CN106925278A - 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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CN106925278A
CN106925278A CN201511030296.2A CN201511030296A CN106925278A CN 106925278 A CN106925278 A CN 106925278A CN 201511030296 A CN201511030296 A CN 201511030296A CN 106925278 A CN106925278 A CN 106925278A
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nano
carbon material
range
weight
metallic atom
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CN106925278B (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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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

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  • Engineering & Computer Science (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

The invention discloses a kind of nano-carbon material containing metallic atom and preparation method and application, the nano-carbon material contains the O elements of 1-15 weight % and the metallic element of 1.1-20 weight %, the content of the O elements determined by the peak of 529.5-530.8eV in XPS is 0.02-0.5 with the ratio of the total amount of the O elements determined by XPS, and the amount of the O elements determined by the peak of 531.0-532.5eV is 0.2-1 with the ratio of the amount of the O elements determined by the peak of 532.6-533.5eV.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 Preparation method and the nano-carbon material containing metallic atom that is prepared by the method, the present invention further relates 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 root It is anti-as the application and a kind of hydrocarbon dehydrogenation of the catalyst of hydrocarbon dehydrogenation reaction according to nano-carbon material containing metallic atom of the invention Induction 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 chain The dehydrogenation reaction of alkane and obtain.Whether dehydrogenation reaction participates in that direct dehydrogenation reaction can be divided into (i.e., according to oxygen Oxygen is not involved in) and oxidative dehydrogenation (that is, oxygen is participated in) two classes.
Polytype nano-carbon material has been demonstrated have to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation There is catalytic effect, oxygen atom is introduced in nano-carbon material can then improve its catalysis activity.
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 receive The content of oxygen-containing functional group in rice carbon material.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and / or strong oxidizing solution (such as H2O2、KMnO4) in carry out back flow reaction, can also be aided in while back flow reaction Heating using microwave or sonic oscillation are carried out, to strengthen the effect of oxidation reaction.But, in strong acid and/or strong oxidizing solution Carrying out back flow reaction may have a negative impact to the skeleton structure of nano-carbon material, or even destroy the bone of nano-carbon material Frame structure.For example：Nano-carbon material is carried out into back flow reaction in nitric acid, although can be introduced on nano-carbon material surface A large amount of oxygen-containing functional groups, but easily cause nano-carbon material to be cut off and/or substantially increase the defect in graphite network structure Position, so as to reduce the performance of nano-carbon material, such as heat endurance.In addition, by strong acid and/or strong oxidizing solution Back flow reaction is carried out, to introduce during oxygen atom, the introduction volume of oxygen atom is high to the dependence of operation condition, fluctuate model Enclose wider.
Although the research about the doping vario-property and its catalytic performance of nano-carbon material achieves many progress, for it In some basic problems do not build consensus yet, still need 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 not It is only capable of in nano-carbon material surface introducing metallic atom, and can stably improves the content of oxygen atom 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 carbon material When expecting the dehydrogenation reaction for 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 feed stock conversion higher 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 raw Sub- nano-carbon material contains C element, O elements and at least one metallic element, and metallic atom nano-carbon material is contained with this On the basis of total amount and in terms of element, the content of O elements is 1-15 weight %, and the total amount of the metallic element is 1.1-20 weights Amount %, the content of C element is 65-97.9 weight %, and this contains in metallic atom nano-carbon material, by x-ray photoelectron energy The total content for composing the oxygen element for determining is IO t, determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum O elements content be IO m, IO m/IO tIn the range of 0.02-0.5；This contains in metallic atom nano-carbon material, by X The amount of the O elements that the peak in X-ray photoelectron spectroscopy X in the range of 531.0-532.5eV determines is IO c, by x-ray photoelectron The amount of the O elements that the peak in power spectrum in the range of 532.6-533.5eV determines is IO e, IO c/IO eIn the range of 0.2-1.
According to the second aspect of the invention, the invention provides a kind of preparation method containing metallic atom nano-carbon material, The method includes for one kind being dispersed with raw material nano carbon material, at least one transistion metal compound and at least one alkalescence The aqueous dispersions of metallic compound are reacted in closed container, and the metallic element in the alkaline metal cpds is selected from Group ia metal element and group iia metallic element, in course of reaction, the temperature of the aqueous dispersions is maintained at 80-300 In the range of DEG C.
According to the third aspect of the present invention, the invention provides a kind of method preparation by according to second aspect of the present invention 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 raw Sub- nano-carbon material is will to be carried out according to present invention one side or the 3rd nano-carbon material containing metallic atom of aspect Prepared by roasting.
According to the fifth aspect of the present invention, the invention provides according to one side of the invention containing metallic atom nanometer 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 presence Or in the absence of oxygen under conditions of, 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 Four contacts of nano-carbon material containing metallic atom of aspect.
Preparation method containing metallic atom nano-carbon material of the invention, can not only stably regulate and control and/or improve nanometer The content of metallic atom and oxygen atom in carbon material, while the structure influence to nano-carbon material in itself is small, preparation containing gold Category atom nano-carbon material has the performance of stabilization.
Nano-carbon material containing metallic atom of the invention shows good catalysis in the dehydrogenation reaction of hydrocarbons Performance, can significantly improve feed stock conversion and selectivity of product.
Brief description of the drawings
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 raw Sub- nano-carbon material contains C element, O elements and at least one metallic element.In the present invention, " at least one " is represented One or more.
Nano-carbon material containing metallic atom of the invention, on the basis of the total amount containing metallic atom nano-carbon material simultaneously In terms of element, the content of O elements is 1-15 weight %, more preferably preferably 3-8 weight %, 4-7.5 weight %, is entered One step is preferably 4.5-7 weight %；The total amount of metallic element be 1.1-20 weight %, preferably 1.7-16 weight %, it is more excellent Elect 2.4-13 weight %, more preferably 2.5-10 weight % as；The content of C element is 65-97.9 weight %, preferably It is 76-95.3 weight %, more preferably more preferably 79.5-93.6 weight %, 83-93 weight %.Wherein, each unit The content of element is determined using X-ray photoelectron spectroscopy.Sample is before testing at a temperature of 150 DEG C in helium atmosphere Dry 3 hours.
