CN107008481B - Heteroatom-containing nano carbon material, preparation method and application thereof, and hydrocarbon dehydrogenation reaction method - Google Patents
Heteroatom-containing nano carbon material, preparation method and application thereof, and hydrocarbon dehydrogenation reaction method Download PDFInfo
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- CN107008481B CN107008481B CN201610055794.0A CN201610055794A CN107008481B CN 107008481 B CN107008481 B CN 107008481B CN 201610055794 A CN201610055794 A CN 201610055794A CN 107008481 B CN107008481 B CN 107008481B
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 326
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 201
- 238000000034 method Methods 0.000 title claims abstract description 154
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 79
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 61
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 61
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 52
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 428
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 214
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000001301 oxygen Substances 0.000 claims abstract description 101
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 101
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 37
- 230000003595 spectral effect Effects 0.000 claims abstract description 12
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 255
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 60
- 238000000026 X-ray photoelectron spectrum Methods 0.000 claims description 60
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 41
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
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- VCJPCEVERINRSG-UHFFFAOYSA-N 1,2,4-trimethylcyclohexane Chemical compound CC1CCC(C)C(C)C1 VCJPCEVERINRSG-UHFFFAOYSA-N 0.000 description 3
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- ODGLTLJZCVNPBU-UHFFFAOYSA-N 2,3,5-trimethylhexane Chemical compound CC(C)CC(C)C(C)C ODGLTLJZCVNPBU-UHFFFAOYSA-N 0.000 description 3
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
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- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
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- DQTVJLHNWPRPPH-UHFFFAOYSA-N 1,2,3-trimethylcyclohexane Chemical compound CC1CCCC(C)C1C DQTVJLHNWPRPPH-UHFFFAOYSA-N 0.000 description 2
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- RUTNOQHQISEBGT-UHFFFAOYSA-N 2,3,4-trimethylhexane Chemical compound CCC(C)C(C)C(C)C RUTNOQHQISEBGT-UHFFFAOYSA-N 0.000 description 2
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- LTHAIAJHDPJXLG-UHFFFAOYSA-N pentan-2-ylbenzene Chemical compound CCCC(C)C1=CC=CC=C1 LTHAIAJHDPJXLG-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
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- 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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/18—Carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention discloses a heteroatom-containing nano carbon material, a preparation method and application thereof, and a hydrocarbon dehydrogenation reaction method
The molar ratio of the content of oxygen elements determined by the spectral peaks of the radicals is greater than 1, and the ratio of the content of nitrogen elements determined by the spectral peaks corresponding to graphitic nitrogen to the content of nitrogen elements determined by the spectral peaks corresponding to pyrrole nitrogen is greater than 1. The nano carbon material containing the heteroatom shows good catalytic activity in the oxidative dehydrogenation reaction of hydrocarbon, and simultaneously keeps the good characteristics of the nano carbon material and has good stability. The preparation method of the heteroatom-containing nano material can stably regulate and control the content and existing form of the heteroatom in the nano carbon material, and has small influence on the structure of the nano carbon material.
Description
Technical Field
The invention relates to a heteroatom-containing nano carbon material, a preparation method and application thereof, and also relates to a hydrocarbon dehydrogenation reaction method.
Background
Carbon materials exist in various morphological structures including carbon nanotubes, graphite, graphene, nanodiamonds, activated carbon, onion carbon, and the like. Compared with the traditional metal oxide catalyst, the carbon material has the advantages of environmental friendliness, reproducibility, low energy consumption and the like, and has good heat-conducting property, so that the carbon material is high in energy utilization rate, and is beneficial to reducing the reaction temperature and improving the product selectivity. Various types of carbon materials have been reported for catalytic reactions such as alkane activation and oxidative dehydrogenation, for example, in the sixty-seven decades of the last century, and researchers have found that coke is capable of catalyzing alkane oxidative dehydrogenation (Journal of Catalysis,31:444-449, 1973).
With the intensive research on nanocarbon materials, researchers began to use Carbon nanotubes for the oxidative dehydrogenation of ethylbenzene (Carbon,42: 2807-. Research shows that the catalytic activity of a pure nano carbon material is not high, but due to the strong controllability of the surface structure, surface modification can be carried out artificially, such as doping of heteroatom functional groups such as oxygen, nitrogen and the like, so as to regulate and control the electron density distribution and acid-base properties of the surface of the nano carbon material and improve the catalytic activity of the nano carbon material (Catalysis Today,102:248-253, 2005).
The nitrogen atoms and the carbon atoms are close in atomic size, so that the nitrogen atoms and the carbon atoms can be doped into a carbon structure skeleton on the surface layer of the nano carbon material, and the electronic characteristics, the acid-base property, the catalytic performance and the like of the nano carbon material are controlled and changed. The nitrogen element to be introduced can be classified into graphite type nitrogen, pyridine type nitrogen, pyrrole type nitrogen, and the like according to the bonding manner of nitrogen with the carbon material.
The aza-nanocarbon material can be used in catalytic reactions due to the influence of nitrogen on electron transfer and acid-base properties of the nanocarbon material. For example, it is reported that nitrogen-doped carbon nanotubes can be used for propane oxidative dehydrogenation, and it is considered that graphitic nitrogen species can greatly improve the conversion efficiency of oxygen molecules, thereby improving the catalytic performance (Chemical Communications,49 (74): 8151-8153, 2013).
The oxidative dehydrogenation of low-carbon paraffin to prepare olefin is one of industrially important reactions, and the oxidative dehydrogenation is an exothermic process and can be realized at a lower operation temperature, so that the method has the advantages of low energy consumption, high energy conversion efficiency and the like compared with the direct dehydrogenation. The low-carbon chain olefin of the oxidative dehydrogenation product is a raw material of various chemical products. Butadiene, for example, is a major raw material for producing synthetic rubbers and resins. At present, catalysts used in the reaction of oxidative dehydrogenation of butane to produce butene and butadiene mainly include conventional noble metal (platinum, palladium, etc.) and transition metal oxide (vanadium oxide, etc.) catalysts and novel carbon material catalysts. The traditional metal catalyst is easy to generate carbon deposit in the reaction process, so that the catalyst is poisoned and inactivated. Although emerging nanocarbon materials exhibit better catalytic activity and stability, further improvements in catalyst activity are desired.
Disclosure of Invention
The invention aims to overcome the technical problem that the catalytic activity of the existing nano carbon material is still not high enough when the existing nano carbon material is used as a catalyst for hydrocarbon oxidative dehydrogenation reaction, and provides a heteroatom-containing nano carbon material which can not only obtain higher catalytic stability but also obviously improve the catalytic activity when used as a catalyst for hydrocarbon oxidative dehydrogenation reaction.
According to a first aspect of the present invention, there is provided a heteroatom-containing nanocarbon material containing an oxygen element, a nitrogen element, a hydrogen element and a carbon element, wherein the content of the oxygen element is 0.9 to 10% by weight, the content of the nitrogen element is 0.1 to 10% by weight, the content of the hydrogen element is 0.1 to 2% by weight and the content of the carbon element is 78 to 98.9% by weight, in terms of elements, based on the total amount of the heteroatom-containing nanocarbon material;
in the X-ray photoelectron spectrum of the heteroatom-containing nano carbon material, the total amount of surface elements of the heteroatom-containing nano carbon material determined by X-ray photoelectron spectrum is used as the reference
The content of oxygen element determined by the peak of the group is 0.1-1 mol%, and the content of oxygen element determined by the peak corresponding to C-O group
The molar ratio of the content of the oxygen element determined by the peak of the group is more than 1; and is
In the X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, the content of nitrogen element determined by the peak corresponding to graphite type nitrogen is 0.5-1 mol%, and the ratio of the content of nitrogen element determined by the peak corresponding to graphite type nitrogen to the content of nitrogen element determined by the peak corresponding to pyrrole type nitrogen is more than 1.
