CN106925326A - A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method - Google Patents

A kind of nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method Download PDF

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CN106925326A
CN106925326A CN201511032378.0A CN201511032378A CN106925326A CN 106925326 A CN106925326 A CN 106925326A CN 201511032378 A CN201511032378 A CN 201511032378A CN 106925326 A CN106925326 A CN 106925326A
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nano
carbon material
range
weight
metallic atom
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CN106925326B (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • C07C2527/24—Nitrogen compounds

Abstract

The invention discloses a kind of nano-carbon material containing metallic atom and preparation method and application, the nano-carbon material contains the metallic element of the O elements of 1-12 weight %, the N element of 0.1-6 weight % and 0.2-15 weight %, and at least part of metallic element is group ia metal element and group iia metallic element.Feed stock conversion and selectivity of product higher can be obtained present invention also offers hydrocarbon dehydrogenation reaction method of the nano-carbon material containing metallic atom as catalyst, the method is used.

Description

A kind of nano-carbon material containing metallic atom 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 containing metallic atom, the invention further relates to a kind of nano carbon material containing metallic atom The preparation method of material and the nano-carbon material containing metallic atom prepared by the method, the present invention further relate to a kind of by will be above-mentioned The nano-carbon material containing metallic atom that nano-carbon material containing metallic atom is calcined and is prepared, the invention further relates to basis Application and a kind of hydrocarbon dehydrogenation reaction side of the nano-carbon material containing metallic atom of the invention as the catalyst of hydrocarbon dehydrogenation reaction Method.
Background technology
The dehydrogenation reaction of hydrocarbons is the important reaction type of a class, such as most of low-carbon (LC) olefine is by low-carbon (LC) The dehydrogenation reaction of alkane and obtain.Whether dehydrogenation reaction participates in that direct dehydrogenation reaction (that is, oxygen can be divided into according to oxygen Gas is not involved in) and oxidative dehydrogenation (that is, oxygen is participated in) two classes.
Polytype nano-carbon material has been demonstrated equal to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation With catalytic effect, introducing oxygen atom and/or nitrogen-atoms can then improve its catalysis activity in nano-carbon material.
Oxygen atom is introduced in nano-carbon material, hydroxyl, carbonyl, carboxyl, ester group can be formed on nano-carbon material surface With the oxygen-containing functional group such as acid anhydrides.
Can realize introducing oxygen atom in nano-carbon material by carrying out oxidation processes to nano-carbon material, so as to increase The content of oxygen-containing functional group in nano-carbon material.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or it is strong Oxidizing solution (such as H2O2、KMnO4) in carry out back flow reaction, can also aid in carrying out heating using microwave while back flow reaction Or sonic oscillation, to strengthen the effect of oxidation reaction.But, carrying out back flow reaction in strong acid and/or strong oxidizing solution can Can have a negative impact to the skeleton structure of nano-carbon material, or even destroy the skeleton structure of nano-carbon material.For example：To receive Rice carbon material carries out back flow reaction in nitric acid, although can introduce a large amount of oxygen-containing functional groups on nano-carbon material surface, but Easily cause nano-carbon material to be cut off and/or substantially increase the defective bit in graphite network structure, so as to reduce nano carbon material The performance of material, such as heat endurance.In addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, it is former to introduce oxygen The period of the day from 11 p.m. to 1 a.m, the introduction volume of oxygen atom is high to the dependence of operation condition, and fluctuation range is wider.
When introducing nitrogen-atoms in nano-carbon material, according to nitrogen-atoms, residing chemical environment is not in nano-carbon material Together, nitrogen-atoms is generally divided into chemical nitrogen and structure nitrogen.Chemical nitrogen is mainly material is appeared in the form of surface functional group Surface, such as amino or nitrosyl radical surface nitrogen-containing functional group.Structure nitrogen refer into nano-carbon material skeleton structure with The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly includes graphite mould nitrogen (i.e.,), pyridine type nitrogen (i.e.,) and pyrrole Cough up type nitrogen (i.e.,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen and Pyrroles's type nitrogen is unsaturated nitrogen atom, while carbon atom is replaced, can often cause to close on the missing of carbon atom, forms defect Position.
Can by introduce in nano-carbon material building-up process nitrogenous feature atmosphere (such as ammonia, nitrogen, urea, Melamine), nitrogen is incorporated into nano carbon material simultaneously in the building-up process of nano-carbon material using high temperature and/or high pressure In the skeleton structure of material and/or surface；Nitrogenous feature atmosphere (such as ammonia, nitrogen can also be placed in by by nano-carbon material Gas, urea, melamine) in, nitrogen is incorporated into the surface of nano-carbon material using high temperature and/or high pressure.High temperature and/or Although high pressure can form structure nitrogen in nano-carbon material, the type of nitrogen containing species depends on reaction condition, not easily-controllable System；Also, the different types of nitrogen containing species for so producing are uneven in the surface distributed of nano-carbon material, cause nitrogenous nanometer The unstable properties of carbon material.Oxidation processes can also be carried out by by nano-carbon material, then be reacted with amine, so as in nanometer Carbon material surface introduces nitrogen-atoms, and the nitrogen-atoms for so introducing is essentially chemical nitrogen.
Although the research about the doping vario-property and its catalytic performance of nano-carbon material achieves many progress, for Some of which basic problem is not built consensus yet, is still needed to doping vario-property nano-carbon material and preparation method thereof and catalysis Performance is furtherd investigate.
The content of the invention
It is an object of the present invention to provide a kind of preparation method containing metallic atom nano-carbon material, using the method Metallic atom can not only be introduced on nano-carbon material surface, and can stably improve heteroatomic content in nano-carbon material, Structure influence simultaneously to nano-carbon material in itself is little.
It is another object of the present invention to provide a kind of nano-carbon material containing metallic atom, this contains metallic atom nano-sized carbon When material is used for the dehydrogenation reaction of hydrocarbons, feed stock conversion and selectivity of product higher can be obtained.
A further object of the present invention is to provide a kind of hydrocarbon dehydrogenation reaction method, and the method can obtain raw material conversion higher Rate and selectivity of product.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material contains C element, O elements, N element and at least one metallic element, with the nano carbon material containing metallic atom On the basis of the total amount of material and in terms of element, the content of O elements is 1-12 weight %, and the content of N element is 0.1-6 weight %, institute The total amount of metallic element is stated for 0.2-15 weight %, the content of C element is 67-98.7 weight %, and at least part of metallic element is Group ia metal element and group iia metallic element,
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron power spectrum is IO t, by The content of the O elements that the peak in x-ray photoelectron power spectrum in the range of 529.5-530.8eV determines is IO m, IO m/IO tIn 0.05- In the range of 0.6；
This contains in metallic atom nano-carbon material, true by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum The amount of fixed O elements is IO c, the amount of the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum is IO e, IO c/IO eIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, determines that this contains metallic atom nano-carbon material by x-ray photoelectron power spectrum In N element total amount be IN t, the amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum It is IN c, IN c/IN tIn the range of 0-0.5, the N determined by the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum The content of element is IN n, IN n/IN tIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, true by the peak in the range of 288.6-288.8eV in x-ray photoelectron power spectrum The amount of fixed C element is IC c, the amount of the C element determined by the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum is IC e, IC c/IC eIn the range of 1-5.
According to the second aspect of the invention, the invention provides a kind of preparation side containing metallic atom nano-carbon material Method, the method includes for one kind being dispersed with raw material nano carbon material, at least one alkaline metal cpds and at least one nitre The aqueous dispersions of acid metal salt are reacted in closed container, and the metallic element in the alkaline metal cpds is selected from IA Race's metallic element and group iia metallic element, in course of reaction, the temperature of the aqueous dispersions is maintained at 80-300 DEG C of scope It is interior.
According to the third aspect of the present invention, the invention provides a kind of by according to second method system of aspect of the invention Standby nano-carbon material containing metallic atom.
According to the fourth aspect of the present invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material is will to be entered according to the nano-carbon material containing metallic atom of present invention one side or the 3rd aspect Prepared by row roasting.
According to the fifth aspect of the present invention, the invention provides being received containing metallic atom according to one side of the invention Rice carbon material, according to third aspect of the present invention nano-carbon material containing metallic atom or according to 4th aspect of the invention Nano-carbon material containing metallic atom as the catalyst of hydrocarbon dehydrogenation reaction application.
According to the sixth aspect of the invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, the method is included in deposits Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with according to one side of the invention containing metal Atom nano-carbon material, according to third aspect of the present invention nano-carbon material containing metallic atom or according to the present invention the 4th The contact of nano-carbon material containing metallic atom of individual aspect.
Preparation method containing metallic atom nano-carbon material of the invention, can not only stably regulate and control and/or improve Metallic atom and heteroatomic content in nano-carbon material, while the structure influence to nano-carbon material in itself is small.Also, according to Preparation method containing metallic atom nano-carbon material of the invention, the nano-carbon material containing metallic atom of preparation has the property of stabilization Energy.
Nano-carbon material containing metallic atom of the invention shows good urging in the dehydrogenation reaction of hydrocarbons Change performance, feed stock conversion and selectivity of product can be significantly improved.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is the transmission electron microscope photo containing metallic atom nano-carbon material prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of the raw material nano carbon material that embodiment 1 is used.
Specific embodiment
In the present invention, nano-carbon material refers at least one-dimensional carbon material less than 100nm of dispersed phase yardstick.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material contains C element, O elements, N element and at least one metallic element.In the present invention, " at least one " table Show one or more.
