CN105817242A - 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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CN105817242A
CN105817242A CN201510703329.9A CN201510703329A CN105817242A CN 105817242 A CN105817242 A CN 105817242A CN 201510703329 A CN201510703329 A CN 201510703329A CN 105817242 A CN105817242 A CN 105817242A
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range
weight
nano
hetero atom
carbon material
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CN105817242B (en
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史春风
荣峻峰
于鹏
谢婧新
宗明生
林伟国
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to EP16742630.3A priority Critical patent/EP3251746A4/en
Priority to KR1020177023979A priority patent/KR102485735B1/en
Priority to PCT/CN2016/000059 priority patent/WO2016119568A1/en
Priority to US15/546,791 priority patent/US10537882B2/en
Priority to JP2017539317A priority patent/JP6867948B2/en
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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

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  • Organic Chemistry (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a nanometer carbon material containing heteroatoms and a preparation method and application thereof. The nanometer carbon material containing heteroatoms comprises, by weight, 1 to 6% of O, 0 to 2% of N and 92 to 99% of C. In an XPS pattern, a ratio of O determined by peaks in a range of 531.0 to 532.5 eV to O determined by peaks in a range of 532.6 to 533.5 eV is 0.2 to 0.8; a ratio of C determined by peaks in a range of 288.6 to 288.8 eV to C determined by peaks in a range of 286.0 to 286.2 eV is 0.2 to 1; and a ratio of the amount of N determined by peaks in a range of 398.5 to 400.1 eV to the total amount of N is 0.7 to 1. The nanometer carbon material containing heteroatoms shows good catalytic performance in the dehydrogenation reaction of hydrocarbons and can obviously improve the conversion rate of raw materials and target product 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
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.
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, carbamide, tripolycyanamide) 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, carbamide, tripolycyanamide).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.
Although achieving many progress about the doping vario-property of nano-carbon material and the research of catalytic performance thereof, but some of which basic problem is built consensus not yet, still needs doping vario-property 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 not only be and little to the structure influence of nano-carbon material itself at nano-carbon material surface introducing hetero-atoms.Further object is that a kind of nano-carbon material Han hetero atom of offer, this contains hetero atom nano-carbon material when the dehydrogenation reaction of hydrocarbons, can not only obtain higher feed stock conversion, and can obtain higher selectivity of product.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 selectivity of product.
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 optional N element, on the basis of this total amount containing hetero atom nano-carbon material and in terms of element, the content of O element is 1-6 weight %, the content of N element is 0-2 weight %, and the content of C element is 92-99 weight %；
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 0.2-0.8；
Described containing 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 0.2-1；
When described containing hetero atom nano-carbon material in the content of N element be more than 0.1 weight % time, 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 0.7-1.
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, described aqueous dispersions is with or without organic base, described organic base is amine and/or quaternary ammonium base, in course of reaction, the temperature of described aqueous dispersions is maintained in the range of 80-220 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 4th 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.
The preparation method containing hetero atom nano-carbon material according to the present invention, can not only stably regulate and control and/or improve content of heteroatoms in nano-carbon material, simultaneously little to the structure influence of nano-carbon material itself, 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 feed stock conversion and selectivity of product.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo containing hetero atom nano-carbon material of preparation embodiment 1 preparation.
Fig. 2 is the transmission electron microscope photo of the raw material nano material with carbon element that preparation embodiment 1 uses.
Fig. 3 is the transmission electron microscope photo containing hetero atom nano-carbon material of preparation embodiment 7 preparation.
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, the described nano-carbon material containing hetero atom contains C element, O element and optional N element.In the present invention, term " optionally " represent with or without.On the basis of the described total amount containing hetero atom nano-carbon material and in terms of element, the content of O element is 1-6 weight %, and the content of N element is 0-2 weight %, and the content of C element is 92-99 weight %.
In one embodiment, described containing when in hetero atom nano-carbon material, the content of N element is less than 0.1 weight %, on the basis of this total amount containing hetero atom nano-carbon material and in terms of element, the content of O can be 2.5-5.8 weight %, it is preferably 3-5.6 weight %, more preferably 4.5-5.5 weight %；The content of C element can be 94.2-97.5 weight %, preferably 94.4-97 weight %, more preferably 94.5-95.5 weight %.According to this embodiment containing hetero atom nano-carbon material when the catalyst of the dehydrogenation reaction as alkane, particularly butane (such as normal butane), while obtaining higher feed stock conversion, 1-alkene (such as 1-butylene) had higher selectivity.
In a kind of embodiment being more highly preferred to, the described nano-carbon material containing hetero atom preferably comprises N element, so can improve the catalytic performance during catalyst as hydrocarbon dehydrogenation reaction further.It is highly preferred that on the basis of the described total amount containing hetero atom nano-carbon material and in terms of element, the content of O element is 2-6 weight %, preferably 3.5-5.5 weight %；The content of N element is 0.2-1.8 weight %, preferably 0.5-1.8 weight %；The content of C element is 92.2-97.8 weight %, preferably 92.7-96 weight %.
In the present invention, 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.Wherein, when the content value of mensuration is less than 0.1 weight %, the content of this element is designated as 0.
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.
Described containing 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 (that is, C=O) 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 (that is, CO) determined is IO e, IO c/IO eIn the range of 0.2-0.8.Described containing hetero atom nano-carbon material in the content of N element be less than 0.1 weight % time, IO c/IO ePreferably in the range of 0.4-0.7, more preferably in the range of 0.55-0.65.Described containing hetero atom nano-carbon material in the content of N element be more than 0.1 weight % time, IO c/IO ePreferably in the range of 0.35-0.85, more preferably in the range of 0.45-0.8.In the present invention, when representing numerical range, " ×-× in the range of " include two binary values.
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。
Described containing in hetero atom nano-carbon material, on the basis of the total amount of the C element determined by x-ray photoelectron power spectrum, 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 more than 20 weight %, it is preferably more than 40 weight %, more than more preferably 50 weight %, more preferably more than 70 weight %.The content of the C element (that is, graphite mould carbon) determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum can be below 95 weight %, below preferably 90 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 more than 5 weight %, more than preferably 10 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 below 80 weight %, below preferably 60 weight %, below more preferably 50 weight %, more preferably below 30 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。
Described containing 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 0.2-1.
Described containing hetero atom nano-carbon material in the content of N element be less than 0.1 weight % time, IC c/IC ePreferably in the range of 0.3-0.9, more preferably in the range of 0.35-0.8, further preferably in the range of 0.5-0.7.Described containing hetero atom nano-carbon material in the content of N element be more than 0.1 weight % time, IC c/IC ePreferably in the range of 0.3-0.98, more preferably in the range of 0.45-0.95.
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。
Described containing hetero atom nano-carbon material possibly together with N element time, 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 0.7-1, preferably in the range of 0.8-0.95.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 0.3, typically in the range of 0.05-0.2.
In the present invention, the area of the N1s spectral peak in x-ray photoelectron power spectrum determine total amount A of N elementN 1N1s spectral peak in x-ray photoelectron power spectrum is divided into two groups of peaks, i.e. spectral peak (corresponding to graphite mould nitrogen species) in the range of 400.6-401.5eV and the spectral peak (nitrogen species in addition to graphite mould nitrogen) in the range of 398.5-400.1eV, determine this two groups of respective areas in peak, 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, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/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.
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.
The present invention one preferred embodiment in, on the basis of the described total amount containing hetero atom nano-carbon material, the content of O element is 2-6 weight %, preferably 4-5.8 weight %, more preferably 4.5-5.5 weight %；The content of N element is 0.2-1.8 weight %, preferably 0.8-1.6 weight %, more preferably 1-1.5 weight %；The content of C element is 92.2-97.8 weight %, preferably 92.6-95.2 weight %, more preferably 93-94.5 weight %.IO c/IO ePreferably in the range of 0.3-0.8, more preferably in the range of 0.35-0.8, further preferably in the range of 0.55-0.78.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 preferably 70-90 weight %, more preferably 75-85 weight %.IC c/IC ePreferably in the range of 0.3-0.9, more preferably in the range of 0.4-0.7, further preferably in the range of 0.45-0.6.IN c/IN tPreferably in the range of 0.7-0.98, more preferably in the range of 0.75-0.96, further preferably in the range of 0.8-0.95.The nano-carbon material containing hetero atom according to this preferred implementation is particularly suitable as the catalyst of butane (such as normal butane) dehydrogenation reaction, particularly alkene particularly butadiene is had higher selectivity.