According to a second aspect of the present invention, there is provided a method for producing a heteroatom-containing nanocarbon material, comprising contacting a raw nanocarbon material with at least one oxidizing agent to obtain an oxidation-treated nanocarbon material, and calcining the oxidation-treated nanocarbon material in an inert atmosphere at a temperature of 500 ℃., wherein the content of oxygen element is 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, more preferably 1 to 2% by weight, and still more preferably 1.5 to 1.8% by weight, in terms of element, based on the total amount of the raw nanocarbon material; the content of the nitrogen element is 2 to 10% by weight, preferably 2 to 5% by weight, more preferably 2.5 to 4% by weight, and further preferably 3 to 3.8% by weight; the content of the hydrogen element is 0.1 to 1% by weight, preferably 0.2 to 0.8% by weight, more preferably 0.4 to 0.7% by weight, and further preferably 0.5 to 0.6% by weight; the content of the carbon element is 86 to 97.8% by weight, preferably 91.7 to 97.3% by weight, more preferably 93.3 to 96.1% by weight, still more preferably 93.8 to 95% by weight,
the total amount of surface elements of the raw nanocarbon material determined by X-ray photoelectron spectroscopy is determined by the X-ray photoelectron spectroscopy
The content of oxygen element determined by the peak of the group is 0.1 to 5 mol%, preferably 1 to 5 mol%, more preferably 2 to 4 mol%, and further preferably 2.5 to 3.5 mol%, and the content of oxygen element determined by the peak corresponding to the C-O group is equivalent to the content of oxygen element determined by the peak corresponding to the C-O group
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-1: 1, preferably 0.3 to 1: 1, more preferably 0.6 to 1: 1, more preferably 0.9 to 1: 1; and is
In the X-ray photoelectron spectrum of the raw nanocarbon material, the content of nitrogen element determined from a peak corresponding to graphite-type nitrogen is 0.1 to 0.5 mol%, preferably 0.2 to 0.45 mol%, more preferably 0.3 to 0.4 mol%, based on the total amount of surface elements of the raw nanocarbon material determined by X-ray photoelectron spectrum, and the molar ratio of the content of nitrogen element determined from a peak corresponding to graphite-type nitrogen to the content of nitrogen element determined from a peak corresponding to pyrrole-type nitrogen is 0.1 to 1: 1, preferably 0.2 to 0.8: 1, more preferably 0.25 to 0.5: 1, more preferably 0.3 to 0.4: 1.
according to a third aspect of the present invention, there is provided a heteroatom-containing nanocarbon material produced by the method according to the second aspect of the present invention.
According to a fourth aspect of the present invention there is provided the use of a heteroatom-containing nanocarbon material according to the first aspect of the invention or according to the third aspect of the invention as a catalyst for the oxidative dehydrogenation of a hydrocarbon.
According to a fifth aspect of the present invention there is provided a process for the oxidative dehydrogenation of a hydrocarbon, the process comprising contacting the hydrocarbon under hydrocarbon oxidative dehydrogenation reaction conditions with a heteroatom-containing nanocarbon material according to the first aspect of the invention or according to the third aspect of the invention.
The heteroatom-containing nanocarbon material according to the present invention shows good catalytic activity in oxidative dehydrogenation of hydrocarbons. Meanwhile, the heteroatom-containing nano carbon material still maintains the good characteristics of the nano carbon material, such as better stability.
The preparation method of the heteroatom-containing nano material can stably regulate and control the content and existing form of the heteroatom in the nano carbon material, and has small influence on the structure of the nano carbon material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is an X-ray photoelectron spectroscopy (XPS) spectrum and a peak of oxygen (O1s) in the nanocarbon material containing hetero atoms prepared in example 1, in which the vertical axis represents the intensity of a signal and the horizontal axis represents binding energy (eV).
FIG. 2 is an XPS spectrum and a peak of oxygen (O1s) in the nanocarbon material containing hetero atoms prepared in comparative example 3, in which the vertical axis represents the intensity of a signal and the horizontal axis represents binding energy (eV).
FIG. 3 is an XPS spectrum and a peak of nitrogen (N1s) in the nanocarbon material containing hetero atoms prepared in example 1, wherein the vertical axis represents the intensity of a signal and the horizontal axis represents the binding energy (eV).
FIG. 4 is an XPS spectrum and a peak of nitrogen (N1s) in the nanocarbon material containing hetero atoms prepared in comparative example 3, in which the vertical axis represents the intensity of a signal and the horizontal axis represents binding energy (eV).
FIG. 5 is laser Raman spectra of the nanocarbon materials containing hetero atoms prepared in example 1 and comparative example 3, in which the vertical axis representsSignal intensity, with the horizontal axis representing wave number (cm)-1)。
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the invention, the nano carbon material refers to a carbon material with at least one dimension of a disperse phase dimension less than 100 nm.
According to a first aspect of the present invention, there is provided a heteroatom-containing nanocarbon material containing an oxygen element, a nitrogen element, a hydrogen element and a carbon element.
The content of the oxygen element in the heteroatom-containing nanocarbon material according to the present invention is 0.9 to 10% by weight, preferably 0.9 to 8.5% by weight, more preferably 1 to 5% by weight, and still more preferably 1.1 to 4.5% by weight, in terms of element, based on the total amount of the heteroatom-containing nanocarbon material; the content of the nitrogen element is 0.1 to 10 wt%, preferably 1 to 6 wt%, more preferably 1.5 to 4 wt%, and further preferably 1.6 to 3 wt%; the content of the hydrogen element is 0.1 to 2% by weight, preferably 0.2 to 1.5% by weight, more preferably 0.3 to 1.2% by weight, and further preferably 0.4 to 0.9% by weight; the content of the carbon element is 78 to 98.9 wt%, preferably 84 to 97.9 wt%, more preferably 89.8 to 97.2 wt%, and further preferably 91.6 to 96.9 wt%. The content of each element in the heteroatom-containing nano carbon material is measured by a combustion method.
According to the heteroatom-containing nanocarbon material of the present invention, the total amount of surface elements of the heteroatom-containing nanocarbon material determined by X-ray photoelectron spectroscopy is determined by X-ray photoelectron spectroscopy
The content of oxygen element determined by the peak of the radical is 0.1 to 1 mol%, preferably 0.4 to 1 mol%, more preferably 0.5 to 1 mol%.
The heteroatom-containing nanocarbon material according to the present inventionThe content of oxygen element determined by the peak corresponding to C-O group in X-ray photoelectron spectrum of nano carbon material and the content of oxygen element determined by the peak corresponding to C-O group
The molar ratio of the oxygen content determined by the peaks of the radicals is greater than 1, preferably from 1.1 to 5: 1, more preferably 1.15 to 3: 1, more preferably 1.25 to 2.8: 1.
the heteroatom-containing nanocarbon material according to the invention has an X-ray photoelectron spectrum corresponding to that of the heteroatom-containing nanocarbon material
The content of oxygen determined by the peak of the radical corresponds to
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-2: 1, preferably 0.2 to 1.5: 1, more preferably 0.25 to 1.1: 1, more preferably 0.35 to 0.95: 1.
according to the heteroatom-containing nanocarbon material of the invention, it is also possible for a certain amount of adsorbed water to be present. In the X-ray photoelectron spectroscopy of the heteroatom-containing nanocarbon material, the content of oxygen element determined from the peak corresponding to the adsorbed water is 5 mol% or less, preferably 0.05 to 3 mol%, more preferably 0.08 to 1.5 mol%, and further preferably 0.3 to 1.2 mol%, based on the total amount of surface elements of the heteroatom-containing nanocarbon material determined by X-ray photoelectron spectroscopy.
In the invention, the content of oxygen elements on the surface of the nano carbon material and the content of each oxygen species are measured by adopting an X-ray photoelectron spectroscopy, and the specific method comprises the following steps:
(1) performing X-ray photoelectron spectroscopy analysis on the nano carbon material to obtain an X-ray photoelectron spectroscopy spectrum, and taking the ratio of the peak area of the 1s spectral peak of one element to the sum of the peak areas of the 1s spectral peaks of the elements as the molar content of the element, wherein the molar content of the oxygen element is recorded as XO；
(2) Subjecting the X-ray toThe peak of O1s spectrum in the photoelectron spectrum (generally appearing in the range of 531-535eV, and the peak area is marked as AO) Performing peak separation, respectively corresponding to
Peaks of the groups (generally in the range 532.3 + -0.2 eV), corresponding to C-O groups (generally in the range 533.7 + -0.2 eV), corresponding to
The spectral peaks of the radicals (generally in the range 531.1. + -. 0.2 eV), and possibly the spectral peaks corresponding to the adsorbed water
(typically occurring in the range 535.5. + -. 0.2 eV), would correspond to
The peak area of the peak of the radical is recorded as ACOOThe peak area corresponding to the peak of the C-O group was taken as AC-OWill correspond to
The peak area of the peak of the radical is recorded as AC＝OThe peak area corresponding to the peak of the adsorbed water was designated as AAdsorbed water；
(3) The following formula is adopted to calculate the equation
Molar content X of oxygen determined by the peaks of the radicalsCOO：
The molar content X of the oxygen element determined from the peak of the spectrum corresponding to the adsorbed water was calculated by the following formulaAdsorbed water：
(4) A is to beC-O/ACOOThe content of oxygen element determined as a peak corresponding to the C-O group and the content of oxygen element determined as a peak corresponding to the C-O group
The molar ratio of the content of the oxygen element determined by the peak of the group;
(5) a is to beC＝O/ACOOAs corresponding to
The content of oxygen determined by the peak of the radical corresponds to
The peak of the radical spectrum determines the molar ratio of the content of the oxygen element.