Nano-carbon material containing metallic atom of the invention, at least part of metallic element is in the periodic table of elements Group ia metal element and group iia metallic element, its instantiation can include but is not limited to lithium, sodium, potassium, beryllium, magnesium, calcium, One or more in barium and strontium.Preferably, at least partly the metallic element is the one kind in sodium, potassium, magnesium, calcium and barium Or it is two or more.
According to specific needs, the nano-carbon material containing metallic atom can also contain other metallic elements.In the present invention A kind of implementation method in, the nano-carbon material containing metallic atom contain at least one first metallic element and it is optional extremely A kind of few second metallic element.
First metallic element is selected from group ia metal element and group iia metallic element in the periodic table of elements, its tool Body example can include but is not limited to one or more in lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, it is described First metallic element be sodium, potassium, magnesium, calcium and barium in one or more.
Second metallic element is the metallic element in addition to group ia metal element and group iia metallic element, is such as selected Group IIIB metallic element, group ivb metallic element, Group VB metallic element, vib metals unit from the periodic table of elements Element, VIIB races metallic element, group VIII metallic element, I B-group metal element, group iib metallic element, group III A Metallic element, group iva metallic element and VA races metallic element.The instantiation of second metallic element can include but Be not limited to scandium, yttrium, thulium (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, Palladium, platinum, copper, silver, gold, zinc, aluminium, germanium, tin, lead and antimony.Preferably, second metallic element is selected from group VIII metal unit Element, group iva metallic element, I B-group metal element and group iib metallic element.It is highly preferred that second metallic element Selected from group VIII metallic element.It is further preferred that second metallic element is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The content of first metallic element and the second metallic element can contain metallic atom nano-carbon material according to this Concrete application occasion is selected.When the nano-carbon material containing metallic atom is used as the catalyst of hydrocarbon dehydrogenation reaction, with this On the basis of the total amount of the metallic element in nano-carbon material containing metallic atom and in terms of element, the content of first metallic element It is 20-100 weight %, more preferably preferably 40-95 weight %, 60-90 weight %；The content of second metallic element is 0-80 weight %, preferably 5-60 weight %, more preferably 10-40 weight %.
In a kind of implementation method being more highly preferred to of the invention, first metallic element is selected from magnesium, calcium and barium, described Second metallic element is selected from iron, cobalt and nickel.In the implementation method being more highly preferred to, with the nano-carbon material containing metallic atom Metallic element total amount on the basis of and in terms of element, the content of first metallic element is preferably 25-85 weight %, more excellent Elect 60-75 weight % as；The content of second metallic element is preferably 15-75 weight %, more preferably 25-40 weight %. Nano-carbon material containing metallic atom according to the preferred embodiment shows more in the catalyst as hydrocarbon dehydrogenation reaction Excellent catalysis activity.
In the implementation method that another kind is more highly preferred to, first metallic element is selected from sodium and potassium, second metal Element is selected from ruthenium, rhodium, palladium and platinum.In the implementation method being more highly preferred to, with the gold in the nano-carbon material containing metallic atom On the basis of the total amount of category element and in terms of element, the content of first metallic element is preferably 20-95 weight %, more preferably 65-90 weight %；The content of second metallic element is preferably 5-80 weight %, more preferably 10-35 weight %.According to this The nano-carbon material containing metallic atom of preferred embodiment shows more excellent in the catalyst as hydrocarbon dehydrogenation reaction Catalysis activity.
Nano-carbon material containing metallic atom of the invention, on the basis of the total amount containing metallic atom nano-carbon material And in terms of element, the content of O elements is 1-12 weight %, more preferably preferably 3-10 weight %, 6-8 weight %；N element Content is 0.1-6 weight %, more preferably preferably 0.5-5.5 weight %, 0.9-5 weight %；The total amount of metallic element is 0.2-15 weight %, preferably 1.5-8 weight %, more preferably 3-6.5 weight %；The content of C element is 67-98.7 weights Amount %, more preferably preferably 76.5-95 weight %, 80.5-90.1 weight %.Wherein, the content of each element uses X-ray light Electronic spectroscopy is determined.Sample is dried 3 hours at a temperature of 150 DEG C in helium atmosphere before testing.
In the present invention, X-ray photoelectron spectroscopic analysis are in Thermo Scientific companies equipped with Thermo Tested on the ESCALab250 type x-ray photoelectron spectroscopies of Avantage V5.926 softwares, excitaton source is monochromatization Al K α X-rays, energy is 1486.6eV, and power is 150W, and penetrating energy used by narrow scan is 30eV, base vacuum during analysis test It is 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage softwares On carry out data processing, quantitative analysis is carried out using sensitivity factor method in analysis module.
Nano-carbon material containing metallic atom of the invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity The total content of the oxygen element that sub- power spectrum determines is IO t, determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum O elements (that is, the oxygen atom being bonded with metallic atom) content be IO m, IO m/IO tIn the range of 0.05-0.6, preferably exist In the range of 0.1-0.55, more preferably in the range of 0.18-0.3.Nano-carbon material containing metallic atom of the invention, by The content of the O elements that the peak in x-ray photoelectron power spectrum in the range of 531.0-533.5eV determines is IO nm, IO nm/IO tIn 0.4- In the range of 0.95, preferably in the range of 0.6-0.9.In the present invention, represent number range when, " ×-× scope It is interior " include two binary values.
In the present invention, the area of the O1s spectral peaks in x-ray photoelectron power spectrum is designated as AO 1, O1s spectral peaks are divided into two groups Peak, A is designated as by the area of the spectral peak (corresponding to the oxygen species being connected with metallic atom) in the range of 529.5-530.8eVO 2, will The area of the spectral peak (corresponding to the oxygen species not being connected with metallic atom) in the range of 531.0-533.5eV is designated as AO 3, wherein, IO m/IO t=AO 2/AO 1, IO nm/IO t=AO 3/AO 1。
Nano-carbon material containing metallic atom of the invention, by 531.0-532.5eV scopes in x-ray photoelectron power spectrum The amount of the O elements (that is, C=O) that interior peak determines is IO c, by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum The amount of the O elements (that is, C-O) of determination is IO e, IO c/IO eIt is more excellent preferably in the range of 0.3-0.95 in the range of 0.2-1 It is selected in the range of 0.6-0.8.In the present invention, by the spectral peak in x-ray photoelectron power spectrum in the range of 531.0-533.5eV (corresponding to the oxygen species not being connected with metallic atom) is further separated into two groups of peaks, i.e., the spectrum in the range of 531.0-532.5eV Peak (corresponding to C=O species) and the spectral peak (corresponding to CO species) in the range of 532.6-533.5eV, will be in 531.0- The area of the spectral peak in the range of 532.5eV is designated as AO 4, the area of the spectral peak in the range of 532.6-533.5eV is designated as AO 5, IO c/IO e=AO 4/AO 5。
Nano-carbon material containing metallic atom of the invention, with the nano-carbon material containing metallic atom by X-ray light It is true by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum on the basis of the total amount of the C element that electron spectrum determines The content of fixed C element (that is, graphite mould carbon) can be 60-95 weight %, preferably 65-85 weight %, more preferably 70-80 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 5- 40 weight %, preferably 15-35 weight %, more preferably 20-30 weight %.In the present invention, by x-ray photoelectron power spectrum The area A of C1s spectral peaksC 1Determine the total amount of C element, the C1s spectral peaks in x-ray photoelectron power spectrum are divided into two groups of peaks, that is, exist Spectral peak (corresponding to graphite mould carbon species) in the range of 284.7-284.9eV and the spectral peak in the range of 286.0-288.8eV (corresponding to non-graphite type carbon species), the area of the spectral peak in the range of 284.7-284.9eV is designated as AC 2, will be in 286.0- The area of the spectral peak in the range of 288.8eV is designated as AC 3, it is true by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum Content=the A of fixed C elementC 2/AC 1, the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum Total content=AC 3/AC 1。
Nano-carbon material containing metallic atom of the invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity The amount of the C element that the peak in sub- power spectrum in the range of 288.6-288.8eV determines is IC c, by 286.0- in x-ray photoelectron power spectrum The amount of the C element that the peak in the range of 286.2eV determines is IC e, IC c/IC eIn the range of 1-5, preferably in the range of 1-3, more It is preferred that in the range of 1.2-2.In the present invention, by the spectral peak in x-ray photoelectron power spectrum in the range of 286.0-288.8eV (corresponding to agraphitic carbon species) is further divided into two groups of peaks, i.e., the spectral peak in the range of 286.0-286.2eV (corresponds to hydroxyl Base and ether type carbon species) and spectral peak (correspond to carboxyl, acid anhydride and ester type carbon species) in the range of 288.6-288.8eV, will The area of the spectral peak in the range of 286.0-286.2eV is designated as AC 4, the area of the spectral peak in the range of 288.6-288.8eV is remembered It is AC 5, IC c/IC e=AC 5/AC 4。
Nano-carbon material containing metallic atom of the invention, determines that this contains metallic atom and receives by x-ray photoelectron power spectrum The total amount of the N element in rice carbon material is IN t, the N determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum The amount of element is IN c, IN c/IN tIn the range of 0-0.5, preferably in the range of 0.01-0.35, more preferably in 0.03-0.15 In the range of.