In another preferred embodiment of the present invention, on the basis of the described total amount containing hetero atom nano-carbon material, the content of O element is 2-6 weight %, preferably 3-5.5 weight %, more preferably 3.5-5 weight %；The content of N element is 0.3-2 weight %, preferably 0.4-1.8 weight %, more preferably 0.5-1.5 weight %；The content of C element is 92-97.7 weight %, preferably 92.7-96.6 weight %, more preferably 93.5-96 weight %.IO c/IO ePreferably in the range of 0.3-0.8, more preferably in the range of 0.4-0.78, further preferably in the range of 0.45-0.75.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 preferably 70-90 weight %, more preferably 70-85 weight %.IC c/IC ePreferably in the range of 0.3-0.9, more preferably in the range of 0.4-0.8, further preferably in the range of 0.45-0.6.IN c/IN tPreferably in the range of 0.7-0.95, more preferably in the range of 0.7-0.9, further preferably in the range of 0.8-0.9.The nano-carbon material containing hetero atom according to this preferred implementation is particularly suitable as the catalyst of propane (such as n-propane) dehydrogenation reaction, particularly to C3Alkene has higher selectivity.
The present invention another preferred embodiment in, on the basis of the described total amount containing hetero atom nano-carbon material, the content of O element is 3-6 weight %, preferably 4-5.8 weight %, more preferably 4.5-5.5 weight %；The content of N element is 0.5-2 weight %, preferably 1-2 weight %, more preferably 1.2-1.8 weight %；The content of C element is 92-96.5 weight %, preferably 92.2-95 weight %, more preferably 92.7-94.3 weight %.IO c/IO ePreferably in the range of 0.3-0.8, more preferably in the range of 0.4-0.75, further preferably in the range of 0.6-0.7.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 preferably 70-80 weight %, more preferably 75-80 weight %.IC c/IC ePreferably in the range of 0.4-0.98, more preferably in the range of 0.7-0.98, further preferably in the range of 0.85-0.95.IN c/IN tPreferably in the range of 0.7-0.95, more preferably in the range of 0.75-0.9, further preferably in the range of 0.8-0.85.The nano-carbon material containing hetero atom according to this preferred implementation is particularly suitable as the catalyst of vinylbenzene dehydrogenation reaction, particularly has higher selectivity to styrene.
Described can exist with common various forms containing hetero atom nano-carbon material, be specifically as follows but be 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.
From improving feed stock conversion and the angle of selectivity of product further, the described specific surface area containing hetero atom multi-walled carbon nano-tubes is preferably 50-500m2/ g, more preferably 80-300m2/ g, more preferably 100-200m2/g.In the present invention, specific surface area is measured by nitrogen adsorption BET method.
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.It is highly preferred that the weight-loss ratio that the described multi-walled carbon nano-tubes containing hetero atom is 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/w800More preferably in the range of 0.02-0.2.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 preferably 50-500m2/ g, more preferably 80-300m2/ g, more preferably 100-200m2/g；And w500/w800Preferably in the range of 0.01-0.5, more preferably in the range of 0.02-0.2.
Described containing in hetero atom nano-carbon material, to oxygen atom and nitrogen-atoms outside other nonmetallic heteroatoms, such as sulphur atom and phosphorus atoms, its content can be customary amount.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, in addition to aforesaid metal elements, it is also possible to containing other metallic atom, other metallic atom described can be such as derive from when preparing nano-carbon material use catalyst.The content of other metallic atom described is generally below 0.5 weight %, below preferably 0.2 weight %, more preferably below 0.1 weight %.
According to the second aspect of the invention, the invention provides a kind of preparation method containing hetero atom nano-carbon material: being reacted in hermetic container by a kind of aqueous dispersions being dispersed with raw material nano material with carbon element, described aqueous dispersions is with or without organic base.
Disperse medium in described aqueous dispersions can be water, it is also possible to for the aqueous solution containing at least one organic base.
When the disperse medium of described aqueous dispersions is water, can efficiently control and/or improve the oxygen atom content in raw material nano material with carbon element, using the catalyst reacted as hydrocarbon such as butane dehydrogenation containing hetero atom nano-carbon material of final preparation, can effectively improve catalytic performance.From improve further final preparation containing hetero atom nano-carbon material as the angle of the catalysis activity during catalyst of hydrocarbon dehydrogenation reaction, raw material nano material with carbon element: H2The weight ratio of O is preferably in the range of 1:2-200, more preferably in the range of 1:5-100, further preferably in the range of 1:10-50.Furthermore it is also possible to be adjusted the consumption of water according to the kind of organic base, so that described organic base can be uniformly dispersed in water and is as the criterion.
Disperse medium at described aqueous dispersions contain water and be dissolved in the water organic base time, using catalyst react as hydrocarbon such as butane dehydrogenation containing hetero atom nano-carbon material of final preparation, the further catalytic performance improved can be obtained.From improve further final preparation containing hetero atom nano-carbon material as the angle of the catalytic performance during catalyst of hydrocarbon dehydrogenation reaction, raw material nano material with carbon element: the weight ratio of organic base is preferably in the range of 1:0.05-20, more preferably in the range of 1:0.1-10, further preferably in the range of 0.5-5.
Described organic base is selected from amine and quaternary ammonium base.
Described quaternary ammonium base is specifically as follows the compound shown in Formulas I:
In Formulas I, R1、R2、R3And R4Can be each C1-C20Alkyl (include C1-C20Straight chained alkyl and C3-C20Branched alkyl) or C6-C12Aryl.Described C1-C20The instantiation of alkyl can include but not limited to: one or more in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl, n-hexyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-octadecane base and AI3-28404 base.Described C6-C12The instantiation of aryl can include but not limited to phenyl, naphthyl, aminomethyl phenyl and ethylphenyl.Preferably, R1、R2、R3And R4It is respectively C1-C10Alkyl (include C1-C10Straight chained alkyl and C3-C10Branched alkyl).It is further preferred that R1、R2、R3And R4It is respectively C1-C6Alkyl (include C1-C6Straight chained alkyl and C3-C6Branched alkyl).
Described amine refers to that the one, two or three hydrogen in amino molecule is replaced by organic group and the material that formed, and described organic group can form circulus with nitrogen atom bonding.Described organic group can be to replace (as hydroxyl replaces) or unsubstituted aliphatic alkyl and/or replace (as hydroxyl replaces) or unsubstituted aromatic hydrocarbyl, described aliphatic alkyl can be replace (as hydroxyl replaces) or unsubstituted representative examples of saturated aliphatic chain alkylene, replace (as hydroxyl replaces) or unsubstituted unsaturated aliphatic chain alkylene, replace (as hydroxyl replaces) or unsubstituted saturated alicyclic hydrocarbon base and replace in (such as hydroxyl replacement) or unsubstituted unsaturated lipid cyclic hydrocarbon radical one or more.Specifically, described amine can be replace (as hydroxyl replace) or unsubstituted representative examples of saturated aliphatic amine, replace (as hydroxyl replace) or unsubstituted unsaturated aliphatic amine, replace (as hydroxyl replace) or unsubstituted saturated fat cyclammonium, replace (as hydroxyl replace) or unsubstituted unsaturated lipid cyclammonium, replace (as hydroxyl replace) or unsubstituted heterocyclic amine and replace (as hydroxyl replace) or unsubstituted arylamine in one or more.