According to the heteroatom-containing nanocarbon material of the present invention, the content of nitrogen element determined from a peak corresponding to graphite type nitrogen is 0.5 to 1 mol%, preferably 0.55 to 1 mol%, more preferably 0.55 to 0.95 mol% in an X-ray photoelectron spectroscopy spectrum of the heteroatom-containing nanocarbon material, based on the total amount of surface elements of the heteroatom-containing nanocarbon material determined by X-ray photoelectron spectroscopy.
According to the heteroatom-containing nanocarbon material of the present invention, the molar ratio of the content of nitrogen element determined by the peak corresponding to graphitic nitrogen to the content of nitrogen element determined by the peak corresponding to pyrrole nitrogen is more than 1, preferably 1.1 to 5: 1, more preferably 1.1 to 4: 1, more preferably 1.2 to 3.5: 1.
according to the heteroatom-containing nanocarbon material of the present invention, in an X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, a molar ratio of a content of nitrogen element determined by a peak corresponding to graphitic nitrogen to a content of nitrogen element determined by a peak corresponding to pyridinium nitrogen is 0.5 to 5: 1, preferably 0.5 to 2: 1, more preferably 0.7 to 1.8: 1.
according to the heteroatom-containing nanocarbon material of the present invention, in an X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, a molar ratio of a content of nitrogen element determined by a peak corresponding to graphitic nitrogen to a content of nitrogen element determined by a peak corresponding to a pyridine-oxidizing species is 2 to 10: 1, preferably 2.2 to 9: 1, more preferably 2.5 to 8: 1.
according to the heteroatom-containing nanocarbon material of the present invention, in the X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, the content of nitrogen element determined from the peak corresponding to the graphitic nitrogen and the content of nitrogen element determined from the peak corresponding to-NO2The molar ratio of the content of nitrogen elements determined by the peak of the group is 2-10: 1, preferably 2.5 to 6: 1, more preferably 3.5 to 5.5: 1.
in the invention, the content of nitrogen elements on the surface of the nano carbon material and the content of each nitrogen species are measured by adopting an X-ray photoelectron spectroscopy, and the specific method comprises the following steps:
(1) performing X-ray photoelectron spectroscopy analysis on the nano carbon material, and taking the ratio of the peak area of the 1s spectral peak of one element to the sum of the peak areas of the 1s spectral peaks of the elements in the obtained X-ray photoelectron spectroscopy as the molar content of the element, wherein the molar content of nitrogen is recorded as XN；
(2) The peak of N1s spectrum (generally appearing in the range of 398-406 eV) in the X-ray photoelectron spectrum is marked as AN) The peak separation was carried out to obtain a peak corresponding to graphite type nitrogen (generally in the range of 401.4. + -. 0.2 eV), a peak corresponding to pyrrole type nitrogen (generally in the range of 400.3. + -. 0.2 eV), a peak corresponding to pyridine type nitrogen (generally in the range of 398.4. + -. 0.2 eV), a peak corresponding to pyridine type nitrogen (generally in the range of 403.5. + -. 0.2 eV), and a peak corresponding to-NO2The peak (generally, the peak appears in the range of 405.5. + -. 0.2 eV), and the peak area corresponding to the peak of graphite type nitrogen was designated as AgThe peak area corresponding to the peak of the pyrrole type nitrogen is designated ApyroThe peak area corresponding to the peak of the pyridine nitrogen is designated ApyriThe peak area corresponding to the peak of the pyridine oxide species was designated Apyri-oWill correspond to-NO2The peak area of the peak was designated as An；
(3) The content X of nitrogen element determined from the peak of the spectrum corresponding to the graphite type nitrogen was calculated by the following formulaNg：
(4) A is to beg/ApyroAs a molar ratio of the content of nitrogen element determined from the peak corresponding to graphite type nitrogen to the content of nitrogen element determined from the peak corresponding to pyrrole type nitrogen;
(5) a is to beg/ApyriAs a molar ratio of the content of nitrogen element determined from the peak corresponding to graphite type nitrogen to the content of nitrogen element determined from the peak corresponding to pyridine type nitrogen;
(6) a is to beg/Apyri-oAs a molar ratio of the content of nitrogen element determined from the peak corresponding to graphite type nitrogen to the content of nitrogen element determined from the peak corresponding to pyridine oxide species;
(7) a is to beg/AnThe content of nitrogen element determined as a peak corresponding to graphite type nitrogen and the content of nitrogen element determined as a peak corresponding to-NO2The peak of the radical spectrum determines the mole ratio of the content of the nitrogen element.
According to the heteroatom-containing nanocarbon material of the present invention, the peak height of the D peak (denoted as I) in the Raman spectrum of the heteroatom-containing nanocarbon materialD) Peak height to G peak (denoted as I)G) Ratio of (1)D/IG0.2-0.4: 1, preferably 0.2 to 0.3: 1. the D peak generally appears at 1400 +/-20 cm-1Here, the G peak generally appears at 1580. + -. 20cm-1To (3).
The heteroatom-containing nanocarbon material according to the present invention may exist in various forms, and specifically, may be, but not limited to, one or a combination of two or more of a heteroatom-containing carbon nanotube, a heteroatom-containing graphene, a heteroatom-containing thin-layer graphite, a heteroatom-containing nanocarbon particle, a heteroatom-containing nanocarbon fiber, a heteroatom-containing nanodiamond, and a heteroatom-containing fullerene. The carbon nano-tube containing the heteroatom can be one or the combination of more than two of single-walled carbon nano-tube containing the heteroatom, double-walled carbon nano-tube containing the heteroatom and multi-walled carbon nano-tube containing the heteroatom. The heteroatom-containing nanocarbon material according to the invention is preferably a heteroatom-containing multiwall carbon nanotube.
According to the heteroatom-containing nano carbon material, the specific surface area of the heteroatom-containing multi-wall carbon nano tube is preferably 50-500m2The catalyst performance of the nanometer carbon material containing hetero atom, especially the catalyst for hydrocarbon material oxidative dehydrogenation, can be further improved. The specific surface area of the multi-walled carbon nanotube containing the heteroatom is more preferably 70 to 300m2(ii) g, more preferably 80 to 200m2(ii) in terms of/g. In the present invention, the specific surface area is measured by the nitrogen adsorption BET method.
According to the heteroatom-containing nano carbon material, the weight loss rate of the heteroatom-containing multi-walled carbon nano tube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01 to 0.3, which enables better catalytic performance, particularly when used as a catalyst for the oxidative dehydrogenation of hydrocarbons. More preferably, the weight loss rate of the multi-walled carbon nanotube containing the heteroatom in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800More preferably in the range of 0.02 to 0.2, still more preferably in the range of 0.05 to 0.15. In the present invention, w800＝W800－W400，w500＝W500－W400，W400The mass loss rate, W, measured at a temperature of 400 deg.C800The mass loss rate, W, measured at a temperature of 800 deg.C500Is the mass loss rate determined at a temperature of 500 ℃; the weight loss rate is measured in an air atmosphere by adopting a thermogravimetric analyzer, the test starting temperature is 25 ℃, and the heating rate is 10 ℃/min; the samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing.
The content of other non-metallic hetero atoms such as sulfur atom and phosphorus atom in the nano carbon material containing hetero atoms according to the present invention may be a conventional content. Generally, in the heteroatom-containing nanocarbon material according to the present invention, the total amount of non-metallic heteroatoms (such as sulfur atoms and phosphorus atoms) other than oxygen atoms and nitrogen atoms may be 5% by weight or less, preferably 2% by weight or less. The heteroatom-containing nanocarbon material according to the present invention may further contain a small amount of metal atoms remaining in the nanocarbon material production process, which are generally derived from a catalyst used in the production of the nanocarbon material, and the content of these remaining metal atoms is generally 5% by weight or less, preferably 3% by weight or less.
According to a second aspect of the present invention, there is provided a method for producing a heteroatom-containing nanocarbon material, the method comprising contacting a raw nanocarbon material with at least one oxidizing agent to obtain an oxidation-treated nanocarbon material, and calcining the oxidation-treated nanocarbon material at a temperature of 500-1200 ℃ in an inert atmosphere.