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 monochrome Change Al K α X-rays, energy is 1486.6eV, and power is 150W, penetrating energy used by narrow scan is 30eV, analysis is surveyed Base vacuum during examination is 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, Data processing is carried out on Thermo Avantage softwares, 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, by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum The content of the O elements (that is, the oxygen atom being bonded with metallic atom) of determination is IO m, IO m/IO tIn the scope of 0.02-0.5 It is interior, preferably in the range of 0.05-0.4, more preferably in the range of 0.05-0.3.It is of the invention to be received containing metallic atom Rice carbon material, the content of the O elements determined by the peak in the range of 531.0-533.5eV in x-ray photoelectron power spectrum is IO nm, IO nm/IO tIn the range of 0.5-0.98, preferably in the range of 0.6-0.95, more preferably in the range of 0.7-0.95.This In invention, when number range is represented, " ×-× in the range of " 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 Group peak, the area of the spectral peak (corresponding to the oxygen species being connected with metallic atom) in the range of 529.5-530.8eV is designated as AO 2, by the area note of the spectral peak (corresponding to the oxygen species not being connected with metallic atom) in the range of 531.0-533.5eV It is 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 532.6-533.5eV in x-ray photoelectron power spectrum In the range of peak determine O elements (that is, C-O) amount be IO e, IO c/IO eIn the range of 0.2-1, preferably in 0.25-0.85 In the range of, more preferably in the range of 0.4-0.8, further preferably in the range of 0.45-0.7.In the present invention, will Spectral peak (corresponding to the oxygen species not being connected with metallic atom) in x-ray photoelectron power spectrum in the range of 531.0-533.5eV Be further separated into two groups of peaks, i.e., spectral peak in the range of 531.0-532.5eV (corresponding to C=O species) and Spectral peak (corresponding to C-O species) in the range of 532.6-533.5eV, by the face of the spectral peak in the range of 531.0-532.5eV Product 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 photoelectricity On the basis of the total amount of the C element that sub- power spectrum determines, by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum The content of the C element (that is, graphite mould carbon) of determination can be 60-98 weight %, preferably 65-95 weight %, it is more excellent Elect 70-90 weight % as；The C element determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum it is total Content can be 2-40 weight %, more preferably preferably 5-35 weight %, 10-30 weight %.In the present invention, by X The area A of the C1s spectral peaks in X-ray photoelectron spectroscopy XC 1The total amount of C element is determined, by x-ray photoelectron power spectrum C1s spectral peaks are divided into two groups of peaks, i.e., spectral peak in the range of 284.7-284.9eV (corresponding to graphite mould carbon species) and Spectral peak (corresponding to non-graphite type carbon species) in the range of 286.0-288.8eV, by the spectrum in the range of 284.7-284.9eV The area at peak is designated as AC 2, the area of the spectral peak in the range of 286.0-288.8eV is designated as AC 3, by x-ray photoelectron Content=the A of the C element that the peak in power spectrum in the range of 284.7-284.9eV determinesC 2/AC 1, by x-ray photoelectron power spectrum Total content=the A of the C element that the peak in the range of middle 286.0-288.8eV determinesC 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 x-ray photoelectron power spectrum The amount of the C element that the peak in the range of 286.0-286.2eV determines is IC e, IC c/IC eIn the range of 0.4-2, preferably exist In the range of 0.45-1.8, more preferably in the range of 0.5-1.5.In the present invention, by x-ray photoelectron power spectrum Spectral peak (corresponding to agraphitic carbon species) in the range of 286.0-288.8eV is further divided into two groups of peaks, that is, exist Spectral peak (correspond to hydroxyl and ether type carbon species) in the range of 286.0-286.2eV and in the range of 288.6-288.8eV Spectral peak (corresponds to carboxyl, acid anhydride and ester type carbon species), and the area of the spectral peak in the range of 286.0-286.2eV is designated as into AC 4, The area of the spectral peak in the range of 288.6-288.8eV is designated as AC 5, IC c/IC e=AC 5/AC 4。
In the present invention, the combination of the position at each peak as corresponding to the summit at the peak can determine that scope determines by mentioned earlier Peak refers to the 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 531.0-532.5eV refers to that the combination corresponding to summit can be in Whole peaks in the range of 531.0-532.5eV.
Nano-carbon material containing metallic atom of the invention, the metallic element is selected from there is catalysis to make hydrocarbon dehydrogenation reaction Metallic element, for example：The metallic element can be group ia metal element, group iia gold in the periodic table of elements One or more combination in category element and transition metal.Preferably, the nano carbon material containing metallic atom Material contains at least one first metallic element and at least one second metallic element, and first metallic element is selected from transition gold Category element, second metallic element is selected from group ia metal element and group iia metallic element, and this contains metallic atom Nano-carbon material shows catalysis activity higher in hydrocarbon dehydrogenation reaction.
First metallic element can selected from Group IIIB metallic element in the periodic table of elements, group ivb metallic element, Group VB metallic element, vib metals element, VIIB races metallic element, group VIII metallic element, IB races metallic element and group iib metallic element.The instantiation of first metallic element can include but is 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, Jin Hexin.Preferably, first metallic element is selected from group VIII metallic element. It is highly preferred that first metallic element is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
Second metallic element is selected from group ia metal element and group iia metallic element, and its instantiation can be wrapped Include but be not limited to one or more in lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, described second Metallic element be sodium, potassium, magnesium, calcium and barium in one or more.First metallic element and the second metal unit The content of element can carry out appropriate selection according to the species of the first metallic element and the second metallic element.Preferably, with institute State on the basis of the total amount containing metallic atom nano-carbon material and in terms of element, the content of first metallic element can be 1-10 weight %, preferably 1.5-8 weight %, more preferably 2-6 weight %, more preferably 2-5 weight %；It is described The content of the second metallic element can be 0.1-10 weight %, more preferably preferably 0.2-8 weight %, 0.4-7 weight %, More preferably 0.5-5 weight %.
Nano-carbon material containing metallic atom of the invention, in a preferred embodiment, the first metal unit Element is selected from iron, cobalt and nickel, and second metallic element is selected from magnesium, calcium and barium, so can further improve according to the present invention Catalysis activity of the nano-carbon material containing metallic atom in hydrocarbon dehydrogenation reaction.This preferred embodiment in, with described On the basis of total amount containing metallic atom nano-carbon material, the content of first metallic element can be 1-10 weight %, excellent Elect 1-5 weight %, more preferably 2-4 weight % as；The content of second metallic element can be 1-10 weight %, excellent Elect 1-6 weight %, more preferably 2.5-4 weight % as.
Nano-carbon material containing metallic atom of the invention, in another preferred embodiment, first metal Element is selected from ruthenium, rhodium, palladium and platinum, and second metallic element is selected from sodium and potassium, so can further improve according to this hair Catalysis activity of the bright nano-carbon material containing metallic atom in hydrocarbon dehydrogenation reaction.This preferred embodiment in, with institute State on the basis of the total amount containing metallic atom nano-carbon material, the content of first metallic element can be 1-10 weight %, Preferably 2-5 weight %；The content of second metallic element is preferably 0.5-8 weight %, preferably 0.6-3 weight %.
Nano-carbon material containing metallic atom of the invention can exist with common various forms, be specifically as follows but not Be limited to CNT containing metallic atom, Graphene containing metallic atom, thin layer graphite containing metallic atom, containing metallic atom nanometer One kind in carbon particle, carbon nano-fiber containing metallic atom, Nano diamond containing metallic atom and fullerene containing metallic atom Or two or more combinations.The CNT containing metallic atom can be SWCN containing metallic atom, containing gold One or more combination in category atom double-walled carbon nano-tube and multi-walled carbon nano-tubes containing metallic atom.According to this hair Bright nano-carbon material containing metallic atom, preferably multi-walled carbon nano-tubes containing metallic atom.