Described unsaturated aliphatic amine refers to the aliphatic streptamine in molecular structure containing unsaturated group, and described unsaturated group is preferably thiazolinyl (that is ,-C=C-).The quantity of described unsaturated group and amino can be each one or more, is not particularly limited.
nullThe method according to the invention，The instantiation of described organic base can include but not limited to methylamine、Dimethylamine、Trimethylamine、Ethamine、Diethylamine、Triethylamine、N-propylamine、Di-n-propylamine、Tri-n-Propylamine、2-aminopropane.、Diisopropylamine、N-butylamine、Di-n-butyl amine、Tri-n-butyl amine、Sec-butylamine、Diisobutyl amine、Triisobutyl amine、Tert-butylamine、N-amylamine、Two n-amylamines、Tri-n-amyl amine、Neopentyl amine、Isobutylcarbylamine、Di-iso-amylamine、Triisoamylamine、Tertiary amylamine、N-hexylamine、1-Aminooctane、Positive nonyl amine、N-Decylamine、N-undecane base amine、Dodecyl amine、Dodecyl-dimethyl amine、N-tridecane base amine、N-tetradecane base amine、Pentadecane base amine、N-hexadecyl amine、Monoethanolamine、Triethanolamine、Triisopropanolamine、Diethanolamine、Two normal propyl alcohol amine、Three normal propyl alcohol amine、Two n-butyl alcohol amine、Three n-butyl alcohol amine、Dodecyl-dimethyl amine、Tetradecyldimethylamine、Hexadecyldimethyl benzyl ammonium amine、Ethylenediamine、Propane diamine、Butanediamine、Pentanediamine、Hexamethylene diamine、Substituted or unsubstituted pyrroles、Substituted or unsubstituted nafoxidine、Substituted or unsubstituted pyridine、Substituted or unsubstituted hexahydropyridine、Substituted or unsubstituted imidazoles、Substituted or unsubstituted pyrazoles、Substituted or unsubstituted quinoline、Substituted or unsubstituted dihydroquinoline、Substituted or unsubstituted tetrahydroquinoline、Substituted or unsubstituted decahydroquinoline、Substituted or unsubstituted isoquinolin、Substituted or unsubstituted pyrimidine、Aniline、Diphenylamines、Benzidine、O-phenylenediamine、M-diaminobenzene.、P-phenylenediamine、O-toluidine、M-toluidine、Open-chain crown ether、2,3-dimethylaniline、2,4-dimethylaniline、2,5-dimethylaniline、2,6-dimethylaniline、3,4-dimethylaniline、3,5-dimethylaniline、2,4,6-trimethylaniline、O ethyl aniline、N-butylaniline、2,6-diethylaniline、Cyclohexylamine、Aminocyclopentane、Hexamethylenetetramine、Diethylenetriamine、Triethylene tetramine、Tetramethylammonium hydroxide、Tetraethyl ammonium hydroxide、TPAOH (includes its various isomers，Such as four n-pro-pyl ammonium hydroxide and tetra isopropyl ammonium hydroxide)、TBAH (includes its various isomers，Such as 4-n-butyl ammonium hydroxide、Four sec-butyl ammonium hydroxide、Four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide (including its various isomers) in one or more.
The method according to the invention, described amine is preferably the compound shown in the compound shown in Formula II, formula III and general formula R12(NH2)2Represent material in one or more,
In Formula II, R5、R6And R7It is respectively H, C1-C6Alkyl or C6-C12Aryl, and R5、R6And R7It is asynchronously H.In the present invention, C1-C6The instantiation of alkyl can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl and n-hexyl.In the present invention, C6-C12The instantiation of aryl include but not limited to phenyl, naphthyl, aminomethyl phenyl and ethylphenyl.
In formula III, R8、R9And R10It is respectively-R11OH or hydrogen, and R8、R9And R10In at least one be-R11OH, R11For C1-C4Alkylidene.In the present invention, C1-C4Alkylidene include C1-C4Straight-chain alkyl-sub-and C3-C4Branched alkylidene, its instantiation can include but not limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene, sub-normal-butyl, isobutylidene and the sub-tert-butyl group.
General formula R12(NH2)2In, R12Can be C1-C6Alkylidene or C6-C12Arlydene.In the present invention, C1-C6Alkylidene include C1-C6Straight-chain alkyl-sub-and C3-C6Branched alkylidene, its instantiation can include but not limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene, sub-normal-butyl, isobutylidene, the sub-tert-butyl group, sub-n-pentyl and sub-n-hexyl.In the present invention, C6-C12The instantiation of arlydene include but not limited to phenylene and naphthylene.
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 80-220 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/or 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 120-180 DEG C.
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/or nitrogen-atoms is as the criterion.Usually, the persistent period of described reaction can be in the range of 0.5-96 hour, preferably in the range of 2-72 hour, more preferably in the range of 20-50 hour.
In a preferred embodiment, described organic base is the quaternary ammonium base shown in Formulas I, preferably one or more in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH and four pentyl ammonium hydroxide, the nano-carbon material containing hetero atom thus prepared is particularly suitable as the catalyst of butane dehydrogenation reaction, can obtain higher butadiene selective.This preferred embodiment in, raw material nano material with carbon element: the weight ratio of organic base is preferably within the scope of 1:0.1-10, more preferably in the range of 0.5-5.This preferred embodiment in, in course of reaction, the temperature of aqueous dispersions is preferably in the range of 90-210 DEG C, more preferably in the range of 140-180 DEG C.
In another preferred embodiment, described organic base is the ethanolamine shown in formula III, be preferably monoethanolamine, diethanolamine and triethanolamine one or more, the nano-carbon material containing hetero atom thus prepared is particularly suitable as the catalyst of dehydrogenating propane reaction, it is possible to obtain higher Propylene Selectivity.This preferred embodiment in, raw material nano material with carbon element: the weight ratio of organic base is preferably within the scope of 1:0.2-10, more preferably in the range of 1:1-5.In course of reaction, the temperature of aqueous dispersions is preferably in the range of 90-160 DEG C, more preferably in the range of 120-150 DEG C.
Another preferred embodiment in, described organic base is general formula R12(NH2)2The material represented, preferably one or more in ethylenediamine, propane diamine, butanediamine, pentanediamine and hexamethylene diamine, the nano-carbon material containing hetero atom thus prepared is particularly suitable as the catalyst of vinylbenzene dehydrogenation reaction, it is possible to obtain higher selectivity of styrene.This preferred embodiment in, raw material nano material with carbon element: the weight ratio of organic base is preferably within the scope of 1:0.2-10, more preferably in the range of 1:1-5.In course of reaction, the temperature of aqueous dispersions is preferably in the range of 100-200 DEG C, more preferably in the range of 120-150 DEG C.
Conventional various methods can be used to form described aqueous dispersions, such as, raw material nano material with carbon element can be dispersed in water (preferably deionized water), then be optionally added into described organic base, 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 40-80kHz, and the persistent period of described sonic oscillation can be 0.1-6 hour, preferably 0.5-2 hour.The method according to the invention, described organic base preferably provides with the form of solution (preferred aqueous solutions).
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 less than 0.1 weight %, preferably not higher than 0.08 weight %, more preferably not above 0.05 weight %.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 %.Described raw material nano material with carbon element is according to the difference in source, it is also possible to containing some metallic elements, such as, derive from the metallic element in the catalyst used when preparing raw material nano material with carbon element.In described raw material nano material with carbon element, the content (in terms of element) of metallic element is general below 2.5 weight %, below preferably 2 weight %, below more preferably 1 weight %, more 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.
According to the preparation method containing hetero atom nano-carbon material of the present invention, the nano-carbon material of various existing forms can be processed, to improve the oxygen atom in this nano-carbon material and/or 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.
According to the preparation method containing hetero atom nano-carbon material of the present invention, 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 50-400m2/ g, more preferably 90-300m2/ g, more preferably 100-200m2/g.The specific surface area of described multi-wall carbon nano-tube 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.
According to the preparation method containing hetero atom nano-carbon material of the present invention, 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.The nano-carbon material containing hetero atom thus prepared demonstrates more preferable catalytic 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 50-400m2/ g, more preferably 90-300m2/ 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.
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 preparation method containing hetero atom nano-carbon material according to the present 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 (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.
According to the preparation method containing hetero atom nano-carbon material of the present invention, the oxygen atom in raw material nano material with carbon element and/or nitrogen atom content can be effectively improved, the configuration of raw material nano material with carbon element will not be produced simultaneously and significantly affect.