According to the method of the present invention, the raw material nanocarbon material contains an oxygen element, a nitrogen element, a hydrogen element and a carbon element, and the content of the oxygen element is 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, more preferably 1 to 2% by weight, and further preferably 1.5 to 1.8% by weight in terms of element, based on the total amount of the raw material nanocarbon material; the content of the nitrogen element is 2 to 10% by weight, preferably 2 to 5% by weight, more preferably 2.5 to 4% by weight, and further preferably 3 to 3.8% by weight; the content of the hydrogen element is 0.1 to 1% by weight, preferably 0.2 to 0.8% by weight, more preferably 0.4 to 0.7% by weight, and further preferably 0.5 to 0.6% by weight; the content of the carbon element is 86 to 97.8 wt%, preferably 91.7 to 97.3 wt%, more preferably 93.3 to 96.1 wt%, and further preferably 93.8 to 95 wt%. The content of each element in the raw material nano carbon material is measured by adopting a combustion method.
The total amount of surface elements of the raw nanocarbon material determined by X-ray photoelectron spectroscopy is determined by the X-ray photoelectron spectroscopy
The content of oxygen element determined by the peak of the radical is 0.1-5 mol%, preferably 1-5 mol%More preferably 2 to 4 mol%, and still more preferably 2.5 to 3.5 mol%.
The raw material nano carbon material has X-ray photoelectron spectrum with oxygen content determined by the peak corresponding to C-O group and the peak corresponding to C-O group
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-1: 1, preferably 0.3 to 1: 1, more preferably 0.6 to 1: 1, more preferably 0.9 to 1: 1.
the raw material nano carbon material has X-ray photoelectron spectrum corresponding to that of
The content of oxygen determined by the peak of the radical corresponds to
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-1: 1, preferably 0.15 to 0.5: 1, more preferably 0.18 to 0.35: 1.
the raw nanocarbon material generally does not contain adsorbed water.
In the X-ray photoelectron spectroscopy of the raw nanocarbon material, the content of nitrogen element determined from a peak corresponding to graphite-type nitrogen is 0.1 to 0.5 mol%, preferably 0.2 to 0.45 mol%, more preferably 0.3 to 0.4 mol%, based on the total amount of surface elements of the raw nanocarbon material determined by the X-ray photoelectron spectroscopy.
In the X-ray photoelectron spectrum of the raw material nano carbon material, the molar ratio of the content of nitrogen element determined by a spectrum peak corresponding to graphite type nitrogen to the content of nitrogen element determined by a spectrum peak corresponding to pyrrole type nitrogen is 0.1-1: 1, preferably 0.2 to 0.8: 1, more preferably 0.25 to 0.5: 1, more preferably 0.3 to 0.4: 1.
in the X-ray photoelectron spectrum of the raw material nano carbon material, the molar ratio of the content of nitrogen element determined by a spectrum peak corresponding to graphite type nitrogen to the content of nitrogen element determined by a spectrum peak corresponding to pyridine type nitrogen is 0.1-2: 1, preferably 0.2 to 1: 1, more preferably 0.3 to 0.8: 1, more preferably 0.4 to 0.5: 1.
in the X-ray photoelectron spectrum of the raw material nano carbon material, the molar ratio of the content of nitrogen element determined by a spectrum peak corresponding to graphite type nitrogen to the content of nitrogen element determined by a spectrum peak corresponding to pyridine oxide species is 0.1-5: 1, preferably 1 to 4.5: 1, more preferably 2 to 4: 1, more preferably 2.5 to 3.5: 1.
the raw material nano carbon material has X-ray photoelectron spectrum, and the content of nitrogen element determined by the peak corresponding to graphite type nitrogen and the content of nitrogen element determined by the peak corresponding to-NO2The molar ratio of the content of nitrogen elements determined by the peak of the group is 0.1-3: 1, preferably 1 to 3: 1, more preferably 1.5 to 2.5: 1, more preferably 1.8 to 2.1: 1.
in the Raman spectrum of the raw material nano carbon material, the ratio I of the peak height of a D peak to the peak height of a G peakD/IGIs 0.01 to 0.2, preferably 0.1 to 0.2, more preferably 0.15 to 0.18.
According to the method of the present invention, the raw material nanocarbon material may be a nanocarbon material in various existing forms. Specifically, the raw material nanocarbon material may be, but is not limited to, one or a combination of two or more of carbon nanotubes, graphene, nanodiamonds, thin-layer graphites, nanocarbon particles, nanocarbon fibers, and fullerenes. The carbon nanotube can be one or the combination of more than two of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube. Preferably, the raw material nanocarbon material is a carbon nanotube, more preferably a multiwall carbon nanotube.
In a preferred embodiment, the raw material nanocarbon material is a multi-walled carbon nanotube, and the specific surface area of the multi-walled carbon nanotube may be 50 to 500m2(ii) in terms of/g. Preferably, the specific surface area of the multi-walled carbon nanotube is 70-300m2When the specific surface area of the multi-wall carbon nano tube is within the range, the finally obtained heteroatom-containing nano carbon material has better catalytic activity, and particularly can obtain better catalytic effect when being used as a catalyst for the oxidative dehydrogenation reaction of hydrocarbon substances. More preferablyThe specific surface area of the multi-wall carbon nano tube is 80-160m2/g。
When the raw material nano carbon material is the multi-walled carbon nanotube, the weight loss rate of the multi-walled carbon nanotube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01-0.3. More preferably, w500/w800In the range of 0.02 to 0.2, the thus-prepared heteroatom-containing nanocarbon material shows a better catalytic effect, particularly when used as a catalyst for oxidative dehydrogenation of hydrocarbon substances. Further preferably, w500/w800In the range of 0.05-0.15.
According to the method of the present invention, the total amount (in terms of elements) of the non-metallic hetero atoms (such as phosphorus atoms and sulfur atoms) other than oxygen atoms and nitrogen atoms in the raw material nanocarbon material may be a conventional amount. Generally, the total amount of the remaining non-metallic hetero atoms other than oxygen atoms and nitrogen atoms in the raw material nanocarbon material is not more than 5% by weight, preferably not more than 2% by weight. According to the method of the present invention, the raw material nanocarbon material may further contain some metal elements, depending on the source, which are generally derived from the catalyst used in the preparation of the raw material nanocarbon material, in an amount of generally 5% by weight or less, preferably 3% by weight or less.
According to the method of the present invention, the raw nanocarbon material may be pretreated (e.g., washed) before use by a method commonly used in the art to remove some impurities from the surface of the raw nanocarbon material; the raw material nano carbon material can also be directly used without pretreatment, and in the embodiment disclosed by the invention, the raw material nano carbon material is not pretreated before being used.
According to the method, the nano-carbon material subjected to oxidation treatment is obtained by contacting the raw material nano-carbon material with the oxidant, and compared with the method that the nano-carbon material is not subjected to oxidant treatment and is directly contacted in the non-active atmosphere at the temperature of 500-1200 ℃, the nano-carbon material containing the heteroatom prepared by the method disclosed by the invention shows more excellent catalytic activity, not only can higher raw material conversion rate be obtained, but also higher product selectivity can be obtained.
According to the method of the present invention, the oxidizing agent is preferably one or two or more of an acid having oxidizing properties, hydrogen peroxide, and an organic peroxide. In a preferred embodiment of the present invention, the oxidizing agent is selected from HNO3、H2SO4One or more than two of hydrogen peroxide and organic peroxide shown in formula I,
In the formula I, R1And R2Each is selected from H, C4-C12Straight or branched alkyl of (2), C6-C12Aryl of (C)7-C12Aralkyl and
and R is1And R2Not simultaneously being H or R3Is C4-C12Straight or branched alkyl or C6-C12Aryl group of (1).
In the present invention, C4-C12Specific examples of the alkyl group of (a) may include, but are not limited to, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl, hexyl (including various isomers of hexyl), cyclohexyl, octyl (including various isomers of octyl), nonyl (including various isomers of nonyl), decyl (including various isomers of decyl), undecyl (including various isomers of undecyl), and dodecyl (including various isomers of dodecyl).
In the present invention, C6-C12Specific examples of the aryl group of (a) may include, but are not limited to, phenyl, naphthyl, methylphenyl and ethylphenyl.
In the present invention, C7-C12Specific examples of the aralkyl group of (a) may include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butylPhenyl isopropyl, phenyl n-pentyl and phenyl n-butyl.
Specific examples of the oxidizing agent may include, but are not limited to: HNO3、H2SO4Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, dicumyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide and lauroyl peroxide.