Nano-carbon material containing metallic atom of the invention, it is preferable that the ratio containing metallic atom multi-walled carbon nano-tubes 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 metallic atom multi-walled carbon nano-tubes Specific 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 100-250m2/g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nano-tubes is 110-180m2/g。 In the present invention, the specific surface area is 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 at 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 excellent It is selected in the range of 0.01-0.5, is so obtained in that more preferable catalytic effect, particularly as hydrocarbons dehydrogenation reaction Catalyst when, more preferable catalytic reaction effect can be obtained.It is highly preferred that w500/w800In the range of 0.05-0.3.This In invention, w800=W800- W400, w500=W500- W400, W400It is to be determined at a temperature of 400 DEG C Mass loss rate, W800It is the mass loss rate determined at a temperature of 800 DEG C, W500It is to be determined at a temperature of 500 DEG C Mass loss rate；The weight-loss ratio is determined using thermogravimetric analyzer in air atmosphere, and test initial temperature is 25 DEG C, Heating rate is 10 DEG C/min；Sample is depressed in 150 DEG C of temperature and 1 normal atmosphere done in helium atmosphere before testing Dry 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 metallic atom 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 100-250m2/ g, more preferably 110-180m2/g；Also, w500/w800In the range of 0.01-0.5, It is preferred that in the range of 0.05-0.3.
Nano-carbon material containing metallic atom of the invention, for other nonmetallic heteroatoms outside oxygen atom, such as nitrogen Atom, sulphur atom and phosphorus atoms, its content can be customary amount.Usually, it is of the invention to be received containing metallic atom In rice carbon material, the total amount of other nonmetallic heteroatoms (such as nitrogen-atoms, sulphur atom and phosphorus atoms) outside oxygen atom can Think below 0.5 weight %, preferably below 0.2 weight %, more preferably below 0.1 weight %, more preferably Below 0.05 weight %.Nano-carbon material containing metallic atom of the invention, in addition to aforesaid metal elements, can also contain There are other metallic atoms, described other metallic atoms for example can be from the catalyst used when preparing nano-carbon material. The content of other metallic atoms is generally below 2.5 weight %, preferably below 1.5 weight %, more preferably Below 0.5 weight %, is still more preferably below 0.2 weight %, particularly preferably below 0.1 weight %.
According to the second aspect of the invention, the invention provides a kind of preparation method containing metallic atom nano-carbon material, The method includes for one kind being dispersed with raw material nano carbon material, at least one transistion metal compound and at least one alkalescence The aqueous dispersions of metallic compound are reacted in closed container, and the metallic element in the alkaline metal cpds is selected from Group ia metal element and group iia metallic element.
The method according to the invention, the metallic element in the transistion metal compound is selected from transition metal, specifically may be used To be selected from, but not limited to, Group IIIB metallic element in the periodic table of elements, group ivb metallic element, Group VB metal unit Element, vib metals element, VIIB races metallic element, group VIII metallic element, I B-group metal element and Group iib metallic element.The instantiation of the metallic element in the transistion metal compound can include but is 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, Jin Hexin.Preferably, the metallic element in the transistion metal compound is selected from the Group VIII metal element.It is highly preferred that metallic element in the transistion metal compound be selected from iron, ruthenium, cobalt, rhodium, Nickel, palladium and platinum.
The transistion metal compound can selected from metal nitrate, metal acetate salt, metal carbonate, metal sulfate, Basic metal carbonates, metal hydroxides, metal chloride and metal complex, more preferably metal nitrate Salt, metal acetate salt, metal carbonate, basic metal carbonates, metal hydroxides and metal complex.
The transistion metal compound can specifically be selected from, but not limited to, nickel nitrate, nickel acetate, nickel sulfate, basic nickel carbonate, Nickel chloride, nickel hydroxide, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, cobalt hydroxide, nitric acid Iron, ferrous acetate, ferric sulfate, basic carbonate iron, iron chloride, iron hydroxide, zinc nitrate, zinc acetate, zinc sulfate, Basic zinc carbonate, zinc chloride, zinc hydroxide, copper nitrate, copper acetate, copper sulphate, basic copper carbonate, copper chloride, hydrogen Cupric oxide, lanthanum nitrate, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, cerous nitrate, cerous carbonate, cerium chloride, cerium hydroxide, Nitric acid ruthenium, ruthenic chloride, hydroxide ruthenium, palladium nitrate, palladium bichloride, palladium dydroxide, palladium, platinum nitrate, platinum chloride, Rhodium nitrate, nitric acid ammonia palladium (such as ammino palladium of nitric acid four), radium chloride and palladium acetylacetonate.
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.It is preferred that Ground, the 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 the metallic element Salt.It is highly preferred that the alkaline metal cpds are selected from hydroxide, the carbon containing the metallic element containing metallic element Hydrochlorate, the acetate containing the metallic element and the bicarbonate containing the metallic element.The alkaline metal cpds Instantiation can be included but is not limited to：Lithium hydroxide, NaOH, potassium hydroxide, beryllium hydroxide, magnesium hydroxide, Calcium hydroxide, barium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium acid carbonate, carbonic acid One or more in hydrogen calcium, saleratus and barium bicarbonate.
The consumption of the method according to the invention, the transistion metal compound and alkaline metal cpds can be according to expection The oxygen element and the content and species of metallic element introduced in raw material nano carbon material are selected.Finally preparing Nano-carbon material containing metallic atom in the catalyst as hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material：Cross Cross metallic compound：The weight ratio of alkaline metal cpds is 1：0.01-10：In the range of 0.01-15, thus prepare Nano-carbon material containing metallic atom can obtain the catalytic effect of further raising in the catalyst as hydrocarbon dehydrogenation reaction.More Preferably, raw material nano carbon material：Transistion metal compound：The weight ratio of alkaline metal cpds is 1：0.02-5：0.05-10 In the range of.It is further preferred that raw material nano carbon material：Transistion metal compound：The weight of alkaline metal cpds Than 1：0.05-1：In the range of 0.08-4.
The method according to the invention, the method according to the invention, the transistion metal compound and the alkalinous metal chemical combination The mol ratio of thing is preferably 1：In the range of 0.5-300, the nano-carbon material containing metallic atom for thus preparing is de- as hydrocarbon Also there is more excellent catalysis activity during the catalyst of hydrogen reaction.It is highly preferred that the transistion metal compound with it is described The mol ratio of alkaline metal cpds is 1：In the range of 0.6-35.
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, Structural form retentivity of the nano-carbon material in processing procedure is more preferable, for example：For CNT, treated Will not be cut off substantially in journey.It is highly preferred that raw material nano carbon material：H2The weight ratio of O is 1：The scope of 50-500 It is interior.It is further preferred that raw material nano carbon material：H2The weight ratio of O is 1：In the range of 120-250.
The method according to the invention, in a preferred embodiment, the metallic element in the transistion metal compound Selected from iron, cobalt and nickel, the metallic element in the alkaline metal cpds is selected from magnesium, calcium and barium, thus prepare containing gold Category atom nano-carbon material can obtain more preferable catalytic reaction effect in the catalyst as hydrocarbon dehydrogenation reaction.Raw material nano Carbon material：Transistion metal compound：The weight ratio of alkaline metal cpds is preferably 1：0.02-2：In the range of 2-10, More preferably 1：0.8-1.2：In the range of 3-5.This preferred embodiment in, transistion metal compound：Alkaline gold Belong to the mol ratio of compound preferably 1：In the range of 1-220, more preferably 1：In the range of 3-5.In the preferred reality In applying mode, raw material nano carbon material：H2The weight ratio of O is preferably 1：In the range of 150-300, more preferably 1： In the range of 220-280.