Nano-carbon material containing metallic atom of the invention, determines that this contains metallic atom and receives by x-ray photoelectron power spectrum The total amount of the N element in rice carbon material is IN t, the N determined by the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum The content of element is IN n, IN n/IN tIn the range of 0.2-1, preferably in the range of 0.5-0.95, more preferably in 0.65-0.92 In the range of.
Nano-carbon material containing metallic atom of the invention, by 400.6-401.5eV scopes in x-ray photoelectron power spectrum Content is relatively low does not contain even for the N element (that is, graphite mould nitrogen) that interior peak determines.Usually, it is of the invention containing metallic atom In nano-carbon material, the amount of the N element determined by the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum is IN g, IN g/IN tTo be not higher than 0.3, typically in the range of 0.02-0.25, preferably in the range of 0.05-0.2.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peaks in x-ray photoelectron power spectrumN 1, by X-ray N1s spectral peaks in photoelectron spectroscopy are divided into three groups of peaks, i.e., the spectral peak in the range of 403.5-406.5eV (corresponds to-NO2Thing Kind), in the range of spectral peak in the range of 400.6-401.5eV (corresponding to graphite mould nitrogen species) and 398.5-400.1eV Spectral peak (removes graphite mould nitrogen and-NO2Nitrogen species outside type nitrogen), the area of the spectral peak in the range of 400.6-401.5eV is remembered It is AN 2, the area of the spectral peak in the range of 398.5-400.1eV is designated as AN 3, by the spectral peak in the range of 403.5-406.5eV Area be designated as AN 4, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, IN n/IN t=AN 4/AN 1, the ratio for obtaining be less than When 0.01, it is believed that without such species, and the content of such species is designated as 0.
In the present invention, the combination of the position at each peak as corresponding to the summit at the peak can determine that scope determines by mentioned earlier Peak refer to peak that combination corresponding to summit can be in such range, a peak can be included within the range, it is also possible to wrap Include more than two peaks.For example：Peak in the range of 398.5-400.1eV refers to that the combination corresponding to summit can be in 398.5- Whole peaks in the range of 400.1eV.
Nano-carbon material containing metallic atom of the invention can exist with common various forms, be specifically as follows but It is not limited to CNT containing metallic atom, Graphene containing metallic atom, thin layer graphite containing metallic atom, nano-sized carbon containing metallic atom One kind in particle, carbon nano-fiber containing metallic atom, Nano diamond containing metallic atom and fullerene containing metallic atom or two Plant the combination of the above.The CNT containing metallic atom can be SWCN containing metallic atom, containing metallic atom One or more combination in double-walled carbon nano-tube and multi-walled carbon nano-tubes containing metallic atom.It is of the invention containing gold Category atom nano-carbon material, preferably multi-walled carbon nano-tubes containing metallic atom.
Nano-carbon material containing metallic atom of the invention, it is preferable that described containing metallic atom multi-walled carbon nano-tubes Specific surface area is 50-500m2/ g, so can further improve the catalytic performance containing metallic atom nano-carbon material, particularly As the catalytic performance of the catalyst of hydrocarbons dehydrogenation reaction.It is highly preferred that this contains the ratio of metallic atom multi-walled carbon nano-tubes Surface area is 80-300m2/g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nano-tubes is 90-250m2/ g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nano-tubes is 120-180m2/g.In the present invention, institute Specific surface area is stated to be determined by nitrogen adsorption BET method.
Nano-carbon material containing metallic atom of the invention, the multi-walled carbon nano-tubes containing metallic atom is in 400-800 DEG C temperature range in weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that In the range of 0.01-0.5, more preferable catalytic effect, particularly urging as hydrocarbons dehydrogenation reaction are so obtained in that During agent, more preferable catalytic effect can be obtained.It is highly preferred that w500/w800In the range of 0.02-0.4.It is further preferred that w500/w800In the range of 0.05-0.15.In the present invention, w800=W800- W400, w500=W500- W400, W400It is at 400 DEG C At a temperature of determine mass loss rate, W800It is the mass loss rate determined at a temperature of 800 DEG C, W500It is at 500 DEG C At a temperature of determine mass loss rate；The weight-loss ratio is determined using thermogravimetric analyzer in air atmosphere, tests initial temperature It it is 25 DEG C, heating rate is 10 DEG C/min；Sample is depressed in helium atmosphere in 150 DEG C of temperature and 1 normal atmosphere before testing Middle drying 3 hours.
It is of the invention it is a kind of preferred embodiment in, the nano-carbon material containing metallic atom is preferably containing metal raw Sub- multi-walled carbon nano-tubes, the specific surface area for containing metallic atom multi-walled carbon nano-tubes is 50-500m2/ g, preferably 80-300m2/ G, more preferably 90-250m2/ g, more preferably 120-180m2/ g, and w500/w800It is excellent in the range of 0.01-0.5 It is selected in the range of 0.02-0.4, more preferably in the range of 0.05-0.15.
Nano-carbon material containing metallic atom of the invention, it is nonmetallic miscellaneous for other outside oxygen atom and nitrogen-atoms Atom, such as sulphur atom and phosphorus atoms, its content can be customary amount.Usually, it is of the invention containing metallic atom nanometer In 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 %, preferably below 0.2 weight %, more preferably below 0.1 weight %, more preferably 0.05 weight Amount below %.Nano-carbon material containing metallic atom of the invention, in addition to aforesaid metal elements, can also contain other metals Atom, described other metallic atoms for example can be from the catalyst used when preparing nano-carbon material.Described other gold The content for belonging to atom is generally below 2.5 weight %, preferably below 2 weight %, more preferably below 1 weight %, more More preferably below 0.5 weight %, particularly preferably below 0.2 weight %.
According to the second aspect of the invention, the invention provides a kind of preparation side containing metallic atom nano-carbon material Method, the method includes for one kind being dispersed with raw material nano carbon material, at least one alkaline metal cpds and at least one nitre The aqueous dispersions of acid metal salt are reacted in closed container.
The method according to the invention, metallic element in the alkaline metal cpds is selected from group ia metal element and the Group IIA metal element, its instantiation can include but is not limited to lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, it is described Metallic element is selected from sodium, potassium, magnesium, calcium and barium.
Preferably, the alkaline metal cpds are selected from the hydroxide containing metallic element and the alkalescence containing metallic element Salt.It is highly preferred that the alkaline metal cpds are selected from the hydroxide containing metallic element, the oxide containing metallic element, contain The organic metal salt of metallic element, the carbonate containing metallic element and bicarbonate and subcarbonate containing metallic element. The instantiation of the alkaline metal cpds can be included but is not limited to：Lithium hydroxide, NaOH, potassium hydroxide, hydrogen-oxygen Change beryllium, magnesia, calcium oxide, barium monoxide, basic magnesium carbonate, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, carbonic acid In sodium, potassium carbonate, calcium carbonate, barium carbonate, sodium acid carbonate, calcium bicarbonate, saleratus and barium bicarbonate one or two with On.It is highly preferred that the alkaline metal cpds are NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide and magnesium hydroxide In one or more.
The method according to the invention, the metallic element in the nitric acid slaine is selected from and can form water-soluble nitric acid metal The metallic element of salt, such as selected from group ia metal element, group iia metallic element, Group IIIB metal unit in the periodic table of elements Element, group ivb metallic element, Group VB metallic element, vib metals element, VIIB races metallic element, group VIII gold Category element, I B-group metal element, group iib metallic element, group III A metallic element, group iva metallic element and VA Race's metallic element.The instantiation of the metallic element in the nitric acid slaine can include but is not limited to lithium, sodium, potassium, magnesium, Calcium, barium, strontium, scandium, yttrium, thulium (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, Nickel, palladium, platinum, copper, silver, gold, zinc, aluminium, germanium, tin and antimony.Preferably, the metallic element in the nitric acid slaine is selected from VIII Race's metallic element, group iva metallic element, I B-group metal element and group iib metallic element.It is highly preferred that the nitric acid Metallic element in slaine is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The consumption of the method according to the invention, the alkaline metal cpds and the nitric acid slaine can be according to expection The content and species of the nitrogen, oxygen element and metallic element that are introduced in raw material nano carbon material are selected.Most The nano-carbon material containing metallic atom for preparing eventually is in the catalyst as hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material： Alkaline metal cpds：The weight ratio of nitric acid slaine is 1：0.01-10：In the range of 0.01-10, thus prepare containing metal Atom nano-carbon material can obtain the catalytic effect of further raising in the catalyst as hydrocarbon dehydrogenation reaction.It is highly preferred that Raw material nano carbon material：Alkaline metal cpds：The weight ratio of nitric acid slaine is 1：0.015-8：In the range of 0.02-5.Enter One step preferably, raw material nano carbon material：Alkaline metal cpds：The weight ratio of nitric acid slaine is 1：0.1-2：0.05-4's In the range of.
The method according to the invention, the method according to the invention, alkaline metal cpds：The mol ratio of nitric acid slaine is excellent It is selected in 1：In the range of 0.001-50, the nano-carbon material containing metallic atom for thus preparing is in the catalyst as hydrocarbon dehydrogenation reaction When also have more excellent catalysis activity.It is highly preferred that alkaline metal cpds：The mol ratio of nitric acid slaine is 1： In the range of 0.002-45.It is further preferred that alkaline metal cpds：The mol ratio of nitric acid slaine is 1：0.004-40's In the range of.
