment 14
Prepared by embodiment 5 containing hetero atom nano-carbon material roasting 2 hours in air atmosphere at a temperature of 450 DEG C.
Embodiment 15
Prepared by embodiment 9 containing hetero atom nano-carbon material roasting 5 hours in air atmosphere at a temperature of 420 DEG C.
Embodiment 16-30 is for illustrating the application containing hetero atom nano-carbon material and the hydrocarbon dehydrogenation reaction method of the present invention.
Embodiment 16-24
Respectively 0.2g (admission space is about 1.5mL) embodiment 1-9 is obtained containing hetero atom nano-carbon material as Catalyst packing in universal fixed bed miniature quartz pipe reactor, miniature quartz pipe reactor two end seal has quartz sand, under the conditions of 0.1MPa and 450 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 0.5 volume %, normal butane and oxygen molar ratio 0.5:1, Balance Air is nitrogen, accounts for surplus) with cumulative volume air speed as 500h-1It is passed through in reactor and reacts, continuously monitoring composition of the reactant mixture of output from reactor, and calculate n-butane conversion, total olefin selectivity and 2-butylene selectivity, react that the results are shown in Table 23 hours and 24 hours.
Comparative example 14-20
Use the method identical with embodiment 16-24 to react, except for the difference that, use the nano-carbon material containing hetero atom prepared by comparative example 1-7 as catalyst respectively.Reaction result is listed in table 2.
Comparative example 21
Use the method identical with embodiment 16-24 to react, except for the difference that, use raw material nano material with carbon element same as in Example 1 as catalyst.Reaction result is listed in table 2.
Comparative example 22
Use the method identical with embodiment 16-24 to react, except for the difference that, use raw material nano material with carbon element same as in Example 5 as catalyst.Reaction result is listed in table 2.
Embodiment 25-30
Use the method identical with embodiment 16-24 to react, except for the difference that, use the nano-carbon material containing hetero atom prepared by embodiment 10-15 as catalyst respectively.Reaction result is listed in table 3.
Comparative example 23-28
Use the method identical with embodiment 16-24 to react, except for the difference that, use the nano-carbon material containing hetero atom prepared by comparative example 8-13 as catalyst respectively.Reaction result is listed in table 3.
Comparative example 29
Use the method identical with embodiment 16-24 to react, except for the difference that, catalyst be by raw material nano material with carbon element same as in Example 1 at a temperature of 380 DEG C in air atmosphere roasting 4 hours and obtain.Reaction result is listed in table 3.
Comparative example 30
Use the method identical with embodiment 16-24 to react, except for the difference that, catalyst be by raw material nano material with carbon element same as in Example 5 at a temperature of 450 DEG C in air atmosphere roasting 2 hours and obtain.Reaction result is listed in table 3.
Table 2
Table 3
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can be carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary repetition, various possible compound modes are illustrated by the present invention the most separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (25)

1. a nano-carbon material Han hetero atom, this contains hetero atom nano-carbon material and contains C element, O element and N element, on the basis of this total amount containing hetero atom nano-carbon material and in terms of element, the content of N element is 0.2-5 weight %, the content of O element is 2-10 weight %, and the content of C element is 85-97.8 weight %；
Determined that this total amount containing the N element in hetero atom nano-carbon material is I by x-ray photoelectron power spectrumN t, the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum the amount of the N element determined is IN c, IN c/IN tIn the range of 0.6-0.95, the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum the amount of the N element determined is IN n, IN n/IN tIn the range of 0.05-0.4；
This contains in hetero atom nano-carbon material, the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum the amount of the O element determined is IO c, the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum the amount of the O element determined is IO e, IO c/IO eIn the range of 0.1-0.5；
This contains in hetero atom nano-carbon material, the peak in the range of 288.6-288.8eV in x-ray photoelectron power spectrum the amount of the C element determined is IC c, the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum the amount of the C element determined is IC e, IC c/IC eIn the range of 0.2-0.8.
The most according to claim 1 containing hetero atom nano-carbon material, wherein, IN c/IN tIn the range of 0.7-0.9, preferably in the range of 0.75-0.85；IN n/IN tIn the range of 0.1-0.3, preferably in the range of 0.15-0.25；IO c/IO eIn the range of 0.15-0.45, preferably in the range of 0.3-0.45；IC c/IC eIn the range of 0.3-0.7, preferably in the range of 0.4-0.6.
The most according to claim 1 and 2 containing hetero atom nano-carbon material, wherein, on the basis of the total amount of the C element determined by x-ray photoelectron power spectrum in this is containing hetero atom nano-carbon material, the content of the C element determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum is 65-96 weight %, it is preferably 70-95 weight %, more preferably 80-95 weight %, more preferably 85-94 weight %, the content of the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum is 4-35 weight %, it is preferably 5-30 weight %, more preferably 5-20 weight %, more preferably 6-15 weight %.
4. according to described in any one in claim 1-3 containing hetero atom nano-carbon material, wherein, by this containing hetero atom nano-carbon material total amount on the basis of and in terms of element, the content of N element is 0.5-4.5 weight %, preferably 1.5-4 weight %；The content of O element is 3-8 weight %, preferably 5-8 weight %；The content of C element is 87.5-96.5 weight %, preferably 88-93.5 weight %.