The method according to the invention, in another preferred embodiment, the metal unit in the transistion metal compound Element is selected from ruthenium, rhodium, palladium and platinum, and the metallic element in the alkaline metal cpds is selected from sodium and potassium, and what is thus prepared contains Metallic atom nano-carbon material can obtain more preferable catalytic reaction effect in the catalyst as hydrocarbon dehydrogenation reaction.Raw material is received Rice carbon material：Transistion metal compound：The weight ratio of alkaline metal cpds is preferably 1：0.02-1：The scope of 0.05-10 It is interior, more preferably 1：0.02-0.3：In the range of 0.06-0.2.This preferred embodiment in, transistion metal compound： The mol ratio of alkaline metal cpds is preferably 1：In the range of 0.5-150, more preferably 1：In the range of 0.8-35. This preferred embodiment in, raw material nano carbon material：H2The weight ratio of O is preferably 1：In the range of 80-300, more It is preferred that 1：In the range of 100-200.
The method according to the invention, the condition of the reaction is being enough to improve the oxygen atom and metal in raw material nano carbon material The content of atom is defined.Preferably, in course of reaction, the temperature of the aqueous dispersions is in the range of 80-300 DEG C. The temperature of the aqueous dispersions is in when within above range, and the oxygen that can not only be effectively improved in raw material nano carbon material is former Son and metal atom content, and the generation of the structural form of raw material nano carbon material will not be significantly affected.It is highly preferred that In course of reaction, the temperature of the aqueous dispersions is in the range of 120-240 DEG C.
The method according to the invention, duration of the reaction can be selected according to the temperature of reaction, with can be Enough oxygen atom is introduced in raw material nano carbon material and metallic atom is defined.Usually, the duration of the reaction can With in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably in the range of 12-48 hours.
Method according to the invention it is possible to the aqueous dispersions are formed using conventional various methods, for example can be by original Material nano-carbon material is dispersed in water (preferably deionized water), is subsequently adding the transistion metal compound and the alkalescence Metallic compound, so as to obtain the aqueous dispersions.In order to further improve the dispersion effect of raw material nano carbon material, together When shorten the scattered time, raw material nano carbon material can be dispersed in water using the method for sonic oscillation.The ultrasound The condition of vibration can be conventional selection, and usually, the frequency of the sonic oscillation can be 20-200kHz, preferably 80-150kHz；The duration of the sonic oscillation can be 0.1-12 hours, preferably 0.2-6 hours, more preferably 1-4 hours.The method according to the invention, the transistion metal compound and the alkaline metal cpds can be with solution The form of (the preferably aqueous solution) is provided, it is also possible to is provided in the form of pure material, is not particularly limited.
The method according to the invention, the content of O elements is not particularly limited in the raw material nano carbon material, can be normal Rule selection.Usually, the content of O elements is not higher than 1 weight % in the raw material nano carbon material, preferably not high In 0.8 weight %, more preferably not above 0.5 weight %, more preferably not higher than 0.3 weight %.According to the present invention Method, in the raw material nano carbon material outside oxygen atom remaining nonmetallic heteroatoms (such as nitrogen-atoms, phosphorus atoms and Sulphur atom) total amount (in terms of element) can be as customary amount.Usually, deoxygenation is former in the raw material nano carbon material The total amount of remaining nonmetallic heteroatoms outside son be not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably To be not higher than 0.1 weight %, still more preferably to be not higher than 0.05 weight %.The method according to the invention, the raw material Nano-carbon material may contain some metallic elements, such as from preparing raw material nano-carbon material according to the difference in source When the catalyst that uses in metallic element.The content (in terms of element) one of metallic element in the raw material nano carbon material As in below 2 weight %, more preferably preferably below 1.8 weight %, more preferably below 1 weight %, 0.5 weight Amount below %, is still more preferably below 0.1 weight %.
The method according to the invention, raw material nano carbon material can carry out pre- place using preceding using method commonly used in the art Reason (as washed), to remove some impurity of raw material nano carbon material surface；Can not also be pre-processed, directly be used. In embodiment disclosed by the invention, 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 the nanometer Oxygen atom and metal atom content in carbon material.The raw material nano carbon material can be but be not limited to CNT, stone One or more in black alkene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene 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.
In a preferred embodiment, the raw material nano carbon material is multi-walled carbon nano-tubes, the multi-wall carbon nano-tube The specific surface area of pipe can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, it is further excellent Elect 120-190m as2/g.When the specific surface area of the multi-wall carbon nano-tube material is within above range, finally give Nano-carbon material containing metallic atom has more preferable catalysis activity, particularly in the catalysis of the dehydrogenation reaction as hydrocarbons During agent, catalysis activity higher is shown.
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 interval is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800Can be In the range of 0.01-0.5, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably 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, institute The specific surface area for stating multi-walled carbon nano-tubes is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, More preferably 120-190m2/g；Weight-loss ratio of the multi-walled carbon nano-tubes in 400-800 DEG C of temperature range be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, preferably In the range of 0.02-0.4, 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 in self-generated pressure Under carry out.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 separate in can also including the mixture obtained from reaction The solid matter for going 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, such as centrifugation, mistake One or more combination in filter 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, Carried out more preferably at a temperature of 120-160 DEG C.The dry duration can be carried out according to dry temperature and mode Selection.Usually, the dry duration can be 0.5-48 hours, more preferably preferably 4-24 hours, 6-12 Hour.The 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 the angle for further improving dry efficiency, the drying is preferably carried out at reduced pressure.
The method according to the invention, can effectively improve the oxygen atom and metal atom content in raw material nano carbon material, together Shi Buhui is produced to the structural form of raw material nano carbon material and significantly affected.
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 raw Sub- 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 raw Sub- 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 3rd Prepared by nano-carbon material containing metallic atom of individual aspect is 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 350-450 DEG C.The duration of the roasting can be according to the temperature of roasting Degree is selected.Usually, the duration of the roasting can be 1-24 hours, preferably 2-12 hours, more preferably It is 2-4 hours.The roasting can be carried out in oxygen-containing atmosphere, it is also possible to be carried out in the atmosphere formed by inert gas. The oxygen-containing atmosphere can be air atmosphere；Can also be mixed atmosphere that oxygen and inert gas are mixed to form, it is described mixed Close in atmosphere, the content of oxygen can be 0.1-22 volumes %.The inert gas can include but is not limited to nitrogen and/or Rare gas, the rare gas can be argon gas and/or helium.Angularly consider from convenience and cost, it is preferable that The roasting is carried out in oxygen-containing atmosphere (such as air atmosphere).