Method according to the invention it is possible to the amount according to raw material nano carbon material is selected the consumption of water.Preferably, Raw material nano carbon material：H2The weight ratio of O is 1：In the range of 5-1000, when the consumption of water is within the scope of being somebody's turn to do, nanometer Structural form retentivity of the carbon material in processing procedure is more preferable, for example：It is basic in processing procedure for CNT Will not be cut off.It is highly preferred that raw material nano carbon material：H2The weight ratio of O is 1：In the range of 10-500.Further preferably Ground, raw material nano carbon material：H2The weight ratio of O is 1：In the range of 50-150.
The method according to the invention, in a preferred embodiment, the metallic element of the alkaline metal cpds Selected from magnesium, calcium and barium, the metallic element of the nitric acid slaine is selected from iron, cobalt and nickel, thus prepare containing metallic atom nanometer Carbon material can obtain more preferable catalytic reaction effect in the catalyst as hydrocarbon dehydrogenation reaction.Raw material nano carbon material：Alkalescence Metallic compound：The weight ratio of nitric acid slaine is preferably 1：0.05-6：In the range of 0.04-6, more preferably 1：0.1-1： In the range of 0.5-4.This preferred embodiment in, alkaline metal cpds：The mol ratio of nitric acid slaine is preferably 1： In the range of 0.03-45, more preferably 1：In the range of 0.4-40.This preferred embodiment in, raw material nano carbon material： H2The weight ratio of O is preferably 1：In the range of 20-200, more preferably 1：In the range of 100-150.
The method according to the invention, in another preferred embodiment, the metal unit of the alkaline metal cpds Element is selected from sodium and potassium, and the metallic element of the nitric acid slaine is selected from ruthenium, rhodium, palladium and platinum, and what is thus prepared receives containing metallic atom Rice carbon material can obtain more preferable catalytic reaction effect in the catalyst as hydrocarbon dehydrogenation reaction.Raw material nano carbon material：Alkali Property metallic compound：The weight ratio of nitric acid slaine is preferably 1：0.01-3：In the range of 0.02-1, more preferably 1：0.1-2： In the range of 0.05-0.1.This preferred embodiment in, alkaline metal cpds：The mol ratio of nitric acid slaine preferably exists 1：In the range of 0.002-6, more preferably 1：In the range of 0.004-0.4.This preferred embodiment in, raw material nano carbon Material：H2The weight ratio of O is preferably 1：In the range of 20-200, more preferably 1：In the range of 50-150.
The method according to the invention, oxygen atom, the nitrogen of the condition of the reaction to be enough to improve in raw material nano carbon material The content of atom and metallic atom is defined.Preferably, in course of reaction, the scope of the temperature of the aqueous dispersions at 80-300 DEG C It is interior.When the temperature of the aqueous dispersions is within above range, in can not only effectively improving raw material nano carbon material Oxygen atom, nitrogen-atoms and metal atom content, and the generation of the structural form of raw material nano carbon material will not be significantly affected.More Preferably, in course of reaction, the temperature of the aqueous dispersions is in the range of 110-220 DEG C.
The method according to the invention, duration of the reaction can be selected according to the temperature of reaction, with can Enough oxygen atoms, nitrogen-atoms and metallic atom is introduced in raw material nano carbon material to be defined.Usually, the reaction continues Time can be in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably in the scope of 24-36 hours It is interior.
Method according to the invention it is possible to form the aqueous dispersions using conventional various methods, for example can be by Raw material nano carbon material is dispersed in water (preferably deionized water), is subsequently adding the alkaline metal cpds and the nitric acid Slaine, so as to obtain the aqueous dispersions.In order to further improve the dispersion effect of raw material nano carbon material, while shorten dividing The scattered time, raw material nano carbon material can be dispersed in water using the method for sonic oscillation.The condition of the sonic oscillation Can be conventional selection, usually, the frequency of the sonic oscillation can be 10-200kHz, preferably 90-140kHz；It is described The duration of sonic oscillation can be 0.1-6 hours, preferably 1-4 hours.The method according to the invention, the alkalinous metal Compound and the nitric acid slaine can each be provided in the form of solution (the preferably aqueous solution), it is also possible to pure material Form is provided, and is not particularly limited.
The method according to the invention, the content of oxygen element and nitrogen is not limited especially in the raw material nano carbon material It is fixed, can be conventional selection.Usually, the content of oxygen element is not higher than 1.5 weight % in the raw material nano carbon material, excellent Elect not higher than 1.2 weight %, more preferably not above 0.5 weight %, more preferably not higher than 0.3 weight % as；Nitrogen unit The content of element is not higher than 0.5 weight %, more preferably not above preferably not higher than 0.2 weight %, 0.1 weight %, enters one Step is preferably not higher than 0.05 weight %, still more preferably to be not higher than 0.02 weight %.The method according to the invention, it is described The total amount of remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) in raw material nano carbon material outside oxygen atom and nitrogen-atoms (in terms of element) can be as customary amount.Usually, remaining in the raw material nano carbon material in addition to oxygen element and nitrogen The total amount (in terms of element) of nonmetallic heteroatoms be not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably Not higher than 0.1 weight %, more preferably not higher than 0.05 weight %.The method according to the invention, the raw material nano carbon Material may contain some metallic elements according to the difference in source, such as used when from preparing raw material nano-carbon material Metallic atom in catalyst.The content (in terms of element) of metallic atom is generally 2.5 weights in the raw material nano carbon material Amount below %, more preferably preferably below 1.8 weight %, below 0.5 weight %, are still more preferably 0.1 weight Amount below %.
The method according to the invention, raw material nano carbon material can be washed using preceding using method commonly used in the art Wash, to remove some impurity of raw material nano carbon material surface；Can not also be washed, directly be used.It is disclosed by the invention In embodiment, raw material nano carbon material is pre-processed using preceding.
Method according to the invention it is possible to the nano-carbon material of various existing forms is processed, so as to improve this receive Oxygen atom, nitrogen-atoms and metal element content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon and receive In mitron, Graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene one or two with On combination.The CNT can be SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes in one kind or Two or more combinations.Preferably, the raw material nano carbon material is CNT, more preferably multi-walled carbon nano-tubes.
The method according to the invention, in a preferred embodiment, the raw material nano carbon material is received for many wall carbon Mitron, the specific surface area of the multi-walled carbon nano-tubes can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100- 260m2/ g, more preferably 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nano-tubes, temperature of the multi-walled carbon nano-tubes at 400-800 DEG C Weight-loss ratio in degree interval is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800Can be in 0.01- In the range of 0.5, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably exist In the range of 0.05-0.15.
In a kind of implementation method being more highly preferred to of the invention, the raw material nano carbon material is multi-walled carbon nano-tubes, The specific surface area of the multi-walled carbon nano-tubes is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, enters One step is preferably 120-190m2/g；Weight-loss ratio of the multi-walled carbon nano-tubes in 400-800 DEG C of temperature range is w800, Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, preferably 0.02-0.4's In the range of, more preferably in the range of 0.05-0.35, further preferably in the range of 0.05-0.15.
The method according to the invention, the reaction is carried out in closed container.The reaction can be in self-generated pressure (i.e., Do not apply pressure additionally) under carry out, it is also possible to carry out under pressure.Preferably, the reaction is entered at autogenous pressures OK.The closed container can be the common reactor that can realize sealing and heating, such as autoclave.
The method according to the invention, isolates solid matter, and will divide in can also including the mixture obtained from reaction The solid matter for separating out is dried, so as to obtain the nano-carbon material containing metallic atom.
Solid matter is isolated in the mixture that can be obtained from reaction using conventional solid-liquid separating method, be such as centrifuged, One or more combination in filtering and decantation.
The dry condition can be conventional selection, be can remove the volatile materials in the solid matter isolated It is accurate.Usually, the drying can be carried out at a temperature of 50-200 DEG C, be carried out preferably at a temperature of 80-180 DEG C, more excellent Carried out at a temperature of being selected in 120-160 DEG C.The dry duration can be selected according to dry temperature and mode. Usually, the dry duration can be 0.5-48 hours, preferably 6-24 hours, more preferably 6-12 hours.Institute Stating drying can be carried out under normal pressure (that is, 1 standard atmospheric pressure), it is also possible to be carried out at reduced pressure.From further raising The angle of dry efficiency is set out, and the drying is preferably carried out at reduced pressure.
The method according to the invention, can effectively improve oxygen atom in raw material nano carbon material, nitrogen-atoms and metal raw Sub- content, while will not be produced to the structural form of raw material nano carbon material significantly affecting.
According to the third aspect of the present invention, the invention provides one kind by prepared according to the methods of the invention containing metal Atom nano-carbon material.
According to the fourth aspect of the present invention, the invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material is by according to the nano-carbon material containing metallic atom of one side of the invention or according to the present invention the Prepared by three nano-carbon materials containing metallic atom of aspect are calcined.
The roasting can be carried out under normal conditions.Preferably, the roasting is carried out at a temperature of 250-500 DEG C. It is highly preferred that the roasting is carried out at a temperature of 300-450 DEG C, carried out at a temperature of such as 350-450 DEG C.The roasting is held The continuous time can be selected according to the temperature of roasting.Usually, the duration of the roasting can be 1-24 hours, preferably It is 2-12 hours, more preferably 2-4 hours.The roasting can be carried out in oxygen-containing atmosphere, it is also possible to by the indifferent gas bodily form Into atmosphere in carry out.The oxygen-containing atmosphere can be air atmosphere；Can also be oxygen mixed with what inert gas was mixed to form Atmosphere is closed, in the mixed atmosphere, the content of oxygen can be 0.1-22 volumes %.The inert gas can include but not limit In nitrogen and/or rare gas, the rare gas can be argon gas and/or helium.Angularly consider from convenience and cost, Preferably, the roasting is carried out in oxygen-containing atmosphere (such as air atmosphere).