According to the third aspect of the present invention, the invention provides a kind of by the method for the present invention prepare 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 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.Usually, described roasting can be carried out at a temperature of 250-500 DEG C, preferably carries out at a temperature of 300-480 DEG C, more preferably carries 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 2-8 hour.Described roasting can be carried out in oxygen-containing atmosphere, it is also possible to carries out in an inert atmosphere.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 inert atmosphere such as the atmosphere formed by rare gas (such as 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, described can be directly used as catalyst containing hetero atom nano-carbon material, it is also possible to use with the form of preformed catalyst.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 %.
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.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.Described hydrocarbon is more preferably one or more in propane, normal butane, iso-butane and vinylbenzene.
Hydrocarbon dehydrogenation reaction method according to the present invention, described reaction can be carried out (i.e. under conditions of there is oxygen, raw material containing hydrocarbon is possibly together with oxygen), it is also possible under conditions of there is not oxygen, (that is, the raw material containing hydrocarbon does not contains oxygen) is carried out.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 0.3-2:1 with the mol ratio of oxygen.
Hydrocarbon dehydrogenation reaction method according to the present invention, can be sent into hydrocarbon and optional oxygen with containing hetero atom nano-carbon material haptoreaction in reactor by carrier gas, and now, the raw material containing hydrocarbon can also contain 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, on the basis of the total amount of described raw material, the content of carrier gas can be 30-99.5 volume %, preferably 50-99 volume %, more preferably 70-98 volume %.
Hydrocarbon dehydrogenation reaction method according to the present invention, the raw material containing hydrocarbon and optional oxygen can be carried out with containing contacting of hetero atom nano-carbon material 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 raw material containing hydrocarbon and optional oxygen can be carried out with containing contacting of hetero atom nano-carbon material, at conventional temperatures 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 350-500 DEG C.Described contact can be carried out under the pressure of 0-10MPa, preferably carries out under the pressure of 0.01-6MPa, more preferably carries out under the pressure of 0.02-3MPa, further preferably carries out under the pressure of 0.05-1.5MPa.In the present invention, pressure is gauge pressure.
The persistent period of described contact can select according to the temperature of contact.Specifically, when dehydrogenation reaction is carried out in fixed bed reactors, the persistent period of contact can be represented with volume space velocity during the gas of raw material.Usually, during the gas of raw material, volume space velocity can be 0.1-10000h-1, preferably 1-6000h-1, more preferably 5-4000h-1, more preferably 10-1000h-1, such as 100-500h-1。
Dehydrogenation reaction method according to the present invention, can be optimized reaction condition according to the kind of the hydrocarbon carrying out dehydrogenation, thus obtain more preferable reaction effect.
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.
Preparation embodiment 1-47 is for preparation nano-carbon material Han hetero atom.
Preparation 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 0.2 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) it is dispersed in 300g deionized water, thus obtain aqueous dispersions, and wherein, carrying out under the conditions of being dispersed in sonic oscillation, sonic oscillation condition includes: frequency is 40kHz, and the time is 2 hours.
(2) aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 140 DEG C, reaction 48 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), be dried 12 hours at a temperature of 120 DEG C after, 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.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 of nano-carbon material.
Preparation comparative example 1
The aqueous dispersions identical with preparation embodiment 1 is placed in the there-necked flask being equipped with condensing tube, there-necked flask is placed in the oil bath that temperature is 140 DEG C, back flow reaction 48 hours at ambient pressure.After reaction terminates, after the temperature in there-necked flask is down to room temperature, reactant mixture is filtered and washs, and collecting solid matter.By the solid matter collected at normal pressure, be dried 6 hours at a temperature of 120 DEG C after, obtain containing hetero atom nano-carbon material.Composition containing hetero atom nano-carbon material and the character of preparation are listed in Table 1.
Preparation embodiment 2
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 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 and the character of preparation are listed in Table 1.
Preparation embodiment 3
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 1, except for the difference that, in step (2), the aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 90 DEG C, reaction 48 hours at autogenous pressures.Composition containing hetero atom nano-carbon material and the character of preparation are listed in Table 1.
Preparation embodiment 4
(1) using 20g, as the multi-walled carbon nano-tubes of raw material nano material with carbon element, (specific surface area is 183m2/ 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 0.03 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 dispersed in 500g deionized water, thus obtain aqueous dispersions, and wherein, carrying out under the conditions of being dispersed in sonic oscillation, sonic oscillation condition includes: frequency is 80kHz, and the time is 0.5 hour.
(2) aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 180 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, be dried 12 hours at a temperature of 120 DEG C after, obtain listing in Table 1 containing hetero atom nano-carbon material, this composition containing hetero atom nano-carbon material and character.
Preparation comparative example 2
The aqueous dispersions identical with preparation embodiment 4 is placed in the there-necked flask being equipped with condensing tube, there-necked flask is placed in the oil bath that temperature is 100 DEG C, back flow reaction 24 hours at ambient pressure.After reaction terminates, after the temperature in there-necked flask is down to room temperature, reactant mixture is filtered and washs, and collecting solid matter.By the solid matter collected at normal pressure, be dried 6 hours at a temperature of 120 DEG C after, obtain containing hetero atom nano-carbon material.Composition containing hetero atom nano-carbon material and the character of preparation are listed in Table 1.
Preparation embodiment 5
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 4, 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 of remaining nonmetallic heteroatoms (p and s) outside denitrogenating with oxygen is 0.01 weight %, and metallic atom total content is 1.6 weight %.Composition containing hetero atom nano-carbon material and the character of preparation are listed in Table 1.
Preparation embodiment 6
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 4, except for the difference that, in step (2), the aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 210 DEG C, reaction 24 hours at autogenous pressures.Composition containing hetero atom nano-carbon material and the character of preparation are listed in Table 1.
Preparation embodiment 7
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 1, except for the difference that, in step (1), after the dispersion in deionized water of raw material nano material with carbon element, TPAOH (providing with the form of 25 weight % aqueous solutions) is provided, wherein, in raw material nano material with carbon element: the weight ratio of TPAOH is that the ratio of 1:0.75 feeds intake.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.Fig. 3 is the transmission electron microscope photo containing hetero atom nano-carbon material of preparation.From figure 3, 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 of nano-carbon material.
Preparation comparative example 3
The aqueous dispersions identical with preparation embodiment 7 is placed in the there-necked flask being equipped with condensing tube, will there-necked flask be placed in the oil bath that temperature is 140 DEG C, back flow reaction 48 hours at ambient pressure.After reaction terminates, after the temperature in there-necked flask is down to room temperature, reactant mixture is filtered and washs, and collecting solid matter.By the solid matter collected at normal pressure, be dried 6 hours at a temperature of 120 DEG C after, obtain containing hetero atom nano-carbon material.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation comparative example 4
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), the HCl of TPAOH equimolar amounts replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation comparative example 5
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), the NH of TPAOH equimolar amounts4Cl replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation comparative example 6
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), the 4-propyl ammonium chloride of TPAOH equimolar amounts replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 8
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), the n-propylamine of TPAOH equimolar amounts replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 9
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), the pyridine of TPAOH equimolar amounts replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 10
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), the cyclohexylamine of TPAOH equimolar amounts replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 11
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), TPAOH ethylenediamine replaces, and the molal quantity of ethylenediamine is 0.5 times of the molal quantity of TPAOH.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 12
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), the diethanolamine of TPAOH equimolar amounts replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 13
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), TPAOH hexamethylenetetramine replaces, 0.25 times of the molal quantity that mole number is TPAOH of hexamethylenetetramine.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 14
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), TPAOH diethylenetriamine replaces, and the molal quantity of diethylenetriamine is 0.3 times of the molal quantity of TPAOH.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 15
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), raw material nano material with carbon element is identical with the raw material nano material with carbon element in preparation embodiment 2.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 16
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (2), the aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 80 DEG C, reaction 48 hours at autogenous pressures.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 17
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 7, except for the difference that, in step (1), in raw material nano material with carbon element: the weight ratio of TPAOH is that the ratio of 1:0.4 feeds intake.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 18
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 4, except for the difference that, in step (1), after the dispersion in deionized water of raw material nano material with carbon element, the form adding tetraethyl ammonium hydroxide (with 20 weight % aqueous dispersions) provides, thus obtaining aqueous dispersions, wherein, in raw material nano material with carbon element: the weight ratio of tetraethyl ammonium hydroxide is that the ratio of 1:5 feeds intake.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation comparative example 7
The aqueous dispersions identical with preparation embodiment 18 is placed in the there-necked flask being equipped with condensing tube, there-necked flask is placed in the oil bath that temperature is 180 DEG C, back flow reaction 24 hours at ambient pressure.After reaction terminates, after the temperature in there-necked flask is down to room temperature, reactant mixture is filtered and washs, and collecting solid matter.By the solid matter collected at normal pressure, be dried 6 hours at a temperature of 120 DEG C after, obtain containing hetero atom nano-carbon material.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 19
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 18, except for the difference that, in step (1), raw material nano material with carbon element is identical with the raw material nano material with carbon element in preparation embodiment 5.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 20
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 18, except for the difference that, in step (2), the aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 200 DEG C, reaction 48 hours at autogenous pressures.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 21
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 18, except for the difference that, in step (1), in raw material nano material with carbon element: the weight ratio of tetraethyl ammonium hydroxide is that the ratio of 1:8 feeds intake.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 2.