5. according to described in any one in claim 1-4 containing hetero atom nano-carbon material, wherein, this contains hetero atom nano-carbon material for containing hetero atom CNT, and this contains hetero atom nano-carbon material and is preferably the multi-walled carbon nano-tubes Han hetero atom.
The most according to claim 5 containing hetero atom nano-carbon material, wherein, the described specific surface area containing hetero atom multi-walled carbon nano-tubes is 50-500m2/ g, preferably 80-300m2/ g, more preferably 90-200m2/g。
7. according to described in claim 5 or 6 containing hetero atom nano-carbon material, wherein, the described multi-walled carbon nano-tubes containing hetero atom weight-loss ratio in the temperature range of 400-800 DEG C is w800, the weight-loss ratio in the temperature range of 400-500 DEG C is w500, w500/w800In the range of 0.01-0.5, preferably in the range of 0.02-0.2, more preferably in the range of 0.1-0.15, described weight-loss ratio measures in air atmosphere.
8. the preparation method containing hetero atom nano-carbon material, the method includes reacting a kind of aqueous dispersions being dispersed with raw material nano material with carbon element in hermetic container, is dissolved with HNO in described aqueous dispersions3, in course of reaction, the temperature of described aqueous dispersions is maintained in the range of 100-250 DEG C.
Method the most according to claim 8, wherein, raw material nano material with carbon element: HNO3Weight ratio be 1:0.1-10, preferably 1:0.15-5, more preferably 1:0.5-3, more preferably 1:1-2；Raw material nano material with carbon element: H2The weight ratio of O is 1:1-200, preferably 1:2-100, more preferably 1:3-50, more preferably 1:3-10.
The most according to claim 8 or claim 9, method, wherein, in course of reaction, the temperature of described aqueous dispersions is maintained in the range of 120-220 DEG C.
11. methods described in any one in-10 according to Claim 8, wherein, the persistent period of described reaction in the range of 0.5-144 hour, preferably in the range of 2-72 hour, more preferably in the range of 10-30 hour.
12. methods described in any one in-11 according to Claim 8, wherein, in described raw material nano material with carbon element, the content of O element is not higher than 1.2 weight %, preferably 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 above 0.1 weight %, the most not higher than 0.05 weight %.
13. methods described in any one in-12 according to Claim 8, wherein, described raw material nano material with carbon element is CNT, and described raw material nano material with carbon element is preferably multi-walled carbon nano-tubes.
14. methods according to claim 13, wherein, the specific surface area of described multi-walled carbon nano-tubes is 20-500m2/ g, preferably 50-300m2/ g, more preferably 100-200m2/g。
15. according to the method described in claim 13 or 14, and wherein, described multi-walled carbon nano-tubes weight-loss ratio in the temperature range of 400-800 DEG C is w800, the weight-loss ratio in the temperature range of 400-500 DEG C is w500, w500/w800In the range of 0.01-0.5, preferably in the range of 0.02-0.2, more preferably in the range of 0.02-0.15, described weight-loss ratio measures in air atmosphere.
16. methods described in any one in-15 according to Claim 8, wherein, the method also includes isolating solid matter from the mixture that reaction obtains, and is dried by isolated solid matter.
17. methods according to claim 16, wherein, described being dried is carried out at a temperature of 50-200 DEG C, preferably carries out at a temperature of 80-180 DEG C, more preferably carries out at a temperature of 100-150 DEG C；The described dry persistent period is 0.5-48 hour, preferably 3-24 hour, more preferably 5-12 hour.
18. 1 kinds by the method described in any one in claim 8-17 prepare containing hetero atom nano-carbon material.
19. 1 kinds of nano-carbon materials Han hetero atom, this contain hetero atom nano-carbon material be by described in any one in claim 1-7 containing carrying out roasting and prepared containing hetero atom nano-carbon material described in hetero atom nano-carbon material or claim 18.
20. is according to claim 19 containing hetero atom nano-carbon material, and wherein, described roasting is carried out at a temperature of 250-500 DEG C, preferably carries out at a temperature of 300-450 DEG C, more preferably carries out at a temperature of 350-450 DEG C；The persistent period of described roasting is 1-24 hour, preferably 2-12 hour, more preferably 2-5 hour.
In 21. claim 1-7 and 18 described in any one containing described in any one in hetero atom nano-carbon material or claim 19-20 containing hetero atom nano-carbon material as the application of the catalyst of hydrocarbon dehydrogenation reaction.
22. application according to claim 21, wherein, described dehydrogenation reaction is carried out in the presence of oxygen.
23. according to the application described in claim 21 or 22, and wherein, described hydrocarbon is alkane, preferably C2-C12Alkane, more preferably normal butane.
24. 1 kinds of hydrocarbon dehydrogenation reaction methods, under conditions of the method is included in presence or absence oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon and contacting containing the nano-carbon material containing hetero atom described in any one in hetero atom nano-carbon material or claim 19-20 described in any one in claim 1-7 and 18.
25. methods according to claim 24, wherein, described hydrocarbon is alkane, preferably C2-C12Alkane, more preferably normal butane.
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