Nano-carbon material containing metallic atom of the invention is received by prepared by the method for the present invention containing metallic atom Rice carbon material has good catalytic performance, and catalysis activity higher is particularly shown in hydrocarbons dehydrogenation reaction.
Nano-carbon material containing metallic atom of the invention is received by prepared by the method for the present invention containing metallic atom Rice carbon material can be directly used as catalyst, it is also possible to be used in the form of preformed catalyst.The preformed catalyst can contain With good grounds nano-carbon material containing metallic atom of the invention or the nano carbon material containing metallic atom prepared by the method for the present invention Material and binding agent.The binding agent can be selected according to the specifically used occasion of the preformed catalyst, disclosure satisfy that Use requirement is defined, for example, can be organic binder bond and/or inorganic binder.The organic binder bond can be common each Polymer-type binding agent is planted, the inorganic binder can be common various heat-resistant inorganic oxides, such as aluminum oxide and/or oxygen SiClx.It is to hydrocarbon dehydrogenation reaction (such as direct dehydrogenation reaction and oxidative dehydrogenation), particularly to oxygen in the preformed catalyst When fluidized dehydrogenation reaction has the preformed catalyst of catalytic action, the binding agent is preferably inorganic binder.The shaped catalyst In agent, the content containing metallic atom nano-carbon material can be selected according to specifically used requirement, be not particularly limited, typically Ground, on the basis of the total amount of the preformed catalyst, the content containing metallic atom nano-carbon material can be 5-95 weights Amount %.
According to the fifth aspect of the present invention, the invention provides being received containing metallic atom according to one side of the invention Rice carbon material, according to third aspect of the present invention nano-carbon material containing metallic atom or according to 4th aspect of the invention Nano-carbon material containing metallic atom as the catalyst of hydrocarbon dehydrogenation reaction application.
Application according to the present invention, the nano-carbon material containing metallic atom is used directly for hydrocarbon dehydrogenation reaction, also may be used To be used for hydrocarbon dehydrogenation reaction after shaping.The dehydrogenation reaction can be carried out in the presence of oxygen, it is also possible to not in the presence of oxygen Carry out.Preferably, the dehydrogenation reaction is carried out in the presence of oxygen, can so obtain more preferable catalytic effect.
According to the sixth aspect of the invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, the method is included in deposits Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with according to one side of the invention containing metal Atom nano-carbon material, according to third aspect of the present invention nano-carbon material containing metallic atom or according to the present invention the 4th The contact of nano-carbon material containing metallic atom of individual aspect.
Hydrocarbon dehydrogenation reaction method of the invention, the nano-carbon material containing metallic atom is used directly for being connect with hydrocarbon Touch, it is also possible to for being contacted with hydrocarbon after the nano-carbon material containing metallic atom is molded.
Hydrocarbon dehydrogenation reaction method of the invention can carry out dehydrogenation to polytype hydrocarbon, so as to obtain unsaturation Hydrocarbon, such as alkene.The method according to the invention is particularly suitable for carrying out dehydrogenation to alkane, so as to obtain unsaturated hydrocarbons, such as alkene.
The method according to the invention, the hydrocarbon is preferably alkane, such as C2-C12Alkane.Specifically, the hydrocarbon can be but Be not limited to ethane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- second Base pentane, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- dimethyl pentanes, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- front threes Base pentane, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4- dimethyl heptanes, 3- ethyl heptanes, 4- ethyl heptanes, 2, 3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- trimethyl cyclohexanes, 2,2,3- trimethyl cyclohexanes, 2,2,4- front threes Base hexane, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyl cyclohexanes, 2,4,4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- methyl -4- ethyl hexanes, 3,3- diethylpentanes, 1- methyl - 2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- ethyl cyclohexanes, n-propyl hexamethylene, isopropyl hexamethylene Alkane, trimethyl-cyclohexane (including various isomers of trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- front threes Butylcyclohexane, 1,2,5- trimethyl-cyclohexanes, 1,3,5- trimethyl-cyclohexanes), n-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyls octane, 4- ethyls octane, 2, 3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- trimethylheptanes, 2,4,5- trimethylheptanes, 2,4,6- front threes Base heptane, 2,2,3- trimethylheptanes, 2,2,4- trimethylheptanes, 2,2,5- trimethylheptanes, 2,2,6- trimethylheptanes, 2, 3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- methyl -3- ethyl heptanes, 2- methyl -4- ethyl heptanes, 2- methyl -5- Ethyl heptane, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyl heptanes, 4- methyl -4- ethyls Heptane, 4- propyl group heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- diethylpentanes, vinylbenzene, 1- In phenyl-propane, 2- phenyl-propanes, 1- phenyl butanes, 2- phenyl butanes, 1- phenyl pentanes, 2- phenyl pentanes and 3- phenyl pentanes One or more combination.It is highly preferred that the hydrocarbon be propane, normal butane, iso-butane and vinylbenzene in one kind or It is two or more.It is further preferred that the hydrocarbon is normal butane.
Hydrocarbon dehydrogenation reaction method of the invention, the reaction can be carried out under conditions of it there is oxygen, it is also possible to Under conditions of in the absence of oxygen.Preferably, hydrocarbon dehydrogenation reaction method of the invention, enters under conditions of it there is oxygen OK.In the method for the present invention when being carried out under conditions of there is oxygen, the consumption of oxygen can be conventional selection.Usually, hydrocarbon Can be 0.01-100 with the mol ratio of oxygen：1, preferably 0.1-10：1, more preferably 0.2-5：1, most preferably 0.5-2： 1。
Hydrocarbon dehydrogenation reaction method of the invention, can by carrier gas by hydrocarbon and optional oxygen send into reactor with The haptoreaction of nano-carbon material containing metallic atom.The carrier gas can be it is conventional at reaction conditions will not be with reactant and instead Answer product that chemical interaction and the gas that will not be decomposed, such as nitrogen, carbon dioxide, rare gas and water steaming occur One or more combination in gas.The consumption of the carrier gas can be conventional selection.Usually, the content of carrier gas can be with It is 30-99.5 volume %, more preferably preferably 50-99 volumes %, 70-98 volumes %.
Hydrocarbon dehydrogenation reaction method of the invention, the temperature of the contact can be conventional selection, to be enough to send out hydrocarbon Raw dehydrogenation reaction is defined.Usually, the contact can be carried out at a temperature of 200-650 DEG C, preferably in 300-600 DEG C of temperature Carried out under degree, carried out more preferably at a temperature of 350-550 DEG C, carried out further preferably at a temperature of 400-450 DEG C.
Hydrocarbon dehydrogenation reaction method of the invention, the contact can be carried out in fixed bed reactors, it is also possible to Carried out in fluidized-bed reactor, be not particularly limited.Preferably, the contact is carried out in fixed bed reactors.
Hydrocarbon dehydrogenation reaction method of the invention, the duration of the contact can be selected according to the temperature of contact Select, contact as described when being carried out in fixed bed reactors, holding for contact can be represented with the volume space velocity of the gas of charging The continuous time.Usually, the volume space velocity of the gas of charging can be 0.1-10000h-1, preferably 1-6000h-1, more preferably 5-5000h-1, more preferably 10-4000h-1, such as 1000-1500h-1。
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, outfit of the X-ray photoelectron spectroscopic analysis in Thermo Scientific companies Have on the ESCALab250 type x-ray photoelectron spectroscopies of Thermo Avantage V5.926 softwares and tested, excitaton source It is monochromatization Al K α X-rays, energy is 1486.6eV, and power is 150W, penetrating energy used by narrow scan is 30eV, analysis test When base vacuum be 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Data processing is carried out on Avantage softwares, quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is being surveyed Depressed in 150 DEG C of temperature and 1 normal atmosphere before examination and dried 3 hours in helium atmosphere.
In following examples and comparative example, thermogravimetric analysis is carried out on TA5000 thermal analyzers, and test condition is air gas Atmosphere, programming rate is 10 DEG C/min, and temperature range is room temperature (25 DEG C) to 1000 DEG C.Sample is before testing in 150 DEG C of temperature Depressed with 1 normal atmosphere and dried 3 hours in helium atmosphere.Using the ASAP2000 types N of Micromertrics companies of the U.S.2 Physical adsorption appearance measurement the specific area.The high-resolution-ration transmission electric-lens produced using FEI Co. of the U.S. analyze raw material nano carbon material And the microscopic appearance containing metallic atom nano-carbon material.
In following examples and comparative example, alkaline metal cpds and nitric acid slaine are each carried in the form of solid matter For.
Embodiment 1-35 is used to illustrate nano-carbon material containing metallic atom of the invention and preparation method thereof.
Embodiment 1
(1) using 20g, used as the multi-walled carbon nano-tubes of raw material nano carbon material, (specific surface area is 136m2/ g, oxygen atom content It is 0.3 weight %, nitrogen atom content is 0.02 weight %, (phosphorus is former for remaining nonmetallic heteroatoms in addition to nitrogen-atoms and oxygen atom Son and sulphur atom) total content be 0.01 weight %, metallic atom total content be 0.1 weight %, in 400-800 DEG C of temperature range Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, purchased from Chinese science Chengdu organic chemistry Co., Ltd of institute) dispersion in deionized water, being dispersed under the conditions of sonic oscillation is carried out, sonic oscillation condition Including：Frequency is 140kHz, and the time is 1 hour.Then, add as the barium hydroxide of alkaline metal cpds and as nitric acid The nickel nitrate of slaine, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Alkaline metal cpds：Nitric acid metal Salt：H2The weight ratio of O is 1：1：0.5：100 ratio feeds intake.