Preparation embodiment 22
(1) 20g is dispersed in 200g deionized water as the multi-walled carbon nano-tubes (identical with the raw material nano material with carbon element in preparation embodiment 1) of raw material nano material with carbon element, wherein, 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.Then, add the diethanolamine as organic base, thus obtain aqueous dispersions, wherein, in raw material nano material with carbon element: the weight ratio of organic base is that the ratio of 1:1 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, be dried 12 hours at a temperature of 120 DEG C after, obtain listing in table 3 containing hetero atom nano-carbon material, this composition containing hetero atom nano-carbon material and character.
Preparation comparative example 8
The aqueous dispersions identical with preparation embodiment 22 is placed in the there-necked flask being equipped with condensing tube, there-necked flask is placed in the oil bath that temperature is 120 DEG C, back flow reaction 24 hours at ambient pressure.After reaction terminates, after the temperature in there-necked flask is down to room temperature, reactant mixture is filtered and washs, and collecting solid matter.By the solid matter collected at normal pressure, be dried 6 hours at a temperature of 120 DEG C after, obtain containing hetero atom nano-carbon material.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 23
(1) 20g is dispersed in 500g deionized water as the multi-walled carbon nano-tubes (identical with the raw material nano material with carbon element in preparation embodiment 4) of raw material nano material with carbon element, wherein, 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.Then, add the triethanolamine as organic base, thus obtain aqueous dispersions, wherein, in raw material nano material with carbon element: the weight ratio of organic base is that the ratio of 1:5 feeds intake.
(2) aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 150 DEG C, reaction 36 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, be dried 8 hours at a temperature of 140 DEG C after, obtain listing in table 3 containing hetero atom nano-carbon material, this composition containing hetero atom nano-carbon material and character.
Preparation embodiment 24
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 22, except for the difference that, in step (2), the aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 90 DEG C, reaction 24 hours at autogenous pressures.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 25
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 22, except for the difference that, in step (1), the multi-walled carbon nano-tubes as raw material nano material with carbon element is identical with the raw material nano material with carbon element in preparation embodiment 2.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 26
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 22, except for the difference that, step (1), in raw material nano material with carbon element: the weight ratio of organic base is that the ratio of 1:0.2 feeds intake.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 27
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 22, except for the difference that, in step (1), the n-butylamine of diethanolamine equimolar amounts replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 28
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 23, except for the difference that, in step (1), the aniline of triethanolamine equimolar amounts replaces.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 29
(1) 20g is dispersed in 250g deionized water as the multi-walled carbon nano-tubes (identical with the raw material nano material with carbon element in preparation embodiment 1) of raw material nano material with carbon element, wherein, 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.Then, add the ethylenediamine as organic base, thus obtain aqueous dispersions, wherein, by raw material nano material with carbon element: the weight ratio of organic base is 1:1.25.
(2) aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 150 DEG C, reaction 48 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, be dried 5 hours at a temperature of 150 DEG C after, obtain listing in table 3 containing hetero atom nano-carbon material, this composition containing hetero atom nano-carbon material and character.
Preparation comparative example 9
The aqueous dispersions identical with preparation embodiment 29 is placed in the there-necked flask being equipped with condensing tube, there-necked flask is placed in the oil bath that temperature is 150 DEG C, back flow reaction 48 hours at ambient pressure.After reaction terminates, after the temperature in there-necked flask is down to room temperature, reactant mixture is filtered and washs, and collecting solid matter.By the solid matter collected at normal pressure, be dried 6 hours at a temperature of 120 DEG C after, obtain containing hetero atom nano-carbon material.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 30
(1) 20g is dispersed in 800g deionized water as the multi-walled carbon nano-tubes (identical with the raw material nano material with carbon element in preparation embodiment 4) of raw material nano material with carbon element, wherein, carry out under the conditions of being dispersed in sonic oscillation, sonic oscillation condition includes: frequency is 60kHz, and the time is 1.5 hours.Then, add the hexamethylene diamine as organic base, thus obtain aqueous dispersions, wherein, by raw material nano material with carbon element: the weight ratio of hexamethylene diamine is 1:4.
(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, be dried 12 hours at a temperature of 120 DEG C after, obtain listing in table 3 containing hetero atom nano-carbon material, this composition containing hetero atom nano-carbon material and character.
Preparation embodiment 31
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 29, except for the difference that, in step (1), the multi-walled carbon nano-tubes as raw material nano material with carbon element is identical with preparation embodiment 2.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 32
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 29, except for the difference that, in step (2), the aqueous dispersions obtained is placed in in teflon-lined autoclave, at a temperature of 200 DEG C, reaction 24 hours at autogenous pressures.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 33
Use method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 29, except for the difference that, in step (1), in raw material nano material with carbon element: the weight ratio of organic base is that the ratio of 1:0.25 feeds intake.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 34
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 29, except for the difference that, in step (1), ethylenediamine ethamine replaces, and the molal quantity of ethamine is 2 times of ethylenediamine.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 35
Using method preparation Han the hetero atom nano-carbon material identical with preparation embodiment 30, except for the difference that, in step (1), hexamethylene diamine triethanolamine replaces, and the mole of triethanolamine is 2 times of the mole of hexamethylene diamine.Composition containing hetero atom nano-carbon material and the character of preparation are listed in table 3.
Preparation embodiment 36
By preparation embodiment 1 obtain containing hetero atom nano-carbon material 350 DEG C of roasting 4 hours in air atmosphere.
Preparation comparative example 10
By preparation comparative example 1 obtain containing hetero atom nano-carbon material 350 DEG C of roasting 4 hours in air atmosphere.
Preparation embodiment 37
By preparation embodiment 7 prepare containing hetero atom nano-carbon material 350 DEG C of roasting 4 hours in air atmosphere.
Preparation comparative example 11-14
Preparation comparative example 11 by preparation comparative example 3 obtain containing hetero atom nano-carbon material 350 DEG C of roasting 4 hours in air atmosphere；Preparation comparative example 12 by preparation comparative example 4 obtain containing hetero atom nano-carbon material 350 DEG C of roasting 4 hours in air atmosphere；Preparation comparative example 13 by preparation comparative example 5 obtain containing hetero atom nano-carbon material 350 DEG C of roasting 4 hours in air atmosphere；Preparation comparative example 14 by preparation comparative example 6 obtain containing hetero atom nano-carbon material 350 DEG C of roasting 4 hours in air atmosphere.Preparation embodiment 38
By preparation embodiment 18 obtain containing hetero atom nano-carbon material 450 DEG C of roasting 2 hours in air atmosphere.
Preparation embodiment 39
By preparation embodiment 19 obtain containing hetero atom nano-carbon material 450 DEG C of roasting 2 hours in air atmosphere.