Nano-carbon material containing metallic atom of the invention or by the method for the present invention prepare containing metallic atom nanometer 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 or by the method for the present invention prepare containing metallic atom nanometer 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, that can expire Sufficient use requirement is defined, for example, can be organic binder bond and/or inorganic binder.The organic binder bond can be common Various polymer-type binding agents, the inorganic binder can be common various heat-resistant inorganic oxides, such as aluminum oxide And/or silica.The preformed catalyst be to hydrocarbon dehydrogenation reaction (such as direct dehydrogenation reaction and oxidative dehydrogenation), When particularly having the preformed catalyst of catalytic action to oxidative dehydrogenation, the binding agent is preferably inorganic binder. In the preformed catalyst, the content containing metallic atom nano-carbon material can be selected according to specifically used requirement, not had It is particularly limited to, it is usually, described containing metallic atom nano-carbon material on the basis of the total amount of the preformed catalyst Content can be 5-95 weight %.
According to the fifth aspect of the present invention, the invention provides according to one side of the invention containing metallic atom nanometer 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, it is also possible to It is 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 presence Or in the absence of oxygen under conditions of, 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 Four contacts of nano-carbon material containing metallic atom of 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 unsaturated hydrocarbons, Such as alkene.The method according to the invention is particularly suitable for carrying out dehydrogenation to alkane, so as to obtain 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- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- dimethyl pentanes, normal octane, 2- Methyl heptane, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethylhexanes, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethylpentanes, 2- methyl -3- ethyls penta Alkane, 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 cyclohexane, 2,2,4- trimethyl cyclohexanes, 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- Diethylpentane, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- methyl -4- ethyl cyclohexanes, positive third Butylcyclohexane, isopropyl cyclohexane, trimethyl-cyclohexane (including various isomers of trimethyl-cyclohexane, such as 1,2,3- Trimethyl-cyclohexane, 1,2,4- trimethyl-cyclohexanes, 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- Trimethylheptane, 2,4,6- trimethylheptanes, 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 heptane, 2- methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3- ethyl heptanes, 5- methyl -3- ethyls Heptane, 4- methyl -4- ethyl heptanes, 4- propyl group heptane, 3,3- diethylhexanes, 3,4- diethylhexanes, 2- methyl -3,3- Diethylpentane, vinylbenzene, 1- phenyl-propanes, 2- phenyl-propanes, 1- phenyl butanes, 2- phenyl butanes, 1- phenyl pentanes, One or more combination in 2- phenyl pentanes and 3- phenyl pentanes.It is highly preferred that the hydrocarbon is propane, positive fourth One or more in alkane, iso-butane and vinylbenzene.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 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 contain Metallic atom nano-carbon material haptoreaction.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 decompose occurs, such as nitrogen, carbon dioxide, rare gas and One or more combination in vapor.The consumption of the carrier gas can be conventional selection.Usually, carrier gas Content can be 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 hydrocarbon Dehydrogenation reaction is defined.Usually, the contact can be carried out at a temperature of 200-650 DEG C, preferably at 300-600 DEG C At a temperature of carry out, 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 in stream 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, contact can be represented with the volume space velocity of the gas of charging Duration.Usually, the volume space velocity of the gas of charging can be 0.1-10000h-1, preferably 1-6000h-1, it is more excellent Elect 5-5000h as-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, X-ray photoelectron spectroscopic analysis Thermo Scientific companies equipped with Tested on the ESCALab250 type x-ray photoelectron spectroscopies of Thermo Avantage V5.926 softwares, excited Source is monochromatization Al K α X-rays, and energy is 1486.6eV, and power is 150W, and penetrating energy used by narrow scan is 30eV, Base vacuum during analysis test is 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, Data processing is carried out on Thermo Avantage softwares, is quantitatively divided using sensitivity factor method in analysis module Analysis.Sample is depressed in 150 DEG C of temperature and 1 normal atmosphere dried 3 hours in helium atmosphere before testing.
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 at 150 DEG C Temperature and 1 normal atmosphere depress in helium atmosphere dry 3 hours.Using Micromertrics companies of the U.S. ASAP2000 types N2Physical adsorption appearance measurement the specific area.The high-resolution-ration transmission electric-lens point produced using FEI Co. of the U.S. Analysis 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 transistion metal compound are each in the form of solid matter There is provided.
Embodiment 1-31 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 contains It is 0.3 weight % to measure, the total content of remaining nonmetallic heteroatoms (nitrogen-atoms, phosphorus atoms and sulphur atom) outside oxygen atom It is 0.03 weight %, metallic atom total content is 0.1 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w800, Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, is organised purchased from Chinese Academy of Sciences Chengdu Learn Co., Ltd) dispersion in deionized water, being dispersed under the conditions of sonic oscillation is carried out, and sonic oscillation condition includes：Frequently Rate is 140kHz, and the time is 1 hour.Then, add as the ferrous acetate of transistion metal compound and as alkalescence gold Belong to the barium hydroxide of compound, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Transistion metal compound： Alkaline metal cpds：H2The weight ratio of O is 1：1：4：250 ratio feeds intake.
(2) aqueous dispersions that will be obtained are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 120 DEG C, React 48 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 is in normal pressure (1 Standard atmospheric pressure, similarly hereinafter), after drying 12 hours at a temperature of 120 DEG C, nano-carbon material containing metallic atom is obtained, this contains The composition of metallic atom nano-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 metallic atom nano-carbon material from Fig. 1 and Fig. 2 Microscopic pattern 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 temperature Spend in the oil bath for 120 DEG C, in back flow reaction under normal pressure 48 hours.After reaction terminates, the temperature drop in there-necked flask is treated To room temperature, reactant mixture is filtered and washed, and is collected solid matter.The solid matter that will be collected into is normal Pressure, dry 12 hours at a temperature of 120 DEG C after, obtain nano-carbon material containing metallic atom.What is prepared receives containing metallic atom The rice composition of carbon material, 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, in step (1), Barium hydroxide is replaced with the barium chloride of equimolar amounts.Prepare the composition containing metallic atom nano-carbon material, specific surface area with 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 matched somebody with somebody The aqueous dispersions of system are free of ferrous acetate, the mole of barium hydroxide and ferrous acetate in embodiment 1 and barium hydroxide it is total Mole is identical.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Comparative example 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, step (1) is matched somebody with somebody The aqueous dispersions of system are free of barium hydroxide, the mole of ferrous acetate and ferrous acetate in embodiment 1 and barium hydroxide it is total Mole is identical.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), Specific surface area as the multi-walled carbon nano-tubes (be 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 weightlessness in 400-500 DEG C of temperature range Rate is w500, w500/w800It is 0.33, oxygen atom content is 0.62 weight %, remaining the nonmetallic miscellaneous original outside oxygen atom The total content of sub (nitrogen-atoms, phosphorus atoms and sulphur atom) is 0.02 weight %, and metallic atom total content 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), The aqueous dispersions that will be obtained in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in spontaneous pressure Reacted 48 hours under power.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 1 In list.
Embodiment 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), By raw material nano carbon material：Transistion metal compound：Alkaline metal cpds：H2The weight ratio of O is 1：0.02：4： 250 ratio feeds intake.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 1 In list.
Embodiment 5
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), By raw material nano carbon material：Transistion metal compound：Alkaline metal cpds：H2The weight ratio of O is 1：1：8：250 Ratio feed intake.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800Listed in table 1.