Preferably, the oxidizing agent is an acid having oxidizing properties. More preferably, the oxidizing agent is HNO3And/or H2SO4. From the viewpoint of further improving the product selectivity of the finally prepared heteroatom-containing nanocarbon material in hydrocarbon oxidative dehydrogenation reaction, the oxidizing agent is more preferably HNO3And H2SO4. Even more preferably, the oxidizing agent is HNO3And H2SO4And HNO3And H2SO4The molar ratio is 1: 2-10, preferably 1: 3-9, more preferably 1: 3.5-8. Particularly preferably, the oxidizing agent is HNO3And H2SO4And HNO3And H2SO4The molar ratio is 1: 3.6-7.2, the prepared nano carbon material containing the heteroatom shows more excellent catalytic activity in the oxidative dehydrogenation reaction of hydrocarbon, and obtains higher product selectivity under the condition of obtaining higher raw material conversion rate.
According to the process of the present invention, the oxidizing agent may be provided in pure form or may be provided in the form of a solution (preferably in the form of an aqueous solution). Where the oxidant is provided in the form of a solution, the concentration of the solution may be conventionally selected.
According to the method of the present invention, the amount of the oxidizing agent may be 500-.
According to the method of the present invention, the raw material nanocarbon can beThe material and the oxidizing agent are contacted in a liquid dispersion medium. The liquid dispersion medium may be selected according to the amount of the raw nanocarbon material used. Preferably, the liquid dispersion medium is water. The amount of the liquid dispersion medium may be selected depending on the amounts of the raw nanocarbon material and the oxidizing agent. Generally, the amount of the liquid dispersion medium may be 500-. The oxidant contains HNO3When used, the liquid dispersion medium is preferably used in such an amount that HNO is present3The concentration in the liquid phase is 1 to 15mol/L, more preferably such that HNO is present3The concentration in the liquid phase is 1.2 to 8mol/L, and it is further preferable that HNO is made to be present3The concentration in the liquid phase is 1.5 to 6.5mol/L, and it is further preferable that HNO is made to be present3The concentration in the liquid phase is 1.5-4 mol/L. In the presence of H in the oxidizing agent2SO4When used, the liquid dispersion medium is preferably used in such an amount that H2SO4The concentration in the liquid phase is 4 to 20mol/L, more preferably such that H2SO4The concentration in the liquid phase is from 5 to 16mol/L, and it is further preferred that H is caused to be present2SO4The concentration in the liquid phase is 7-15 mol/L.
According to the method of the invention, the raw nanocarbon material is contacted with the oxidizing agent at a temperature of 10-50 ℃, e.g., at a temperature of 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃,19 ℃,20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃,31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃,42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃,49 ℃ or 50 ℃. Compared with the method that the raw material nano carbon material is contacted with the oxidant at the temperature higher than 50 ℃, the method can obviously improve the catalytic activity of the finally prepared nano carbon material containing the heteroatom in the oxidation dehydrogenation reaction of hydrocarbon under the same conditions, and obtain higher raw material conversion rate and product selectivity. From the viewpoint of further improving the catalytic activity of the finally prepared heteroatom-containing nanocarbon material in the oxidative dehydrogenation of hydrocarbon substances, the raw nanocarbon material is contacted with the oxidant at a temperature of 20 to 50 ℃. More preferably, the raw nanocarbon material is contacted with the oxidizing agent at a temperature of 40 to 50 ℃.
According to the method of the present invention, the raw material nanocarbon material is contacted with the oxidizing agent preferably in the presence of ultrasonic waves from the viewpoint of further improving the catalytic activity of the finally prepared heteroatom-containing nanocarbon material in the oxidative dehydrogenation reaction of hydrocarbon substances. The contacting in the presence of ultrasonic waves may be achieved by placing the raw nanocarbon material and the oxidizing agent in an ultrasonic cleaner. The frequency of the ultrasonic wave can be 25-100kHz, and is preferably 40-60 kHz.
According to the method of the present invention, the time for which the raw nanocarbon material is contacted with the oxidizing agent may be selected according to the temperature at which the contact is performed. In general, the duration of the contact may be from 0.5 to 10 hours, preferably from 1 to 6 hours.
According to the method of the present invention, when the raw nanocarbon material is brought into contact with the oxidizing agent in the liquid dispersion medium, after the contact is completed, the method of the present invention further comprises separating a solid matter from the mixture obtained by the contact, and drying the solid matter, thereby obtaining the oxidation-treated nanocarbon material.
The solid matter can be separated from the mixture obtained by the contact by a common solid-liquid separation method such as one or a combination of two or more of centrifugation, filtration and decantation. The separated solid material is preferably dried after washing with water (e.g. deionized water) to neutrality (typically to a pH of 6-7 for the wash water). The drying conditions are such that the liquid dispersion medium contained in the separated solid matter can be removed. In general, the drying may be carried out at a temperature of from 80 to 180 ℃ and preferably at a temperature of from 100 ℃ to 140 ℃. The duration of the drying may be selected according to the temperature at which the drying is carried out. In general, the duration of the drying may be from 0.5 to 24 hours, preferably from 1 to 20 hours, more preferably from 6 to 16 hours, such as from 8 to 16 hours. The drying may be performed in an oxygen-containing atmosphere or in an oxygen-free atmosphere. Such as an air atmosphere, and a non-oxygen-containing atmosphere such as a nitrogen atmosphere, a group zero gas atmosphere (e.g., an argon atmosphere).
According to the method of the present invention, the oxidation-treated nanocarbon material obtained by contacting the raw nanocarbon material with an oxidizing agent is calcined at a temperature of 500-1200 ℃ in an inert atmosphere. Compared with the calcination in the non-active atmosphere at the temperature lower than 500 ℃, the heteroatom-containing nano carbon material obtained by the calcination in the non-active atmosphere at the temperature of 500-1200 ℃ shows more excellent catalytic activity in the oxidative dehydrogenation reaction of hydrocarbon substances, and can obviously improve the conversion rate of raw materials and the selectivity of products. Preferably, the calcination is carried out at a temperature of 700-. From the viewpoint of further improving the product selectivity (particularly, the selectivity for olefin) of the finally produced heteroatom-containing nanocarbon material in the oxidative dehydrogenation of hydrocarbon substances, the calcination is further preferably carried out at a temperature of 800-1100 ℃. From the viewpoint of further improving the product selectivity (particularly the selectivity to olefin), the calcination is further preferably carried out at a temperature of 900-1100 ℃, particularly preferably at a temperature of 1000-1100 ℃.
The duration of the firing may be selected according to the temperature at which the firing is carried out. In general, the duration of the calcination may be from 0.5 to 24 hours, preferably from 1 to 8 hours, more preferably from 2 to 5 hours.
According to the method of the present invention, the oxidation-treated nanocarbon material is calcined in an inert atmosphere. The inert atmosphere refers to a chemically inert atmosphere. The inert gas atmosphere may be specifically an atmosphere formed by an inert gas, and the inert gas may be, for example, one or two or more of nitrogen and a group zero gas (e.g., helium, argon). Preferably, the oxidation-treated nanocarbon material is calcined in a nitrogen atmosphere.
According to a third aspect of the present invention, there is provided a heteroatom-containing nanocarbon material produced by the method according to the second aspect of the present invention.
The heteroatom-containing nano carbon material or the heteroatom-containing nano carbon material prepared by the method has good catalytic performance, and particularly shows higher catalytic activity in the oxidative dehydrogenation reaction of hydrocarbon substances.
The heteroatom-containing nanocarbon material according to the invention or the heteroatom-containing nanocarbon material prepared by the process of the invention can be used as such as a catalyst or can be used in the form of a shaped catalyst. The shaped catalyst may contain a heteroatom-containing nanocarbon material according to the invention or a heteroatom-containing nanocarbon material prepared by the method of the invention and a binder. The binder may be selected according to the specific application of the formed catalyst, and may be, for example, an organic binder and/or an inorganic binder, so as to meet the application requirements.
According to a fourth aspect of the present invention there is provided the use of a heteroatom-containing nanocarbon material according to the first aspect of the invention or a heteroatom-containing nanocarbon material according to the third aspect of the invention as a catalyst for the oxidative dehydrogenation of hydrocarbons.
According to the application of the invention, the heteroatom-containing nano carbon material can be directly used for hydrocarbon oxidative dehydrogenation reaction, and can also be used for hydrocarbon oxidative dehydrogenation reaction after being formed.
According to a fifth aspect of the present invention there is provided a process for the dehydrogenation of a hydrocarbon, the process comprising contacting the hydrocarbon with a heteroatom-containing nanocarbon material according to the first aspect of the invention or a heteroatom-containing nanocarbon material according to the third aspect of the invention under hydrocarbon oxidative dehydrogenation reaction conditions.