(2) aqueous dispersions that will be obtained are in the autoclave with polytetrafluoroethyllining lining, in 150 DEG C of temperature Under, react 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened Kettle, reactant mixture is filtered and washed, and collected solid matter.(1 standard is big in normal pressure for the solid matter that will be collected into Air pressure, similarly hereinafter), after drying 12 hours at a temperature of 120 DEG C, nano-carbon material containing metallic atom is obtained, this contains metallic atom and receives The rice composition of carbon material, specific surface area and w500/w800Listed in table 1.
Fig. 1 is the transmission electron microscope photo containing metallic atom nano-carbon material for preparing, and Fig. 2 is as many of raw material The transmission electron microscope photo of wall carbon nano tube.Be can be seen that containing the microcosmic of metallic atom nano-carbon material from Fig. 1 and Fig. 2 Form is good, shows that course of reaction is little to the structure influence of nano-carbon material.
Comparative example 1
Aqueous dispersions same as Example 1 are placed in and are equipped with the there-necked flask of condenser pipe, the there-necked flask is placed in During temperature is 150 DEG C of oil bath, in back flow reaction under normal pressure 24 hours.After reaction terminates, treat that the temperature in there-necked flask is down to After room temperature, reactant mixture is filtered and washed, and is collected solid matter.The solid matter that will be collected into is in normal pressure, 120 After being dried 12 hours at a temperature of DEG C, nano-carbon material containing metallic atom is obtained.Prepare containing metallic atom nano-carbon material Composition, specific surface area and w500/w800Listed in table 1.
Comparative example 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, step (1) is prepared Aqueous dispersions be free of nitric acid slaine.Wherein, by raw material nano carbon material：Alkaline metal cpds：Nitric acid slaine：H2O Weight ratio be 1：1：0：100 ratio feeds intake.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Comparative example 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, step (1) is prepared Aqueous dispersions be free of alkaline metal cpds.Wherein, by raw material nano carbon material：Alkaline metal cpds：Nitric acid slaine： H2The weight ratio of O is 1：0：0.5：100 ratio feeds intake.The composition containing metallic atom nano-carbon material, the specific surface area for preparing And w500/w800Listed in table 1.
Comparative example 4
In deionized water, ultrasound is dispersed in by using the nano-carbon material dispersion prepared with the identical method of comparative example 2 Carried out under oscillating condition, sonic oscillation condition includes：Frequency is 140kHz, and the time is 1 hour.Then, add as nitric acid gold Belong to the nickel nitrate of salt, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material (the raw material nano carbon used in comparative example 2 The amount of material)：Nitric acid slaine：H2The weight ratio of O is 1：0.5：100 ratio feeds intake.
The aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 150 DEG C, React 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reactor is opened, Reactant mixture is filtered and washed, and is collected solid matter.The solid matter that will be collected into is in normal pressure, 120 DEG C of temperature After being dried 12 hours under degree, nano-carbon material containing metallic atom is obtained, this contains the composition of metallic atom nano-carbon material, specific surface Product and w500/w800Listed in table 1.
Embodiment 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), make For the specific surface area of the multi-walled carbon nano-tubes (being purchased from Shandong great Zhan nano materials Co., Ltd) of raw material nano carbon material is 251m2/ g, the weight-loss ratio in 400-800 DEG C of temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range It is w500, w500/w800Be 0.33, oxygen atom content is 0.62 weight %, nitrogen atom content is 0.01 weight %, except nitrogen-atoms and The total content of remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) outside oxygen atom is 0.01 weight %, metallic atom total content It is 0.08 weight %.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (2), will The aqueous dispersions for obtaining are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in self-generated pressure Lower reaction 24 hours.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), press Raw material nano carbon material：Alkaline metal cpds：Nitric acid slaine：H2The weight ratio of O is 1：6：0.5：100 ratio feeds intake. The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 5
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), press Raw material nano carbon material：Alkaline metal cpds：Nitric acid slaine：H2The weight ratio of O is 1：1：0.04：100 ratio feeds intake. The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 6
Nano-carbon material containing metallic atom is prepared using method same as Example 1, the difference is that, nickel nitrate with etc. rub The plumbi nitras of your amount replaces.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 1 List.
Embodiment 7
Using 20g, used as the multi-walled carbon nano-tubes of raw material nano carbon material, (specific surface area is 183m2/ g, oxygen atom content is 0.2 weight %, nitrogen atom content is 0.01 weight %, remaining the nonmetallic heteroatoms (phosphorus atoms in addition to nitrogen-atoms and oxygen atom And sulphur atom) total content be 0.04 weight %, metallic atom total content be 0.03 weight %, 400-800 DEG C of humidity province Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.07, purchased from China Chengdu organic chemistry Co., Ltd of the academy of sciences) dispersion in deionized water, being dispersed under the conditions of sonic oscillation is carried out, sonic oscillation Condition includes：Frequency is 90kHz, and the time is 4 hours.Then, NaOH and the conduct as alkaline metal cpds are added The palladium nitrate of nitric acid slaine, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Alkaline metal cpds：Nitric acid Slaine：H2The weight ratio of O is 1：0.5：0.1：150 ratio feeds intake.
(2) aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, in 120 DEG C of temperature Under, react 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened Kettle, reactant mixture is filtered and washed, and collected solid matter.The solid matter that will be collected into normal pressure, 160 DEG C At a temperature of dry 6 hours after, obtain nano-carbon material containing metallic atom, this contains the composition of metallic atom nano-carbon material, compares table Area and w500/w800Listed in table 1.
Embodiment 8
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), make For the specific surface area of the multi-walled carbon nano-tubes (being purchased from Shandong great Zhan nano materials Co., Ltd) of raw material nano carbon material is 103m2/ g, w500/w800Be 0.23, oxygen atom content be 1.1 weight %, nitrogen atom content be 0.03 weight %, denitrogenate with outside oxygen Remaining nonmetallic heteroatoms (p and ses) total content be 0.01 weight %, metallic atom total content be 1.6 weight %.Prepare The composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 9
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (2), will The aqueous dispersions for obtaining are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in self-generated pressure Lower reaction 24 hours.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 10
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), alkali Property metallic compound and nitric acid slaine gross weight keep it is constant under conditions of, make alkaline metal cpds：Nitric acid slaine Mol ratio be 1：6.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Arranged in table 1 Go out.
Embodiment 11
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium is replaced with the nickel nitrate of equimolar amounts.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/ w800Listed in table 1.
Embodiment 12
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium is replaced with the barium nitrate of equimolar amounts.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/ w800Listed in table 1.
Embodiment 13
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium is replaced with potassium nitrate, calcium nitrate and sodium nitrate, nitric acid in the gross weight and embodiment 7 of sodium nitrate, potassium nitrate and calcium nitrate The weight of palladium is identical, and the mol ratio of potassium nitrate, calcium nitrate and sodium nitrate is 1：1：1.The nano-carbon material containing metallic atom for preparing Composition, specific surface area and w500/w800Listed in table 1.
Embodiment 14
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium is replaced with the plumbi nitras of equimolar amounts.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/ w800Listed in table 1.
Embodiment 15
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium is replaced with the cobalt nitrate of equimolar amounts.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/ w800Listed in table 1.
Embodiment 16
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium is replaced with copper nitrate and zinc nitrate, and the gross weight of copper nitrate and zinc nitrate is identical with the weight of palladium nitrate in embodiment 7, nitre Sour copper is 2 with the mol ratio of zinc nitrate：1.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/ w800Listed in table 1.
Embodiment 17
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), nitre Sour palladium is replaced with the platinum nitrate of equimolar amounts.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/ w800Listed in table 1.
Embodiment 18
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), hydrogen Sodium oxide molybdena is replaced with the calcium hydroxide of equimolar amounts.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 19
Nano-carbon material containing metallic atom is prepared using method same as Example 7, unlike, in step (1), hydrogen Sodium oxide molybdena is replaced with the magnesium hydroxide of equimolar amounts.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 20
Nano-carbon material containing metallic atom is prepared using method same as Example 1, difference is as follows：
In step (1), by the dispersion of raw material nano carbon material in deionized water, it is subsequently adding as alkaline metal cpds Potassium hydroxide and the nitric acid ruthenium as nitric acid slaine, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Alkali Property metallic compound：Nitric acid slaine：H2The weight ratio of O is 1：2：0.05：50 ratio feeds intake；
In step (2), the aqueous dispersions that will be obtained in the autoclave with polytetrafluoroethyllining lining, in 220 DEG C At a temperature of, react 36 hours at autogenous pressures.
The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 2.
Comparative example 5
It is equipped with being placed in the identical aqueous dispersions of embodiment 20 in the there-necked flask of condenser pipe, the there-necked flask is placed in During temperature is 220 DEG C of oil bath, in back flow reaction under normal pressure 36 hours.After reaction terminates, treat that the temperature in there-necked flask is down to After room temperature, reactant mixture is filtered and washed, and is collected solid matter.The solid matter that will be collected into is in normal pressure, 120 After being dried 12 hours at a temperature of DEG C, nano-carbon material containing metallic atom is obtained.Prepare containing metallic atom nano-carbon material Composition, specific surface area and w500/w800Listed in table 2.