Embodiment 6
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 %, the total content of remaining nonmetallic heteroatoms (nitrogen-atoms, phosphorus atoms and sulphur atom) outside oxygen atom is 0.05 Weight %, metallic atom total content is 0.03 weight %, and the weight-loss ratio in 400-800 DEG C of temperature range is w800, Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.07, is organised purchased from Chinese Academy of Sciences Chengdu Learn Co., Ltd) dispersion in deionized water, being dispersed under the conditions of sonic oscillation is carried out, and sonic oscillation condition includes：Frequently Rate is 90kHz, and the time is 4 hours.Then, add as the palladium of transistion metal compound and as alkalinous metal The potassium carbonate of compound, so as to obtain aqueous dispersions, wherein, by raw material nano carbon material：Transistion metal compound：Alkali Property metallic compound：H2The weight ratio of O is 1：0.2：0.1：150 ratio feeds intake.
(2) aqueous dispersions that will be obtained are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 220 DEG C, React 12 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 is in normal pressure, 160 After being dried 8 hours at a temperature of DEG C, nano-carbon material containing metallic atom is obtained, this contains the group of metallic atom nano-carbon material Into, specific surface area and w500/w800Listed in table 1.
Comparative example 5
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), Potassium carbonate with etc. the potassium chloride of weight replace.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 7
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), Specific surface area as the multi-walled carbon nano-tubes (be purchased from Shandong great Zhan nano materials Co., Ltd) of raw material nano carbon material is 103m2/ g, w500/w800It is 0.23, oxygen atom content is 1.1 weight %, remaining nonmetallic heteroatoms outside oxygen atom The total content of (nitrogen-atoms, phosphorus atoms and sulphur atom) is 0.04 weight %, and metallic atom total content is 1.6 weight %.System The standby composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 8
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (2), The aqueous dispersions that will be obtained are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 280 DEG C, spontaneous Reacted 12 hours under pressure.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table Listed in 1.
Embodiment 9
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), In the aqueous dispersions for obtaining, under conditions of the gross weight of transistion metal compound and alkaline metal cpds keeps constant, make Transistion metal compound：The mol ratio of alkaline metal cpds is 1：10.The group containing metallic atom nano-carbon material for preparing Into, specific surface area and w500/w800Listed in table 1.
Embodiment 10
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), Potassium carbonate is replaced with potassium hydroxide, and the mole of potassium hydroxide is 2 times of the mole of potassium carbonate.Prepare containing metal raw The composition of sub- nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 11
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), Potassium carbonate is replaced with sodium acid carbonate, and the mole of sodium acid carbonate is 2 times of the mole of potassium carbonate in embodiment 6.Prepare The composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 12
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), Palladium is replaced with the palladium acetylacetonate of equimolar amounts.The composition containing metallic atom nano-carbon material, the specific surface area for preparing And w500/w800Listed in table 1.
Embodiment 13
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), Palladium is replaced with the cobalt acetate of equimolar amounts.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 14
Nano-carbon material containing metallic atom is prepared using method same as Example 6, unlike, in step (1), Palladium is replaced with the nickel acetate of equimolar amounts.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 1.
Embodiment 15
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 transition metal compound The palladium acetylacetonate of thing and the NaOH as alkaline metal cpds, so as to obtain aqueous dispersions, wherein, by raw material Nano-carbon material：Transistion metal compound：Alkaline metal cpds：H2The weight ratio of O is 1：0.05：0.2：120 Ratio feeds intake；
In step (2), the aqueous dispersions that will be obtained in the autoclave with polytetrafluoroethyllining lining, in 120 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.
Comparative example 6
It is equipped with being placed in the identical aqueous dispersions of embodiment 15 in the there-necked flask of condenser pipe, the there-necked flask is placed in During temperature is 120 DEG C of oil bath, in back flow reaction under normal pressure 36 hours.After reaction terminates, the temperature in there-necked flask is treated After being down to room temperature, reactant mixture is filtered and washed, and is collected solid matter.The solid matter that will be collected into exists Normal pressure, dry 12 hours at a temperature of 120 DEG C after, obtain nano-carbon material containing metallic atom.Prepare containing metallic atom The composition of nano-carbon material, specific surface area and w500/w800Listed in table 2.
Comparative example 7
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, in step (1), NaOH is replaced with the sodium sulphate of equimolar amounts.Prepare the composition containing metallic atom nano-carbon material, specific surface area with And w500/w800Listed in table 2.
Embodiment 16
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, in step (2), The aqueous dispersions that will be obtained 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/w800In table 2 In list.
Embodiment 17
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, 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 with And w500/w800Listed in table 2.
Embodiment 18
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 15, unlike, in step (1), Under conditions of the gross weight of transistion metal compound and transistion metal compound keeps constant, make transistion metal compound：Alkali Property metallic compound mol ratio be 1：20.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 2.
Embodiment 19
Nano-carbon material containing metallic atom is prepared using method same as Example 6, difference is as follows：
In step (1), the aqueous solution for preparing aqueous dispersions contains as the palladium and work of transistion metal compound It is the sodium acid carbonate of alkaline metal cpds, wherein, by raw material nano carbon material：Transistion metal compound：Alkalinous metal Compound：H2The weight ratio of O is 1：0.4：1：150 ratio feeds intake；
In step (2), the aqueous dispersions that will be obtained in the autoclave with polytetrafluoroethyllining lining, in 240 At a temperature of DEG C, react 12 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 20
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (1), As the multi-walled carbon nano-tubes of raw material nano carbon material with embodiment 7.The composition containing metallic atom nano-carbon material of preparation, 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 19, unlike, in step (1), By raw material nano carbon material：Transistion metal compound：Alkaline metal cpds：H2The weight ratio of O is 1：0.02：1： 150 ratio feeds intake.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 2 In list.
Embodiment 22
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (1), By raw material nano carbon material：Transistion metal compound：Alkaline metal cpds：H2The weight ratio of O is 1：0.1：10： 150 ratio feeds intake.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 2 In list.
Embodiment 23
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (2), The aqueous dispersions that will be obtained in the autoclave with polytetrafluoroethyllining lining, at a temperature of 270 DEG C, in spontaneous pressure Reacted 12 hours under power.The composition containing metallic atom nano-carbon material, specific surface area and the w for preparing500/w800In table 2 In list.
Embodiment 24
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (1), Palladium is replaced with the nickelous carbonate of equimolar amounts.Prepare the composition containing metallic atom nano-carbon material, specific surface area and w500/w800Listed in table 2.
Embodiment 25
Nano-carbon material containing metallic atom is prepared using with the identical method of embodiment 19, unlike, in step (1), Sodium acid carbonate is replaced with the magnesium hydroxide of equimolar amounts.The composition containing metallic atom nano-carbon material, the specific surface area for preparing And w500/w800Listed in table 2.