According to the hydrocarbon oxidative dehydrogenation reaction method, the heteroatom-containing nano carbon material can be directly used for contacting with hydrocarbon, or the heteroatom-containing nano carbon material can be formed and then used for contacting with hydrocarbon.
The hydrocarbon dehydrogenation reaction process according to the present invention can dehydrogenate various types of hydrocarbons to obtain unsaturated hydrocarbons such as olefins. The process according to the invention is particularly suitable for dehydrogenating alkanes, thereby obtaining alkenes.
In the present invention,the hydrocarbon is preferably an alkane, such as C2-C12Of (a) an alkane. Specifically, the hydrocarbon may be, but not limited to, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2, 3-dimethylbutane, cyclohexane, methylcyclopentane, n-heptane, 2-methylhexane, 3-methylhexane, 2-ethylpentane, 3-ethylpentane, 2, 3-dimethylpentane, 2, 4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2, 3-dimethylhexane, 2, 4-dimethylhexane, 2, 5-dimethylhexane, 3-ethylhexane, 2, 3-trimethylpentane, 2,3, 3-trimethylpentane, 2,4, 4-trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2, 3-dimethylheptane, 2, 4-dimethylheptane, 3-ethylheptane, 4-ethylheptane, 2,3, 4-trimethylhexane, 2,3, 5-trimethylhexane, 2,4, 5-trimethylhexane, 2, 3-trimethylhexane, 2, 4-trimethylhexane, 2, 5-trimethylhexane, 2,3, 3-trimethylhexane, 2,4, 4-trimethylhexane, 2-methyl-3-ethylhexane, 2-methyl-4-ethylhexane, 3-methyl-3-ethylhexane, 3-methyl-4-ethylhexane, 3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropylcyclohexane, trimethylcyclohexane (including various isomers of trimethylcyclohexane, such as 1,2, 3-trimethylcyclohexane, 1,2, 4-trimethylcyclohexane, 1,2, 5-trimethylcyclohexane, 1,3, 5-trimethylcyclohexane), n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2, 3-dimethyloctane, 2, 4-dimethyloctane, 3-ethyloctane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-, 4-ethyloctane, 2,3, 4-trimethylheptane, 2,3, 5-trimethylheptane, 2,3, 6-trimethylheptane, 2,4, 5-trimethylheptane, 2,4, 6-trimethylheptane, 2, 3-trimethylheptane, 2, 4-trimethylheptane, 2, 5-trimethylheptane, 2, 6-trimethylheptane, 2,3, 3-trimethylheptane, 2,4, 4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl-3-ethylheptane, 5-methyl-3-ethylheptane, 4-methyl-4-ethylheptane, 4-propylheptane3, 3-diethylhexane, 3, 4-diethylhexane, 2-methyl-3, 3-diethylpentane, phenylethane, 1-phenylpropane, 2-phenylpropane, 1-phenylbutane, 2-phenylbutane, 1-phenylpentane, 2-phenylpentane and 3-phenylpentane.
More preferably, the hydrocarbon is one or two or more of propane, n-butane, isobutane and phenylethane. Further preferably, the hydrocarbon is n-butane.
The amount of oxygen used in the hydrocarbon dehydrogenation process according to the present invention may be conventionally selected. Generally, the molar ratio of hydrocarbon to oxygen may be from 0.2 to 3: 1, preferably 0.5 to 2.5: 1, more preferably 1-2: 1.
according to the hydrocarbon dehydrogenation reaction method, the hydrocarbon and optional oxygen can be fed into the reactor by the carrier gas to contact and react with the heteroatom-containing nano carbon material. The carrier gas may be a commonly used gas that does not chemically interact with the reactants and the reaction product under the reaction conditions and does not undergo decomposition, such as one or a combination of two or more of nitrogen, carbon dioxide, a noble gas, and water vapor. The amount of carrier gas may be conventionally selected. Generally, the carrier gas may be present in an amount of 30 to 99.5% by volume, preferably 50 to 99% by volume, more preferably 70 to 98% by volume.
In the process for the dehydrogenation of hydrocarbons according to the present invention, the temperature of the contacting may be conventionally selected to be sufficient for the dehydrogenation of hydrocarbons to take place. Generally, the contacting may be performed at a temperature of 200-650 ℃, preferably at a temperature of 300-600 ℃, more preferably at a temperature of 350-550 ℃, and even more preferably at a temperature of 400-450 ℃.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the contact may be performed in a fixed bed reactor or a fluidized bed reactor, and is not particularly limited. Preferably, the contacting is carried out in a fixed bed reactor.
According to the hydrocarbon dehydrogenation process of the present invention, the duration of the contact may be selected according to the temperature of the contact, for example, when the contact is carried out in a fixed bed reactor, the gas atmosphere of the feed may be usedThe space velocity represents the duration of contact. Generally, the gas hourly space velocity of the feed can be 500-2000h-1Preferably 800--1。
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, X-ray photoelectron spectroscopy was carried out on an ESCALB 250 type X-ray photoelectron spectrometer equipped with Thermo Avantage V5.926 software, manufactured by Thermo Scientific, with an excitation source of monochromated Al K α X rays, an energy of 1486.6eV, a power of 150W, a transmission energy for narrow scanning of 30eV, and a base vacuum of 6.5 × 10 for analytical tests-10mbar, electron binding energy was corrected for the C1s peak (284.6eV) of elemental carbon, data processed on ThermoAvantage software, and quantified in the analytical module using the sensitivity factor method. The samples were dried at a temperature of 150 c and 1 atm under a helium atmosphere for 3 hours before testing.
In the following examples and comparative examples, elemental analysis was performed on an Elementar Micro Cube analyzer and raman spectroscopic analysis was performed on a JY LabRAM HR raman analyzer.
In the following examples and comparative examples, thermogravimetric analysis was performed on a TA5000 thermal analyzer under air atmosphere at a temperature rise rate of 10 ℃/min and in the temperature range of room temperature (25 ℃) to 1000 ℃. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing. The method adopts ASAP2000 type N of Micromertrics corporation in America2The physical adsorption apparatus measures the specific surface area.
Examples 1 to 13 are for illustrating the heteroatom-containing nanocarbon material of the present invention and the method for preparing the same.
Example 1
(1) 10g of multiwall carbon nanotubes (specific surface area: 83 m) as a raw nanocarbon material2The weight loss rate of the material in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w8000.09, from Chengdu organic chemistry, Ltd, China academy of sciences) and 500mL of acid solution (H)2SO4Is 1380g/L, HNO3227.5g/L and the solvent of the acid solution is water), and the obtained dispersion is put into an ultrasonic cleaner for ultrasonic treatment, wherein the temperature of the dispersion in the ultrasonic cleaner is controlled at 50 ℃, the duration of the ultrasonic treatment is 6 hours, and the frequency of the ultrasonic wave is 45 kHz. And after the ultrasonic treatment is finished, filtering the dispersion liquid, washing the collected solid matters by using deionized water until the pH value of the washing liquid is in the range of 6-7, and drying the washed solid matters for 12 hours at the temperature of 120 ℃ in an air atmosphere to obtain the nano carbon material subjected to oxidation treatment.
(2) The oxidized nanocarbon material was calcined at a temperature of 700 ℃ for 5 hours in a nitrogen atmosphere to obtain a heteroatom-containing nanocarbon material according to the invention, the composition and property parameters of which are listed in table 1.
Example 2
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that, in the step (2), the nanocarbon material subjected to oxidation treatment was calcined at a temperature of 500 ℃ for 5 hours in a nitrogen atmosphere. The composition and property parameters of the prepared heteroatom-containing nanocarbon material are listed in table 1.
Comparative example 1
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that, in the step (2), the nanocarbon material subjected to oxidation treatment was calcined at a temperature of 400 ℃ for 5 hours in a nitrogen atmosphere. The composition and property parameters of the prepared heteroatom-containing nanocarbon material are listed in table 1.
Comparative example 2
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that the step (2) was not performed (i.e., the oxidized nanocarbon material was not calcined, and was directly used as a heteroatom-containing nanocarbon material). The composition and property parameters of the prepared heteroatom-containing nanocarbon material are listed in table 1.
Comparative example 3
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that the multiwall carbon nanotubes as the raw nanocarbon material were directly fed to the step (2) to be calcined. The compositions of the prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Comparative example 4
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that no oxidizing agent was used in step (1). The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Comparative example 5
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 2, except that, in the step (2), the nanocarbon material subjected to oxidation treatment was calcined at a temperature of 500 ℃ for 5 hours in an air atmosphere. The composition and property parameters of the prepared heteroatom-containing nanocarbon material are listed in table 1.