Preparation embodiment 40
By preparation embodiment 22 obtain containing hetero atom nano-carbon material 400 DEG C of roasting 4 hours in air atmosphere.
Preparation comparative example 15
By preparation comparative example 8 obtain containing hetero atom nano-carbon material 400 DEG C of roasting 4 hours in air atmosphere.
Preparation embodiment 41
By preparation embodiment 23 obtain containing hetero atom nano-carbon material 380 DEG C of roasting 6 hours in air atmosphere.
Preparation embodiment 42
By preparation embodiment 26 obtain containing hetero atom nano-carbon material 400 DEG C of roasting 5 hours in air atmosphere.
Preparation embodiment 43
By preparation embodiment 28 obtain containing hetero atom nano-carbon material 380 DEG C of roasting 6 hours in air atmosphere.
Preparation embodiment 44
By preparation embodiment 29 obtain containing hetero atom nano-carbon material 410 DEG C of roasting 5 hours in air atmosphere.
Preparation comparative example 16
By preparation comparative example 9 prepare containing hetero atom nano-carbon material 410 DEG C of roasting 5 hours in air atmosphere.
Preparation embodiment 45
By preparation embodiment 30 obtain containing hetero atom nano-carbon material 370 DEG C of roasting 8 hours in air atmosphere.
Preparation embodiment 46
By preparation embodiment 33 obtain containing hetero atom nano-carbon material 410 DEG C of roasting 5 hours in air atmosphere.
Preparation embodiment 47
By preparation embodiment 35 obtain containing hetero atom nano-carbon material 370 DEG C of roasting 8 hours in air atmosphere.
Embodiment 1-67 is for the method that the present invention is described.
Embodiment 1-8
Respectively using 0.2g (admission space is 1.5mL) 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, the unstrpped gas containing hydrocarbon and oxygen is passed through in reactor and reacts.
Wherein, be respectively adopted preparation embodiment 1-3 and 7 and preparation embodiment 36 preparation containing hetero atom nano-carbon material as in the embodiment of catalyst, in unstrpped gas, the concentration of normal butane is 1 volume %, normal butane and oxygen molar ratio 0.5:1, surplus is the nitrogen as carrier gas, and reaction is carried out under conditions of 0.1MPa and 450 DEG C, and the cumulative volume air speed of unstrpped gas is 500h-1；
Be respectively adopted preparation embodiment 4-6 prepare containing hetero atom nano-carbon material as in the embodiment of catalyst, in unstrpped gas, the concentration of normal butane is 1.5 volume %, normal butane and oxygen molar ratio 2:3, surplus is the nitrogen as carrier gas, reaction is carried out under conditions of 0MPa and 420 DEG C, and the cumulative volume air speed of unstrpped gas is 100h-1。
Continuously monitoring composition of the reactant mixture of output from reactor, and calculate n-butane conversion, total olefin selectivity and 1-butylene selectivity, reacts that the results are shown in Table 43 hours and 24 hours.
Embodiment 9
Using method same as in Example 1 by n butane oxidation, except for the difference that, reaction is carried out under the conditions of 0.5MPa and 400 DEG C.Experimental result is listed in table 4.
Embodiment 10
Using method the same as in Example 4 by n butane oxidation, except for the difference that, reaction is carried out under the conditions of 0MPa and 450 DEG C.Experimental result is listed in table 4.
Comparative example 1
Use method same as in Example 1 by n butane oxidation, except for the difference that, use the nano-carbon material containing hetero atom of preparation comparative example 1 preparation as catalyst.Experimental result is listed in table 4.
Comparative example 2
Use method the same as in Example 4 by n butane oxidation, except for the difference that, use the nano-carbon material containing hetero atom of preparation comparative example 2 preparation as catalyst.Experimental result is listed in table 4.
Comparative example 3
Use method same as in Example 1 by n butane oxidation, except for the difference that, use the material carbon material in preparation embodiment 1 as catalyst.Experimental result is listed in table 4.
Comparative example 4
Use method the same as in Example 4 by n butane oxidation, except for the difference that, use the material carbon material in preparation embodiment 4 as catalyst.Experimental result is listed in table 4.
Comparative example 5
Use method same as in Example 1 by n butane oxidation, except for the difference that, use the nano-carbon material containing hetero atom of preparation comparative example 10 preparation as catalyst.Experimental result is listed in table 4.
Table 4
Embodiment 11-30
Respectively using 0.2g (volume is 1.5mL) 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, the unstrpped gas containing hydrocarbon and oxygen is passed through in reactor and reacts.
Wherein, be respectively adopted preparation embodiment 1,7-17,36 and 37 preparation containing hetero atom nano-carbon material as in the embodiment of catalyst, in unstrpped gas, the concentration of normal butane is 2 volume %, normal butane and oxygen molar ratio 1:3, surplus is the nitrogen as carrier gas, and reaction is carried out under conditions of 0.1MPa and 400 DEG C, and the cumulative volume air speed of unstrpped gas is 200h-1；
Be respectively adopted preparation embodiment 18-21,38 and 39 preparation containing hetero atom nano-carbon material as in the embodiment of catalyst, in unstrpped gas, the concentration of normal butane is 1 volume %, normal butane and oxygen molar ratio 1:1.5, surplus is the nitrogen as carrier gas, reaction is carried out under conditions of 0.5MPa and 420 DEG C, and the cumulative volume air speed of unstrpped gas is 500h-1。
Continuously monitoring composition of the reactant mixture of output from reactor, and calculate n-butane conversion, total olefin selectivity and butadiene selective, reacts that the results are shown in Table 53 hours and 24 hours.
Comparative example 6-9
Use the method identical with embodiment 11 by n butane oxidation, except for the difference that, be respectively adopted the preparation nano-carbon material containing hetero atom prepared of comparative example 3-6 as catalyst.Experimental result is listed in table 5.
Comparative example 10
Use the method identical with embodiment 23 by n butane oxidation, except for the difference that, use the nano-carbon material containing hetero atom of preparation comparative example 7 preparation as catalyst.Experimental result is listed in table 5.
Comparative example 11
Use the method identical with embodiment 12 by n butane oxidation, except for the difference that, use the material carbon material in preparation embodiment 7 as catalyst.Experimental result is listed in table 5.
Comparative example 12
Use the method identical with embodiment 23 by n butane oxidation, except for the difference that, use the material carbon material in preparation embodiment 18 as catalyst.Experimental result is listed in table 5.
Comparative example 13-16
Use the method oxidizing n-butane identical with embodiment 28, except for the difference that, be respectively adopted the nano-carbon material containing hetero atom prepared by preparation comparative example 11-14 as catalyst.Experimental result is listed in table 5.
Embodiment 31-33
Use the method identical with embodiment 11 by n butane oxidation, except for the difference that, be respectively adopted carrying out under the conditions of 0.1MPa and 450 DEG C as catalyst, reaction containing hetero atom nano-carbon material of preparation embodiment 1,7 and 8 preparation.Experimental result is listed in table 5.
Embodiment 34-37
Using the method identical with embodiment 23 by n butane oxidation, except for the difference that, be respectively adopted prepared by preparation embodiment 18-21 is carried out as the embodiment of catalyst, reaction containing hetero atom nano-carbon material under the conditions of 0.1MPa and 400 DEG C.Experimental result is listed in table 5.
Table 5
Embodiment 38-48
Respectively using 0.2g (volume is 1.5mL) 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, the unstrpped gas containing hydrocarbon and oxygen is passed through in reactor and reacts.
Wherein, it is respectively adopted in the embodiment containing hetero atom nano-carbon material of preparation embodiment 22,24-27,40,42 and 43 preparation, in unstrpped gas, the concentration of propane is 1 volume %, propane and mol ratio 1:3 of oxygen, surplus is the nitrogen as carrier gas, and reaction is carried out under conditions of 0.2MPa and 480 DEG C, and the cumulative volume air speed of unstrpped gas is 150h-1；
It is respectively adopted in the embodiment containing hetero atom nano-carbon material of preparation embodiment 23,28 and 41 preparation, in unstrpped gas, the concentration of propane is 4 volume %, propane and mol ratio 0.5:1 of oxygen, surplus is the nitrogen as carrier gas, reaction is carried out under conditions of 0.1MPa and 420 DEG C, and the cumulative volume air speed of unstrpped gas is 20h-1。
Monitoring composition of the reactant mixture of output from reactor continuously, and calculate conversion of propane and C3Olefine selective, reacts that the results are shown in Table 63 hours and 24 hours.