Embodiment 26
Nano-carbon material containing metallic atom prepared by embodiment 1 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 8
Nano-carbon material containing metallic atom prepared by comparative example 1 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 9
Nano-carbon material containing metallic atom prepared by comparative example 2 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 10
Nano-carbon material containing metallic atom prepared by comparative example 3 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Comparative example 11
Nano-carbon material containing metallic atom prepared by comparative example 4 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 27
Nano-carbon material containing metallic atom prepared by embodiment 2 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 28
Nano-carbon material containing metallic atom prepared by embodiment 3 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 29
Nano-carbon material containing metallic atom prepared by embodiment 4 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 30
Nano-carbon material containing metallic atom prepared by embodiment 5 is calcined 4 hours in air atmosphere at a temperature of 350 DEG C.
Embodiment 31
It is small that nano-carbon material containing metallic atom prepared by embodiment 19 is calcined 2 in air atmosphere at a temperature of 450 DEG C When.
Embodiment 32-62 is used to illustrate the application containing metallic atom nano-carbon material of the invention and hydrocarbon dehydrogenation reaction method.
Embodiment 32-56
The nano-carbon material containing metallic atom for respectively being prepared by 0.2g (admission space is 1.9mL) embodiment 1-25 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 435 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 1.98 volume %, normal butane With oxygen molar ratio 0.5：1, the balance of nitrogen as carrier gas) with cumulative volume air speed as 1200h-1It is passed through in reactor Row reaction, the composition of the reactant mixture that continuous monitoring is exported from reactor, and calculate n-butane conversion, total olefin Selectivity and 1- butylene selectivity, the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 12-18
Reacted using with embodiment 32-56 identical methods, unlike, prepared using comparative example 1-7 respectively Nano-carbon material containing metallic atom is used as catalyst.Reaction result is listed in table 3.
Comparative example 19
Reacted using with embodiment 32-56 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 20
Reacted using with embodiment 32-56 identical methods, unlike, use raw material same as Example 6 Nano-carbon material is used as catalyst.Reaction result is listed in table 3.
Embodiment 57-62
Reacted using with embodiment 32-56 identical methods, unlike, use prepared by embodiment 26-31 containing Metallic atom CNT is used as catalyst.Reaction result is listed in table 4.
Comparative example 21-24
Reacted using with embodiment 32-56 identical methods, unlike, using comparative example 8-11 prepare containing gold Category atom CNT is used as catalyst.Reaction result is listed in table 4.
Comparative example 25
Reacted using with embodiment 32-56 identical methods, unlike, catalyst is will be same as Example 1 Raw material nano carbon material in 350 DEG C of air atmospheres obtained from roasting 4 hours.Reaction result is listed in table 4.
Comparative example 26
Reacted using with embodiment 32-56 identical methods, unlike, catalyst is will be same as Example 5 Raw material nano carbon material in 300 DEG C of air atmospheres obtained from roasting 12 hours.Reaction result is listed in table 4.
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, can carry out various simple variants to technical scheme, These 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 contradiction In the case of, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is to various Possible combination 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 this hair Bright thought, it should equally be considered as content disclosed in this invention.

Claims (31)

1. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material contain C element, O elements and At least one metallic element, on the basis of the total amount containing metallic atom nano-carbon material and in terms of element, O elements contain It is 1-15 weight % to measure, and the total amount of the metallic element is 1.1-20 weight %, and the content of C element is 65-97.9 weight %,
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, The content of the O elements determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum is IO m, IO m/IO t In the range of 0.02-0.5；
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 O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum Amount be IO e, IO c/IO eIn the range of 0.2-1.
2. nano-carbon material containing metallic atom according to claim 1, wherein, IO m/IO tIn the scope of 0.05-0.4 It is interior, preferably in the range of 0.05-0.3；IO c/IO eIn the range of 0.25-0.85, preferably in the range of 0.4-0.8, More preferably in the range of 0.45-0.7.
3. nano-carbon material containing metallic atom according to claim 1 and 2, wherein, this contains metallic atom nanometer In carbon material, the amount of the C element determined by the peak in the range of 288.6-288.8eV in x-ray photoelectron power spectrum 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 0.4-2 In the range of, preferably in the range of 0.45-1.8, more preferably in the range of 0.5-1.5.
4. the nano-carbon material containing metallic atom according to any one in claim 1-3, wherein, metal is contained with this On the basis of the total amount of the C element determined by x-ray photoelectron power spectrum in atom nano-carbon material, by x-ray photoelectron energy The content of the C element that the peak in spectrum in the range of 284.7-284.9eV determines is 60-98 weight %, preferably 65-95 weight %, more preferably 70-90 weight %, the C determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum The content of element is 2-40 weight %, more preferably preferably 5-35 weight %, 10-30 weight %.
5. the nano-carbon material containing metallic atom according to any one in claim 1-4, wherein, metal is contained with this On the basis of the total amount of atom nano-carbon material and in terms of element, the content of O elements is 3-8 weight %, preferably 4-7.5 weights Amount %, more preferably 4.5-7 weight %, the content of C element is 76-95.3 weight %, preferably 79.5-93.6 weight %, More preferably 83-93 weight %, the total amount of the metallic element is 1.7-16 weight %, preferably 2.4-13 weight %, more Preferably 2.5-10 weight %.
6. the nano-carbon material containing metallic atom according to any one in claim 1-5, wherein, this contains metal raw Sub- nano-carbon material contains at least one first metallic element and at least one second metallic element, first metallic element Selected from transition metal, group VIII metallic element is preferably selected from, is more preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium And platinum；Second metallic element be selected from group ia metal element and group iia metallic element, be preferably selected from sodium, potassium, Magnesium, calcium and barium.
7. nano-carbon material containing metallic atom according to claim 6, wherein, with the nano-sized carbon containing metallic atom On the basis of the total amount of material and in terms of element, the content of first metallic element is 1-10 weight %, preferably 1.5-8 Weight %, more preferably 2-6 weight %, more preferably 2-5 weight %, the content of second metallic element is 0.1-10 Weight %, preferably 0.2-8 weight %, more preferably 0.4-7 weight %, more preferably 0.5-5 weight %.
8. the nano-carbon material containing metallic atom according to any one in claim 1-7, wherein, this contains metal raw Sub- nano-carbon material is CNT containing metallic atom；Preferably, it is containing metallic atom that this contains metallic atom nano-carbon material Multi-walled carbon nano-tubes.
9. nano-carbon material containing metallic atom according to claim 8, wherein, it is described containing many wall carbon of metallic atom The specific surface area of nanotube is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-250m2/ g, it is further excellent Elect 110-180m as2/g。
10. nano-carbon material containing metallic atom according to claim 8 or claim 9, wherein, it is described many containing metallic atom Weight-loss ratio of the wall carbon nano tube in 400-800 DEG C of temperature range is w800, the mistake in 400-500 DEG C of temperature range Rate is w again500, w500/w800In the range of 0.01-0.5, preferably in the range of 0.05-0.3, the weight-loss ratio is in sky Determined in gas atmosphere.
A kind of 11. preparation methods containing metallic atom nano-carbon material, the method includes for one kind being dispersed with raw material nano carbon The aqueous dispersions of material, at least one transistion metal compound and at least one alkaline metal cpds are in closed container Reacted, the metallic element in the alkaline metal cpds is selected from group ia metal element and group iia metallic element, In course of reaction, the temperature of the aqueous dispersions is maintained in the range of 80-300 DEG C.