Embodiment 21
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, in step (2), The aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 260 DEG C, in spontaneous pressure Reacted 36 hours under power.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Arranged in table 2 Go out.
Embodiment 22
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, received as raw material The multi-walled carbon nano-tubes of rice carbon material is with embodiment 2.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 2.
Embodiment 23
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 20, unlike, in step (1), Under conditions of the gross weight of alkaline metal cpds and nitric acid slaine keeps constant, make alkaline metal cpds：Nitric acid metal The mol ratio of salt is 1：0.1.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 2 List.
Embodiment 24
Nano-carbon material containing metallic atom is prepared using method same as Example 7, difference is as follows：
In step (1), by the dispersion of raw material nano carbon material in deionized water, it is subsequently adding as alkaline metal cpds Barium hydroxide and the cobalt nitrate as nitric acid slaine, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Alkali Property metallic compound：Nitric acid slaine：H2The weight ratio of O is 1：0.1：4：150 ratio feeds intake；
In step (2), the aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, in 110 At a temperature of DEG C, react 36 hours at autogenous pressures.
The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 2.
Embodiment 25
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 24, unlike, in step (1), As the multi-walled carbon nano-tubes of raw material nano carbon material with embodiment 8.The composition containing metallic atom nano-carbon material, the ratio for preparing Surface area and w500/w800Listed in table 2.
Embodiment 26
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 24, unlike, in step (1), By raw material nano carbon material：Alkaline metal cpds：Nitric acid slaine：H2The weight ratio of O is 1：8：4：150 ratio feeds intake. The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 2.
Embodiment 27
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 24, unlike, in step (1), By raw material nano carbon material：Alkaline metal cpds：Nitric acid slaine：H2The weight ratio of O is 1：0.1：0.02：150 ratio Feed intake.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 2.
Embodiment 28
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 24, unlike, in step (2), The aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, in spontaneous pressure Reacted 36 hours under power.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Arranged in table 2 Go out.
Embodiment 29
It is small that nano-carbon material containing metallic atom prepared by embodiment 1 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Comparative example 6
It is small that nano-carbon material containing metallic atom prepared by comparative example 1 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Comparative example 7
It is small that nano-carbon material containing metallic atom prepared by comparative example 2 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Comparative example 8
It is small that nano-carbon material containing metallic atom prepared by comparative example 3 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Comparative example 9
It is small that nano-carbon material containing metallic atom prepared by comparative example 4 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Embodiment 30
It is small that nano-carbon material containing metallic atom prepared by embodiment 2 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Embodiment 31
It is small that nano-carbon material containing metallic atom prepared by embodiment 3 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Embodiment 32
It is small that nano-carbon material containing metallic atom prepared by embodiment 4 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Embodiment 33
It is small that nano-carbon material containing metallic atom prepared by embodiment 5 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Embodiment 34
It is small that nano-carbon material containing metallic atom prepared by embodiment 6 is calcined 4 in air atmosphere at a temperature of 350 DEG C When.
Embodiment 35
It is small that nano-carbon material containing metallic atom prepared by embodiment 24 is calcined 2 in air atmosphere at a temperature of 450 DEG C When.
Embodiment 36-70 is used to illustrate the application containing metallic atom nano-carbon material of the invention and hydrocarbon dehydrogenation reaction side Method.
Embodiment 36-63
The nano-carbon material containing metallic atom for respectively being prepared by 0.2g (admission space is 1.9mL) embodiment 1-28 is used as urging Agent is seated in universal fixed bed miniature quartz pipe reactor, and the end seal of miniature quartz pipe reactor two has quartz sand, Under the conditions of 0.1MPa and 440 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 1.98 volume %, normal butane and oxygen Gas mol ratio 0.5：1, the balance of nitrogen as carrier gas) with cumulative volume air speed as 1200h-1It is passed through in reactor and is reacted, The composition of the reactant mixture that continuous monitoring is exported from reactor, and it is selective and total to calculate n-butane conversion, total olefin Butylene selectivity, the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 10-14
Reacted using with embodiment 36-63 identical methods, unlike, prepared using comparative example 1-5 respectively Nano-carbon material containing metallic atom is used as catalyst.Reaction result is listed in table 3.
Comparative example 15
Reacted using with embodiment 36-63 identical methods, unlike, use raw material same as Example 1 Nano-carbon material is used as catalyst.Reaction result is listed in table 3.
Comparative example 16
Reacted using with embodiment 36-63 identical methods, unlike, use raw material same as Example 7 Nano-carbon material is used as catalyst.Reaction result is listed in table 3.
Embodiment 64-70
Reacted using with embodiment 36-63 identical methods, unlike, use prepared by embodiment 29-35 containing Metallic atom CNT is used as catalyst.Reaction result is listed in table 4.
Comparative example 17-20
Reacted using with embodiment 36-63 identical methods, unlike, using comparative example 6-9 prepare containing gold Category atom CNT is used as catalyst.Reaction result is listed in table 4.
Comparative example 21
Reacted using with embodiment 36-63 identical methods, unlike, catalyst is will be same as Example 1 Raw material nano carbon material in the air atmosphere at a temperature of 350 DEG C obtained from roasting 4 hours.Reaction result is arranged in table 4 Go out.
Comparative example 22
Reacted using with embodiment 36-63 identical methods, unlike, catalyst is will be same as Example 7 Raw material nano carbon material in the air atmosphere at a temperature of 300 DEG C obtained from roasting 12 hours.Reaction result is arranged in table 4 Go out.
Table 3
Table 4
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (34)

1. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material contain C element, O elements, N element and At least one metallic element, on the basis of the total amount containing metallic atom nano-carbon material and in terms of element, the content of O elements is 1-12 weight %, the content of N element is 0.1-6 weight %, and the total amount of the metallic element is 0.2-15 weight %, C element Content be 67-98.7 weight %, at least part of metallic element be group ia metal element and group iia metallic element,
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron power spectrum is IO t, penetrated by X The content of the O elements that the peak in photoelectron spectra in the range of 529.5-530.8eV determines is IO m, IO m/IO t0.05-0.6's In the range of；
This contains in metallic atom nano-carbon material, is determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum The amount of O elements is IO c, the amount of the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum is IO e, IO c/IO eIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, and the N in the nano-carbon material containing metallic atom is determined by x-ray photoelectron power spectrum The total amount of element is IN t, the amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is IN c, IN c/IN tIn the range of 0-0.5, the N units determined by the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum The content of element is IN n, IN n/IN tIn the range of 0.2-1；
This contains in metallic atom nano-carbon material, is determined by the peak in the range of 288.6-288.8eV in x-ray photoelectron power spectrum The amount of C element is IC c, the amount of the C element determined by the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum is IC e, IC c/IC eIn the range of 1-5.
2. nano-carbon material containing metallic atom according to claim 1, wherein, IO m/IO tIt is excellent in the range of 0.1-0.55 It is selected in the range of 0.18-0.3；IO c/IO eIn the range of 0.3-0.95, preferably in the range of 0.6-0.8；IN c/IN t In the range of 0.01-0.35, preferably in the range of 0.03-0.15；IN n/IN tIn the range of 0.5-0.95, preferably exist In the range of 0.65-0.92；IC c/IC eIn the range of 1-3, preferably in the range of 1.2-2.
3. nano-carbon material containing metallic atom according to claim 1 and 2, wherein, with the nano carbon material containing metallic atom On the basis of the total amount of the C element determined by x-ray photoelectron power spectrum in material, by 284.7-284.9eV in x-ray photoelectron power spectrum In the range of peak determine C element content be 60-95 weight %, preferably 65-85 weight %, more preferably 70-80 weight Amount %, the content of the C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum is 5-40 weight %, Preferably 15-35 weight %, more preferably 20-30 weight %.
4. the nano-carbon material containing metallic atom according to any one in claim 1-3, wherein, by x-ray photoelectron Power spectrum determines that the total amount of the N element in the nano-carbon material containing metallic atom is IN t, by 400.6- in x-ray photoelectron power spectrum The amount of the N element that the peak in the range of 401.5eV determines is IN g, IN g/IN tTo be not higher than 0.3, preferably in the scope of 0.02-0.25 It is interior, more preferably in the range of 0.05-0.2.
5. the nano-carbon material containing metallic atom according to any one in claim 1-4, wherein, metallic atom is contained with this On the basis of the total amount of nano-carbon material and in terms of element, the content of O elements is 3-10 weight %, preferably 6-8 weight %；C units The content of element is 76.5-95 weight %, preferably 80.5-90.1 weight %；The content of N element is 0.5-5.5 weight %, preferably It is 0.9-5 weight %；The total amount of the metallic element is 1.5-8 weight %, preferably 3-6.5 weight %.
6. the nano-carbon material containing metallic atom according to any one in claim 1-5, wherein, this contains metallic atom and receives Rice carbon material contains the first metallic element and optional second metallic element, and first metallic element is selected from the periodic table of elements Middle group ia metal element and group iia metallic element, are preferably selected from sodium, potassium, magnesium, barium and calcium；The second metallic element choosing Group VIII metallic element, I B-group metal element, group iib metallic element and group iva metal unit from the periodic table of elements Element, is preferably selected from group VIII metallic element, is more preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
7. nano-carbon material containing metallic atom according to claim 6, wherein, with this containing metallic atom nano-carbon material On the basis of total amount and in terms of element, the content of first metallic element is 20-100 weight %, preferably 40-95 weight %, More preferably 60-90 weight %；The content of second metallic element be 0-80 weight %, preferably 5-60 weight %, it is more excellent Elect 10-40 weight % as.