Comparative example 17
Use the method identical with embodiment 38 by oxidation of propane, except for the difference that, use the nano-carbon material containing hetero atom of preparation comparative example 8 preparation as catalyst.Experimental result is listed in table 6.
Comparative example 18
Use the method identical with embodiment 38 by oxidation of propane, except for the difference that, use the material carbon material in preparation embodiment 22 as catalyst.Experimental result is listed in table 6.
Comparative example 19
Use the method identical with embodiment 39 by oxidation of propane, except for the difference that, use the material carbon material in preparation embodiment 23 as catalyst.Experimental result is listed in table 6.
Comparative example 20
Use the method identical with embodiment 45 by oxidation of propane, except for the difference that, use the nano-carbon material containing hetero atom of preparation comparative example 15 preparation as catalyst.Experimental result is listed in table 6.
Embodiment 49-51
Use the method propane oxide identical with embodiment 38, except for the difference that, be respectively adopted carrying out under conditions of 0MPa and 440 DEG C as catalyst, reaction containing hetero atom nano-carbon material of preparation embodiment 22,26 and 27 preparation.Experimental result is listed in table 6.
Embodiment 52
Using the method propane oxide identical with embodiment 39, except for the difference that, reaction is carried out under conditions of 1MPa and 360 DEG C.Experimental result is listed in table 6.
Table 6
Embodiment 53-63
Respectively using 0.2g (admission space is 1.5mL) 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, the unstrpped gas containing vinylbenzene and oxygen is passed through in reactor and reacts.
Wherein, it is respectively adopted and prepares in the embodiment containing hetero atom nano-carbon material prepared by embodiment 29,31-34,43 and 46, in unstrpped gas, the concentration of vinylbenzene is 2 volume %, vinylbenzene and mol ratio 1:1 of oxygen, surplus is the nitrogen as carrier gas, and reaction is carried out under conditions of 0.1MPa and 400 DEG C, and the cumulative volume air speed of unstrpped gas is 250h-1；
It is respectively adopted in the embodiment containing hetero atom nano-carbon material of preparation embodiment 30,35,45 and 47 preparation, in unstrpped gas, the concentration of vinylbenzene is 3 volume %, vinylbenzene and mol ratio 2:1 of oxygen, surplus is the nitrogen as carrier gas, reaction is carried out under conditions of 0.5MPa and 380 DEG C, and the cumulative volume air speed of unstrpped gas is 100h-1。
Continuously monitoring composition of the reactant mixture of output from reactor, and calculate vinylbenzene conversion ratio and selectivity of styrene, reacts that the results are shown in Table 73 hours and 24 hours.
Comparative example 21
Use the method identical with embodiment 53 to be aoxidized by vinylbenzene, except for the difference that, use the nano-carbon material containing hetero atom of preparation comparative example 9 preparation as catalyst.Experimental result is listed in table 7.
Comparative example 22
Use the method identical with embodiment 53 to be aoxidized by vinylbenzene, except for the difference that, use the raw material nano material with carbon element in preparation embodiment 29 as catalyst.Experimental result is listed in table 7.
Comparative example 23
Use the method identical with embodiment 54 to be aoxidized by vinylbenzene, except for the difference that, use the raw material nano material with carbon element in preparation embodiment 30 as catalyst.Experimental result is listed in table 7.
Comparative example 24
Use the method identical with embodiment 60 to be aoxidized by vinylbenzene, except for the difference that, use the nano-carbon material containing hetero atom of preparation comparative example 16 preparation as catalyst.Experimental result is listed in table 7.
Embodiment 64-66
Use the method identical with embodiment 53 to be aoxidized by vinylbenzene, except for the difference that, be respectively adopted carrying out under conditions of 1MPa and 450 DEG C as catalyst, reaction containing atom nano-carbon material of preparation embodiment 29,33 and 34 preparation.Experimental result is listed in table 7.
Embodiment 67
Using the method identical with embodiment 54 to be aoxidized by vinylbenzene, except for the difference that, reaction is carried out under conditions of 0MPa and 300 DEG C.Experimental result is listed in table 7.
Table 7

Claims (36)

1. a nano-carbon material Han hetero atom, this contains hetero atom nano-carbon material and contains C element, O element and optional N element, on the basis of this total amount containing hetero atom nano-carbon material and in terms of element, the content of O element is 1-6 weight %, the content of N element is 0-2 weight %, and the content of C element is 92-99 weight %；
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 0.2-0.8；
Described containing 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 0.2-1；
When described containing hetero atom nano-carbon material in the content of N element be more than 0.1 weight % time, 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 0.7-1.
The most according to claim 1 containing hetero atom nano-carbon material, wherein, described is less than 0.1 weight % containing the content of N element in 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 O is 2.5-5.8 weight %, it is preferably 3-5.6 weight %, more preferably 4.5-5.5 weight %；The content of C element is 94.2-97.5 weight %, preferably 94.4-97 weight %, more preferably 94.5-95.5 weight %.
The most according to claim 1 and 2 containing hetero atom nano-carbon material, wherein, described is less than 0.1 weight %, I containing the content of N element in hetero atom nano-carbon materialO c/IO eIn the range of 0.4-0.7, preferably in the range of 0.55-0.65；IC c/IC ePreferably in the range of 0.3-0.9, more preferably in the range of 0.35-0.8, further preferably in the range of 0.5-0.7.
The most according to claim 1 containing hetero atom nano-carbon material, wherein, on the basis of the described total amount containing hetero atom nano-carbon material and in terms of element, the content of O element is 2-6 weight %, preferably 3.5-5.5 weight %；The content of N element is 0.2-1.8 weight %, preferably 0.5-1.8 weight %；The content of C element is 92.2-97.8 weight %, preferably 92.7-96 weight %.
5. according to described in claim 1 or 4 containing hetero atom nano-carbon material, wherein, described is more than 0.1 weight % containing the content of N element in hetero atom nano-carbon material, IO c/IO eIn the range of 0.35-0.85, preferably in the range of 0.45-0.8；IC c/IC eIn the range of 0.3-0.98, preferably in the range of 0.45-0.95.
6. according to described in any one in claim 1,4 and 5 containing hetero atom nano-carbon material, wherein, IN c/IN tIn the range of 0.8-0.95.
7. according to described in any one in claim 1-6 containing hetero atom nano-carbon material, wherein, described containing in hetero atom nano-carbon material, on the basis of the total amount of the C element determined by x-ray photoelectron power spectrum, 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 more than 20 weight %, it is preferably more than 40 weight %, more than more preferably 50 weight %, more preferably more than 70 weight %；And 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 below 95 weight %, below preferably 90 weight %.
8. according to described in any one in claim 1-7 containing hetero atom nano-carbon material, wherein, this contains hetero atom nano-carbon material for containing hetero atom CNT, is preferably the multi-walled carbon nano-tubes Han hetero atom.
The most according to claim 8 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 100-200m2/g。
The most according to claim 8 or claim 9 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, described weight-loss ratio measures in air atmosphere.
11. according to described in any one in claim 1-10 containing hetero atom nano-carbon material, wherein, on the basis of the described total amount containing hetero atom nano-carbon material, the content of O element is 2-6 weight %, preferably 4-5.8 weight %, more preferably 4.5-5.5 weight %；The content of N element is 0.2-1.8 weight %, preferably 0.8-1.6 weight %, more preferably 1-1.5 weight %；The content of C element is 92.2-97.8 weight %, preferably 92.6-95.2 weight %, more preferably 93-94.5 weight %；
IO c/IO ePreferably in the range of 0.3-0.8, more preferably in the range of 0.35-0.8, further preferably in the range of 0.55-0.78；
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 preferably 70-90 weight %, more preferably 75-85 weight %；
IC c/IC ePreferably in the range of 0.3-0.9, more preferably in the range of 0.4-0.7, further preferably in the range of 0.45-0.6；
IN c/IN tPreferably in the range of 0.7-0.98, more preferably in the range of 0.75-0.96, further preferably in the range of 0.8-0.95.