Example 3
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that in the step (1), H was added to the acid solution2SO4Has a concentration of 0g/L, HNO3The concentration of (3) was 227.5 g/L. The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 4
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that in the step (1), H was added to the acid solution2SO4Is 1380g/L, HNO3The concentration of (2) is 0 g/L. The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 5
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that in the step (1), the acid solution was replaced with hydrogen peroxide of the same volume (the concentration of hydrogen peroxide in hydrogen peroxide was 330 g/L). The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 6
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that, in the step (2), the calcination temperature was 800 ℃. The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Comparative example 6
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 6, except that the multiwall carbon nanotubes as the raw nanocarbon material were directly fed to the step (2) to be calcined. The compositions of the prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 7
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that, in the step (2), the calcination temperature was 900 ℃. The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Comparative example 7
A heteroatom-containing nanocarbon material was produced in the same manner as in example 7, except that the multiwall carbon nanotubes as the raw nanocarbon material were directly fed to the step (2) to be calcined. The compositions of the prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 8
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that, in the step (2), the calcination temperature was 1000 ℃. The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Comparative example 8
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 8, except that the multiwall carbon nanotubes as the raw nanocarbon material were directly fed to the step (2) to be calcined. The compositions of the prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 9
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that, in the step (2), the calcination temperature was 1100 ℃. The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Comparative example 9
A heteroatom-containing nanocarbon material was produced in the same manner as in example 9, except that the multiwall carbon nanotubes as the raw nanocarbon material were directly fed to the step (2) to be calcined. The compositions of the prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 10
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that, in the step (2), the calcination temperature was 1200 ℃. The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 11
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that in the step (1), H was added to the acid solution2SO4Has a concentration of 1220g/L, HNO3The concentration of (2) was 390 g/L. The prepared heteroatom-containing nanocarbon materials and their property parameters are listed in table 1.
Example 12
(1) 10g of multiwall carbon nanotubes (specific surface area: 153 m) as a raw nanocarbon material2The weight loss rate of the material in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w8000.15, available from Beijing Deke island gold technologies, Ltd.) and 500mL of acid solution (H)2SO4Is 1380g/L, HNO3126g/L, the solvent of the acid solution is water), and the obtained dispersion is placed in an ultrasonic cleaner for ultrasonic treatment, wherein the temperature of the dispersion in the ultrasonic cleaner is controlled to be 40 ℃, the duration of the ultrasonic treatment is 2 hours, and the frequency of the ultrasonic wave is 60 kHz. And after the ultrasonic treatment is finished, filtering the dispersion liquid, washing the collected solid matters by using deionized water until the pH value of the washing liquid is in the range of 6-7, and drying the washed solid matters in an air atmosphere at the temperature of 100 ℃ for 16 hours to obtain the nano carbon material subjected to oxidation treatment.
(2) The oxidized nanocarbon material was calcined at a temperature of 1000 ℃ for 3 hours in a nitrogen atmosphere to obtain a heteroatom-containing nanocarbon material according to the invention, the composition and property parameters of which are listed in table 1.
Example 13
(1) 10g of the nanocarbon material multi-walled carbon nanotubes (same as in example 12) and 500mL of an acid solution (H)2SO4Has a concentration of 690g/L, HNO3114g/L, the solvent of the acid solution is water), and the obtained dispersion is placed in an ultrasonic cleaner for ultrasonic treatment, wherein the temperature of the dispersion in the ultrasonic cleaner is controlled to be 25 ℃, the duration of the ultrasonic treatment is 1 hour, and the frequency of the ultrasonic wave is 40 kHz. And after the ultrasonic treatment is finished, filtering the dispersion liquid, washing the collected solid matters by using deionized water until the pH value of the washing liquid is in the range of 6-7, and drying the washed solid matters for 8 hours at the temperature of 140 ℃ in an air atmosphere to obtain the nano carbon material subjected to oxidation treatment.
(2) The oxidized nanocarbon material was calcined at 900 ℃ for 2 hours in a nitrogen atmosphere to obtain a heteroatom-containing nanocarbon material according to the invention, the composition and property parameters of which are listed in table 1.
Experimental examples 1-13 are provided to illustrate the use of the heteroatom-containing nanocarbon material of the present invention and the dehydrogenation reaction method of hydrocarbons.
Experimental examples 1 to 13
The heteroatom-containing nanocarbon materials prepared in examples 1 to 13 were used as a catalyst for oxidative dehydrogenation of n-butane, as follows.
0.2g (packing volume of 0.5mL) of the heteroatom-containing nanocarbon material prepared in examples 1 to 13 as a catalyst was packed in a universal fixed bed miniature quartz tube reactor each having quartz sand sealed at both ends, and a gas containing n-butane and oxygen (concentration of n-butane of 0.7 vol%, molar ratio of n-butane to oxygen of 1: 2, and balance of nitrogen as a carrier gas) was fed at a total volume space velocity of 1000h under normal pressure (i.e., 1 atm) and 450 deg.C-1Introducing into a reactor for reaction, continuously monitoring the composition of the reaction mixture output from the reactor, and calculating n-butane conversion rate, total olefin selectivity and butadiene selectivityAnd total yield of olefins (total yield of olefins ═ n-butane conversion × total olefin selectivity), the results of the 5-hour reaction are shown in table 2.
Experimental comparative examples 1 to 9
Hydrocarbon oxidative dehydrogenation reactions were carried out in the same manner as in experimental examples 1 to 13, except that the heteroatom-containing nanocarbon materials prepared in comparative examples 1 to 9 were packed in a universal type fixed bed microtquartz tube reactor as catalysts, respectively. The results of the reaction for 5 hours are shown in Table 2.
Comparative Experimental examples 1-2
The hydrocarbon oxidative dehydrogenation reactions were carried out in the same manner as in experimental examples 1 to 13, except that the raw material nanocarbon materials in step (1) of examples 1 and 12 were packed as catalysts in a universal type fixed bed microtquartz tube reactor, respectively. The results of the reaction for 5 hours are shown in Table 2.
The results of table 2 confirm that the nanocarbon material containing hetero atoms according to the present invention shows good catalytic performance in oxidative dehydrogenation of hydrocarbons, and not only can obtain higher conversion rate of raw materials, but also can obtain higher product selectivity and total olefin yield.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the foregoing embodiments may be combined in any suitable manner without contradiction, and various combinations that are possible in the present invention are not described separately in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
TABLE 2
1: the raw material nanocarbon material in example 1
2: the raw material nanocarbon material in example 12.
Claims (105)
1. A method for preparing a heteroatom-containing nano-carbon material comprises the steps of contacting a raw nano-carbon material with an oxidant to obtain an oxidized nano-carbon material, and roasting the oxidized nano-carbon material at the temperature of 500-1200 ℃ in an inactive atmosphere, wherein the contacting is carried out at the temperature of 20-50 ℃, and the oxidant is HNO3And H2SO4And HNO3And H2SO4In a molar ratio of 1: 2 to 10, the raw material nanocarbon material containing an oxygen element, a nitrogen element, a hydrogen element and a carbon element, the content of the oxygen element being 0.1 to 3% by weight, the content of the nitrogen element being 2 to 10% by weight, the content of the hydrogen element being 0.1 to 1% by weight and the content of the carbon element being 86 to 97.8% by weight, in terms of elements, based on the total amount of the raw material nanocarbon material, the molar ratio of the content of the nitrogen element determined from a peak corresponding to graphite-type nitrogen to the content of the nitrogen element determined from a peak corresponding to pyrrole-type nitrogen in an X-ray photoelectron spectrum of the raw material nanocarbon material, based on the total amount of surface elements of the raw material nanocarbon material determined from X-ray photoelectron spectrum, being 0.3 to 0.4: 1,
the total amount of surface elements of the raw nanocarbon material determined by X-ray photoelectron spectroscopy is determined by the X-ray photoelectron spectroscopy
The content of oxygen element determined by the peak of the group is 0.1-5 mol%, and the content of oxygen element determined by the peak corresponding to C-O group
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-1: 1;
in the X-ray photoelectron spectrum of the raw nanocarbon material, based on the total amount of surface elements of the raw nanocarbon material determined by the X-ray photoelectron spectrum, the content of nitrogen elements determined by a peak corresponding to graphite-type nitrogen is 0.1 to 0.5 mol%, and the molar ratio of the content of nitrogen elements determined by a peak corresponding to graphite-type nitrogen to the content of nitrogen elements determined by a peak corresponding to pyrrole-type nitrogen is 0.1 to 1: 1; and is
In the Raman spectrum of the raw material nano carbon material, the ratio I of the peak height of a D peak to the peak height of a G peakD/IG0.01-0.2;
the heteroatom-containing nanocarbon material contains oxygen element, nitrogen element, hydrogen element and carbon element, wherein the content of the oxygen element is 0.9-10 wt%, the content of the nitrogen element is 0.1-10 wt%, the content of the hydrogen element is 0.1-2 wt% and the content of the carbon element is 78-98.9 wt% in terms of elements based on the total amount of the heteroatom-containing nanocarbon material;
in the X-ray photoelectron spectrum atlas of the heteroatom-containing nano carbon material, the total amount of surface elements of the heteroatom-containing nano carbon material determined by X-ray photoelectron spectrum is used as a reference
The content of oxygen element determined by the peak of the group is 0.1-1 mol%, and the content of oxygen element determined by the peak corresponding to C-O group
Oxygen content determined by the spectral peaks of the radicalsThe molar ratio of the amounts is 1.1-5: 1;
in the X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, the content of nitrogen element determined by the peak corresponding to graphite type nitrogen is 0.5 to 1 mol%, and the ratio of the content of nitrogen element determined by the peak corresponding to graphite type nitrogen to the content of nitrogen element determined by the peak corresponding to pyrrole type nitrogen is 1.1 to 5: 1; and is
In the Raman spectrum of the heteroatom-containing nano carbon material, the ratio I of the peak height of a D peak to the peak height of a G peakD/IG0.2-0.4: 1.