8. nano-carbon material containing metallic atom according to claim 6, wherein, first metallic element is selected from magnesium, calcium And barium, second metallic element is selected from iron, cobalt and nickel, with the total amount of the metallic element in the nano-carbon material containing metallic atom On the basis of and in terms of element, the content of first metallic element is 25-85 weight %, preferably 60-75 weight %；Described The content of two metallic elements is 15-75 weight %, preferably 25-40 weight %；Or
First metallic element is selected from sodium and potassium, and second metallic element is selected from ruthenium, rhodium, palladium and platinum, and metal raw is contained with this On the basis of the total amount of the metallic element in sub- nano-carbon material and in terms of element, the content of first metallic element is 20-95 Weight %, preferably 65-90 weight %；The content of second metallic element is 5-80 weight %, preferably 10-35 weights Amount %.
9. the nano-carbon material containing metallic atom according to any one in claim 1-8, wherein, this contains metallic atom and receives Rice carbon material is CNT containing metallic atom；Preferably, it is containing many wall carbon of metallic atom that this contains metallic atom nano-carbon material Nanotube.
10. nano-carbon material containing metallic atom according to claim 9, wherein, the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 50-500m2/ g, preferably 80-300m2/ g, more preferably 90-250m2/ g, more preferably 120- 180m2/g。
11. nano-carbon material containing metallic atom according to claim 9 or 10, wherein, it is described containing many wall carbon of metallic atom Weight-loss ratio of the nanotube in 400-800 DEG C of temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, preferably in the range of 0.02-0.4, more preferably in the scope of 0.05-0.15 Interior, the weight-loss ratio is determined in air atmosphere.
A kind of 12. preparation methods containing metallic atom nano-carbon material, the method includes for one kind being dispersed with raw material nano carbon materials The aqueous dispersions of material, at least one alkaline metal cpds and at least one nitric acid slaine are carried out instead in closed container Should, the metallic element in the alkaline metal cpds is selected from group ia metal element and group iia metallic element, course of reaction In, the temperature of the aqueous dispersions is maintained in the range of 80-300 DEG C.
13. methods according to claim 12, wherein, raw material nano carbon material：Alkaline metal cpds：Nitric acid slaine Weight ratio 1：0.01-10：In the range of 0.01-10, preferably 1：0.015-8：In the range of 0.02-5, more preferably 1： 0.1-2：In the range of 0.05-4；
Raw material nano carbon material：H2The weight ratio of O is 1：In the range of 5-1000, preferably 1：In the range of 10-500, more preferably 1：In the range of 50-150.
14. method according to claim 12 or 13, wherein, alkaline metal cpds：The mol ratio of nitric acid slaine exists 1：In the range of 0.001-50, preferably 1：In the range of 0.002-45, more preferably 1：In the range of 0.004-40.
15. method according to any one in claim 12-14, wherein, the metallic element in the nitric acid slaine Selected from group ia metal element, group iia metallic element, group VIII metallic element, I B-group metal unit in the periodic table of elements Element, group iib metallic element and group iva metallic element, are preferably selected from group VIII metallic element, be more preferably selected from iron, ruthenium, Cobalt, rhodium, nickel, palladium and platinum.
16. method according to any one in claim 12-15, wherein, the alkaline metal cpds are selected from containing gold Belong to the hydroxide and the basic salt containing metallic element of element, be preferably selected from the hydroxide containing metallic element.
17. method according to any one in claim 12-16, wherein, the metal in the alkaline metal cpds Element is selected from group ia metal element and group iia metallic element, is preferably selected from sodium, potassium, magnesium, barium and calcium.
18. method according to any one in claim 12-16, wherein, the metal unit of the alkaline metal cpds Element is selected from magnesium, calcium and barium, and the metallic element of the nitric acid slaine is selected from iron, cobalt and nickel, raw material nano carbon material：Alkalinous metal Compound：The weight ratio of nitric acid slaine is 1：0.05-6：In the range of 0.04-6, preferably 1：0.1-1：The scope of 0.5-4 It is interior, alkaline metal cpds：The mol ratio of nitric acid slaine is 1：In the range of 0.03-45, preferably 1：The scope of 0.4-40 It is interior, raw material nano carbon material：H2The weight ratio of O is 1：In the range of 20-200, preferably 1：In the range of 100-150；Or
The metallic element of the alkaline metal cpds is selected from sodium and potassium, the metallic element of the nitric acid slaine be selected from ruthenium, rhodium, Palladium and platinum, raw material nano carbon material：Alkaline metal cpds：The weight ratio of nitric acid slaine is 1：0.01-3：The model of 0.02-1 In enclosing, preferably 1：0.1-2：In the range of 0.05-0.1, alkaline metal cpds：The mol ratio of nitric acid slaine is 1： In the range of 0.002-6, preferably 1：In the range of 0.004-0.4, raw material nano carbon material：H2The weight ratio of O is 1：20- In the range of 200, preferably 1：In the range of 50-150.
19. method according to any one in claim 12-18, wherein, in course of reaction, the temperature of the aqueous dispersions Degree is maintained in the range of 110-220 DEG C.
20. method according to any one in claim 12-19, wherein, the duration of the reaction is in 0.5-96 In the range of hour, preferably in the range of 2-72 hours, more preferably in the range of 24-36 hours.
21. method according to any one in claim 12-20, wherein, in the raw material nano carbon material, N element Content be not higher than 0.5 weight %, more preferably not above preferably not higher than 0.2 weight %, 0.1 weight %, further Preferably not higher than 0.05 weight %, is not higher than 1.5 still more preferably to be not higher than the content of 0.02 weight %, O element Weight %, preferably not higher than 1.2 weight %, more preferably not above 0.5 weight %, more preferably not higher than 0.3 weight Amount %, the total amount of metallic element is below 2.5 weight %, more preferably preferably below 1.8 weight %, 0.5 weight % Hereinafter, still more preferably it is below 0.1 weight %.
22. method according to any one in claim 12-21, wherein, the raw material nano carbon material is carbon nanometer Pipe；Preferably, the raw material nano carbon material is multi-walled carbon nano-tubes.
23. methods according to claim 22, wherein, the specific surface area of the multi-walled carbon nano-tubes is 50-500m2/ g, it is excellent Elect 80-300m as2/ g, more preferably 100-260m2/ g, more preferably 120-190m2/g。
24. method according to claim 22 or 23, wherein, humidity province of the multi-walled carbon nano-tubes at 400-800 DEG C Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the model of 0.01-0.5 In enclosing, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably 0.05-0.15's In the range of, the weight-loss ratio is determined in air atmosphere.
25. method according to any one in claim 12-24, wherein, the method is also included from mixing that reaction is obtained Solid matter is isolated in compound, and the solid matter that will be isolated is dried.
26. methods according to claim 25, wherein, the drying is carried out at a temperature of 50-200 DEG C, preferably in 80- Carried out at a temperature of 180 DEG C, carried out more preferably at a temperature of 120-160 DEG C, the dry duration is that 0.5-48 is small When, preferably 6-24 hours, more preferably 6-12 hours.
Nano-carbon material containing metallic atom prepared by the method in a kind of 27. 12-26 as claim described in any one.
A kind of 28. nano-carbon materials containing metallic atom, this contain metallic atom nano-carbon material be will be in claim 1-11 arbitrarily The nano-carbon material containing metallic atom described in nano-carbon material containing metallic atom or claim 27 described in one is roasted Prepared by burning.
29. nano-carbon materials containing metallic atom according to claim 28, wherein, temperature of the roasting at 250-500 DEG C Carried out under degree, carried out preferably at a temperature of 300-450 DEG C, the duration of the roasting is 1-24 hours, preferably 2-12 Hour, more preferably 2-4 hours.
Nano-carbon material containing metallic atom or claim 28-29 in 30. claim 1-11 and 27 described in any one Nano-carbon material containing metallic atom described in middle any one as the catalyst of hydrocarbon dehydrogenation reaction application.
31. applications according to claim 30, wherein, the dehydrogenation reaction is carried out in the presence of oxygen.
32. application according to claim 30 or 31, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, it is more excellent Elect normal butane as.
A kind of 33. hydrocarbon dehydrogenation reaction methods, the method is included in presence or absence of under conditions of oxygen, in hydrocarbon dehydrogenation reaction bar Under part, by nano-carbon material containing metallic atom or claim described in any one in hydrocarbon and claim 1-11 and 27 The contact of nano-carbon material containing metallic atom in 28-29 described in any one.
34. methods according to claim 33, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably Normal butane.
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CN110538670A (en) * 2018-05-28 2019-12-06 中国石油化工股份有限公司 Catalytic oxidation catalyst, preparation method thereof and cyclohexane oxidation method
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CN109647393A (en) * 2017-10-12 2019-04-19 中国石油化工股份有限公司 Catalyst and preparation method thereof for preparing isobutene through dehydrogenation of iso-butane
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CN112642481A (en) * 2019-10-10 2021-04-13 中国石油化工股份有限公司 Catalyst for preparing dialkyl carbonate from dialkyl oxalate, preparation method thereof and method for preparing dialkyl carbonate
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