12. according to described in any one in claim 1-10 containing hetero atom nano-carbon material, wherein, on the basis of the described total amount containing hetero atom nano-carbon material, the content of O element is 2-6 weight %, preferably 3-5.5 weight %, more preferably 3.5-5 weight %；The content of N element is 0.3-2 weight %, preferably 0.4-1.8 weight %, more preferably 0.5-1.5 weight %；The content of C element is 92-97.7 weight %, preferably 92.7-96.6 weight %, more preferably 93.5-96 weight %；
IO c/IO ePreferably in the range of 0.3-0.8, more preferably in the range of 0.4-0.78, further preferably in the range of 0.45-0.75；
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 preferably 70-90 weight %, more preferably 70-85 weight %；
IC c/IC ePreferably in the range of 0.3-0.9, more preferably in the range of 0.4-0.8, further preferably in the range of 0.45-0.6；
IN c/IN tPreferably in the range of 0.7-0.95, more preferably in the range of 0.7-0.9, further preferably in the range of 0.8-0.9.
13. according to described in any one in claim 1-10 containing hetero atom nano-carbon material, wherein, on the basis of the described total amount containing hetero atom nano-carbon material, the content of O element is 3-6 weight %, preferably 4-5.8 weight %, more preferably 4.5-5.5 weight %；The content of N element is 0.5-2 weight %, preferably 1-2 weight %, more preferably 1.2-1.8 weight %；The content of C element is 92-96.5 weight %, preferably 92.2-95 weight %, more preferably 92.7-94.3 weight %；
IO c/IO ePreferably in the range of 0.3-0.8, more preferably in the range of 0.4-0.75, further preferably in the range of 0.6-0.7；
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 preferably 70-80 weight %, more preferably 75-80 weight %；
IC c/IC ePreferably in the range of 0.4-0.98, more preferably in the range of 0.7-0.98, further preferably in the range of 0.85-0.95；
IN c/IN tPreferably in the range of 0.7-0.95, more preferably in the range of 0.75-0.9, further preferably in the range of 0.8-0.85.
14. 1 kinds of preparation methoies 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, described aqueous dispersions is with or without organic base, described organic base is amine and/or quaternary ammonium base, in course of reaction, the temperature of described aqueous dispersions is maintained in the range of 80-220 DEG C.
15. methods according to claim 14, wherein, raw material nano material with carbon element: H2The weight ratio of O is in the range of 1:2-200, preferably in the range of 1:5-100, more preferably in the range of 1:10-50.
16. according to the method described in claims 14 or 15, wherein, described aqueous dispersions contains at least one organic base, raw material nano material with carbon element: the weight ratio of organic base is in the range of 1:0.05-20, preferably in the range of 1:0.1-10, more preferably in the range of 0.5-5.
17. according to the method described in any one in claim 14-16, and wherein, described organic base is selected from the compound shown in the compound shown in the compound shown in Formulas I, Formula II, formula III and general formula R12(NH2)2The material represented, R12For C1-C6Alkylidene or C6-C12Arlydene,
In Formulas I, R1、R2、R3And R4It is respectively C1-C20Alkyl or C6-C12Aryl；
In Formula II, R5、R6And R7It is respectively H, C1-C6Alkyl or C6-C12Aryl, and R5、R6And R7It is asynchronously H；
In formula III, R8、R9And R10It is respectively-R11OH, hydrogen or C1-C6Alkyl, and R8、R9And R10In at least one be-R11OH, R11For C1-C4Alkylidene.
18. according to the method described in any one in claim 14-17, and wherein, in course of reaction, the temperature of described aqueous dispersions is maintained in the range of 120-180 DEG C.
19. according to the method described in any one in claim 14-18, wherein, the persistent period of described reaction in the range of 0.5-96 hour, preferably in the range of 2-72 hour, more preferably in the range of 20-50 hour.
20. according to the method described in any one in claim 14-19, and 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 less than 0.1 weight %, preferably not higher than 0.08 weight %, more preferably not above 0.05 weight %.
21. according to the method described in any one in claim 14-20, and wherein, described raw material nano material with carbon element is CNT, preferably multi-walled carbon nano-tubes.
22. methods according to claim 21, wherein, the specific surface area of described multi-walled carbon nano-tubes is 20-500m2/ g, preferably 50-400m2/ g, more preferably 90-300m2/ g, more preferably 100-200m2/g。
23. according to the method described in claim 21 or 22, 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, described weight-loss ratio measures in air atmosphere.
24. according to the method described in any one in claim 14-23, and wherein, the method also includes isolating solid matter from the mixture that reaction obtains, and is dried by isolated solid matter.
25. methods according to claim 24, wherein, described being dried is carried out at a temperature of 50-200 DEG C, preferably carry out at a temperature of 80-180 DEG C, more preferably carry 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.
26. according to the method described in any one in claim 14,15 and 20-25, wherein, described organic base is the compound shown in Formulas I, preferably one or more in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH and four pentyl ammonium hydroxide
In Formulas I, R1、R2、R3And R4It is respectively C1-C20Alkyl or C6-C12Aryl；
Further, raw material nano material with carbon element: the weight ratio of organic base is within the scope of 1:0.1-10, preferably in the range of 0.5-5, in course of reaction, the temperature of aqueous dispersions is in the range of 90-210 DEG C, preferably in the range of 140-180 DEG C.
27. according to the method described in any one in claim 14,15 and 20-25, and wherein, described organic base is the compound shown in formula III, preferably monoethanolamine, diethanolamine and triethanolamine one or more,
In formula III, R8、R9And R10It is respectively-R11OH, hydrogen or C1-C6Alkyl, and R8、R9And R10In at least one be-R11OH, R11For C1-C4Alkylidene；
Further, raw material nano material with carbon element: the weight ratio of organic base is within the scope of 1:0.2-10, preferably in the range of 1:1-5；In course of reaction, the temperature of aqueous dispersions is in the range of 90-160 DEG C, preferably in the range of 120-150 DEG C.
28. according to the method described in any one in claim 14,15 and 20-25, and wherein, described organic base is general formula R12(NH2)2The material represented, R12For C1-C6Alkylidene or C6-C12Arlydene, preferably one or more in ethylenediamine, propane diamine, butanediamine, pentanediamine and hexamethylene diamine；
Further, raw material nano material with carbon element: the weight ratio of organic base is within the scope of 1:0.2-10, preferably in the range of 1:1-5；In course of reaction, the temperature of aqueous dispersions is in the range of 100-200 DEG C, preferably in the range of 120-150 DEG C.
29. 1 kinds by the method described in any one in claim 14-28 prepare containing hetero atom nano-carbon material.
30. 1 kinds of nano-carbon materials Han hetero atom, this contain hetero atom nano-carbon material be by described in any one in claim 1-13 containing carrying out roasting and prepared containing hetero atom nano-carbon material described in hetero atom nano-carbon material or claim 29.
31. is according to claim 30 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 300-480 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 2-8 hour.
In 32. claim 1-13 and 29 described in any one containing described in any one in hetero atom nano-carbon material or claim 30-31 containing hetero atom nano-carbon material as the application of the catalyst of hydrocarbon dehydrogenation reaction.
33. application according to claim 32, wherein, described dehydrogenation reaction is carried out in the presence of oxygen.
34. according to the application described in claim 32 or 33, and wherein, described hydrocarbon is alkane, preferably C2-C12Alkane, more preferably one or more in propane, normal butane, iso-butane and vinylbenzene.
35. 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 30-31 described in any one in claim 1-13 and 29.
36. methods according to claim 35, wherein, described hydrocarbon is alkane, preferably C2-C12Alkane, more preferably one or more in propane, normal butane, iso-butane and vinylbenzene.
CN201510703329.9A 2015-01-27 2015-10-26 One kind nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method Active CN105817242B (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
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