12. methods according to claim 11, wherein, the metallic element in the transistion metal compound is selected from Group VIII metallic element, is preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum；In the alkaline metal cpds Metallic element is selected from group ia metal element and group iia metallic element, is preferably selected from sodium, potassium, magnesium, calcium and barium；
The transistion metal compound is preferably selected from metal nitrate, metal acetate salt, metal carbonate, basic metal carbon Hydrochlorate, metal hydroxides and metal complex；The alkaline metal cpds are preferably selected from the hydrogen-oxygen containing metallic element Compound, the carbonate containing the metallic element, the acetate containing the metallic element and the bicarbonate containing the metallic element Salt.
13. method according to claim 11 or 12, wherein, raw material nano carbon material：Transistion metal compound： The weight ratio of alkaline metal cpds is 1：0.01-10：In the range of 0.01-15, preferably 1：0.02-5：0.05-10 In the range of, more preferably 1：0.05-1：In the range of 0.08-4；
Raw material nano carbon material：H2The weight ratio of O is 1：In the range of 5-1000, preferably 1：The scope of 50-500 It is interior, more preferably 1：In the range of 120-250.
14. method according to any one in claim 11-13, wherein, transistion metal compound：Alkaline gold Belong to the mol ratio of compound 1：In the range of 0.5-300, preferably 1：In the range of 0.6-35.
15. method according to any one in claim 11-14, wherein, in the transistion metal compound Metallic element is selected from iron, cobalt and nickel, and the metallic element in the alkaline metal cpds is selected from magnesium, calcium and barium, and raw material is received Rice carbon material：Transistion metal compound：The weight ratio of alkaline metal cpds is 1：0.02-2：It is excellent in the range of 2-10 It is selected in 1：0.8-1.2：In the range of 3-5, transistion metal compound：The mol ratio of alkaline metal cpds is 1：1-220 In the range of, preferably 1：In the range of 3-5, raw material nano carbon material：H2The weight ratio of O is 1：The model of 150-300 In enclosing, preferably 1：In the range of 220-280；Or
Metallic element in the transistion metal compound is selected from ruthenium, rhodium, palladium and platinum, in the alkaline metal cpds Metallic element is selected from sodium and potassium, raw material nano carbon material：Transistion metal compound：The weight ratio of alkaline metal cpds is 1： 0.02-1：In the range of 0.05-10, preferably 1：0.02-0.3：In the range of 0.06-0.2, transistion metal compound：Alkali The mol ratio of property metallic compound is 1：In the range of 0.5-150, preferably 1：In the range of 0.8-35, raw material nano Carbon material：H2The weight ratio of O is 1：In the range of 80-300, preferably 1：In the range of 100-200.
16. method according to any one in claim 11-15, wherein, in course of reaction, the moisture dissipates The temperature of liquid is maintained in the range of 120-240 DEG C.
17. method according to any one in claim 11-16, 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 12-48 hours.
18. method according to any one in claim 11-17, wherein, in the raw material nano carbon material, The content of O elements is not higher than 1 weight %, more preferably not above preferably not higher than 0.8 weight %, 0.5 weight %, More preferably be not higher than 0.3 weight %, the total amount of metallic element in below 2 weight %, preferably below 1.8 weight %, More preferably below 1 weight %, more preferably below 0.5 weight %, are still more preferably below 0.1 weight %.
19. method according to any one in claim 11-18, wherein, the raw material nano carbon material is carbon Nanotube；Preferably, the raw material nano carbon material is multi-walled carbon nano-tubes.
20. methods according to claim 19, wherein, the specific surface area of the multi-walled carbon nano-tubes is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, more preferably 120-190m2/g。
21. method according to claim 19 or 20, wherein, the multi-walled carbon nano-tubes is at 400-800 DEG C Weight-loss ratio in temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800 In the range of 0.01-0.5, preferably in the range of 0.02-0.4, the weight-loss ratio is determined in air atmosphere.
22. method according to any one in claim 11-21, wherein, the method also includes being obtained from reaction Mixture in isolate solid matter, and the solid matter that will be isolated is dried.
23. methods according to claim 22, wherein, the drying is carried out at a temperature of 50-200 DEG C, excellent Carried out at a temperature of being selected in 80-180 DEG C, carried out more preferably at a temperature of 120-160 DEG C, the dry duration is 0.5-48 hours, preferably 4-24 hours, more preferably 6-12 hours.
Nano-carbon material containing metallic atom prepared by the method in a kind of 24. 11-23 as claim described in any one.
A kind of 25. nano-carbon materials containing metallic atom, it is that will appoint in claim 1-10 that this contains metallic atom nano-carbon material Nano-carbon material containing metallic atom described in meaning one or the nano-carbon material containing metallic atom described in claim 24 are carried out Prepared by roasting.
26. nano-carbon materials containing metallic atom according to claim 25, wherein, the roasting is at 250-500 DEG C At a temperature of carry out, carried out preferably at a temperature of 350-450 DEG C, duration of the roasting is 1-24 hours, excellent Elect as 2-12 hours, more preferably 2-4 hours.
Nano-carbon material containing metallic atom or claim in 27. claim 1-10 and 24 described in any one Nano-carbon material containing metallic atom in 25-26 described in any one as the catalyst of hydrocarbon dehydrogenation reaction application.
28. applications according to claim 27, wherein, the dehydrogenation reaction is carried out in the presence of oxygen.
29. application according to claim 27 or 28, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane Hydrocarbon, more preferably normal butane.
A kind of 30. hydrocarbon dehydrogenation reaction methods, the method is included in presence or absence of under conditions of oxygen, anti-in hydrocarbon dehydrogenation Should under the conditions of, by the nano-carbon material containing metallic atom described in any one in hydrocarbon and claim 1-10 and 24 or The contact of nano-carbon material containing metallic atom in claim 25-26 described in any one.
31. methods according to claim 30, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, More preferably normal butane.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1911502A (en) * 2006-09-05 2007-02-14 大庆石油管理局 Nanometer grade low carbon paraffin dehydrogen catalyst
CN101718011A (en) * 2009-11-16 2010-06-02 天津工业大学 Method for preparing carbon nanofibers
CN101774573A (en) * 2010-02-08 2010-07-14 哈尔滨工业大学 Method for amination of carbon nano tube
US20110123409A1 (en) * 2007-11-30 2011-05-26 Cuong Phamhuu Chemical reactor with nanometric superstructure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1911502A (en) * 2006-09-05 2007-02-14 大庆石油管理局 Nanometer grade low carbon paraffin dehydrogen catalyst
US20110123409A1 (en) * 2007-11-30 2011-05-26 Cuong Phamhuu Chemical reactor with nanometric superstructure
CN101718011A (en) * 2009-11-16 2010-06-02 天津工业大学 Method for preparing carbon nanofibers
CN101774573A (en) * 2010-02-08 2010-07-14 哈尔滨工业大学 Method for amination of carbon nano tube

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DA YOUNG JANG ET AL: "Oxidative dehydrogenation of n-butane on nano-carbon catalysts having graphitic structures", 《RSC CHEM INTERMED》 *

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