2. the method according to claim 1, wherein the content of the oxygen element is 0.5 to 2.5 wt%, the content of the nitrogen element is 2 to 5 wt%, the content of the hydrogen element is 0.2 to 0.8 wt%, and the content of the carbon element is 91.7 to 97.3 wt% in terms of element based on the total amount of the raw nanocarbon material.
3. The method according to claim 2, wherein the content of the oxygen element is 1 to 2% by weight, the content of the nitrogen element is 2.5 to 4% by weight, the content of the hydrogen element is 0.4 to 0.7% by weight, and the content of the carbon element is 93.3 to 96.1% by weight, in terms of element, based on the total amount of the raw nanocarbon material.
4. The method according to claim 3, wherein the content of the oxygen element is 1.5 to 1.8 wt%, the content of the nitrogen element is 3 to 3.8 wt%, the content of the hydrogen element is 0.5 to 0.6 wt%, and the content of the carbon element is 93.8 to 95 wt% in terms of element based on the total amount of the raw nanocarbon material.
5. The method according to claim 1, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to the total amount of surface elements of the raw nanocarbon material determined by the X-ray photoelectron spectrum
The content of oxygen element determined by the peak of the radical is 1-5 mol%, the content of oxygen element determined by the peak corresponding to C-O radical and the content of oxygen element determined by the peak corresponding to C-O radical
The molar ratio of the content of oxygen element determined by the peak of the group is 0.3-1: 1.
6. the method according to claim 5, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to the total amount of surface elements of the raw nanocarbon material determined by the X-ray photoelectron spectrum
The content of oxygen element determined by the peak of the cluster is 2-4 mol%, and the content of oxygen element determined by the peak corresponding to CO group
The molar ratio of the content of oxygen element determined by the peak of the group is 0.6-1: 1.
7. the method according to claim 6, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to the total amount of surface elements of the raw nanocarbon material determined by the X-ray photoelectron spectrum
The content of oxygen element determined by the peak of the group is 2.5-3.5 mol%, the content of oxygen element determined by the peak corresponding to C-O group and the content of oxygen element determined by the peak corresponding to C-O group
The molar ratio of the content of oxygen element determined by the peak of the group is 0.9-1: 1.
8. the method according to claim 1, wherein in the X-ray photoelectron spectrum of the raw material nanocarbon material, the content of nitrogen element determined from a peak corresponding to graphite type nitrogen is 0.2 to 0.45 mol%, and the molar ratio of the content of nitrogen element determined from a peak corresponding to graphite type nitrogen to the content of nitrogen element determined from a peak corresponding to pyrrole type nitrogen is 0.2 to 0.8: 1.
9. the method according to claim 8, wherein in the X-ray photoelectron spectroscopy of the raw material nanocarbon material, a content of nitrogen element determined from a peak corresponding to graphite type nitrogen is 0.3 to 0.4 mol%, and a molar ratio of the content of nitrogen element determined from a peak corresponding to graphite type nitrogen to the content of nitrogen element determined from a peak corresponding to pyrrole type nitrogen is 0.25 to 0.5, based on a total amount of surface elements of the raw material nanocarbon material determined from X-ray photoelectron spectroscopy: 1.
10. the method as claimed in any one of claims 1 to 9, wherein the oxidizing agent is used in an amount of 500-50000 parts by weight with respect to 100 parts by weight of the raw nanocarbon material.
11. The method as claimed in claim 10, wherein the oxidizing agent is used in an amount of 1000-30000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
12. The method as claimed in claim 11, wherein the oxidizing agent is used in an amount of 1500-20000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
13. The method as claimed in claim 12, wherein the oxidizing agent is used in an amount of 4000-10000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
14. The method as claimed in claim 13, wherein the oxidizing agent is used in an amount of 6000-9000 parts by weight with respect to 100 parts by weight of the raw nanocarbon material.
15. The method of claim 1, wherein the feedstock nanocarbon material is contacted with the oxidizing agent in the presence of ultrasound.
16. The method of claim 15, wherein the frequency of the ultrasonic waves is 25-100 kHz.
17. The method of any one of claims 1-9 and 15-16, wherein the duration of the contacting is 0.5-10 hours.
18. The method of claim 17, wherein the duration of the contacting is 1-6 hours.
19. The method of any one of claims 1-9 and 15-16, wherein the contacting is performed in water.
20. The method as claimed in claim 19, wherein the amount of water is 500-10000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
21. The method as claimed in claim 20, wherein the amount of water is 1000-8000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
22. The method as claimed in claim 21, wherein the amount of water is 3000-6000 parts by weight relative to 100 parts by weight of the raw nanocarbon material.
23. The method according to any one of claims 1 to 9 and 15 to 16, further comprising separating a solid substance from the contacted mixture and drying the solid substance to obtain the oxidation-treated nanocarbon material.
24. The method of claim 23, wherein the drying is performed at a temperature of 80-180 ℃ and the duration of the drying is 0.5-24 hours.
25. The method as claimed in claim 24, wherein the drying is carried out at a temperature of 100-140 ℃ and the duration of the drying is 1-20 hours.
26. The method of claim 25, wherein the drying is for a duration of 6-16 hours.
27. The method as claimed in any one of claims 1-9 and 15-16, wherein the calcination is carried out at a temperature of 700-.
28. The method as claimed in claim 27, wherein the calcination is carried out at a temperature of 800-.
29. The method as claimed in claim 28, wherein the firing is carried out at a temperature of 900-1100 ℃.
30. The method as claimed in claim 29, wherein the calcination is carried out at a temperature of 1000-.
31. The method of any of claims 1-9 and 15-16, wherein the duration of the roasting is 0.5-24 hours.
32. The method of claim 31, wherein the duration of the firing is 1-8 hours.
33. The method of claim 32, wherein the duration of the firing is 2-5 hours.
34. The method of any of claims 1-9 and 15-16, wherein the inert atmosphere is a nitrogen atmosphere.
35. The method according to any one of claims 1 to 9 and 15 to 16, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to that of X-ray photoelectron spectroscopy
The content of oxygen determined by the peak of the radical corresponds to
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-1: 1.
36. the method of claim 35, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to that of claim 35
The content of oxygen determined by the peak of the radical corresponds to
The molar ratio of the content of oxygen element determined by the peak of the group is 0.15-0.5: 1.
37. the method of claim 36, wherein the raw nanocarbon material has an X-ray photoelectron spectrum corresponding to that of claim 36
The content of oxygen determined by the peak of the radical corresponds to
Oxygen content determined by the spectral peaks of the radicalsThe molar ratio of the amounts is 0.18-0.35: 1.
38. the method according to any one of claims 1 to 9 and 15 to 16, wherein in the X-ray photoelectron spectrum of the raw nanocarbon material, a molar ratio of a content of nitrogen element determined from a peak corresponding to graphite-type nitrogen to a content of nitrogen element determined from a peak corresponding to pyridine-type nitrogen is 0.1 to 2: 1.
39. the method according to claim 38, wherein in the X-ray photoelectron spectrum of the raw nanocarbon material, a molar ratio of a content of nitrogen element determined from a peak corresponding to graphite-type nitrogen to a content of nitrogen element determined from a peak corresponding to pyridine-type nitrogen is from 0.2 to 1: 1.
40. the method according to claim 39, wherein in the X-ray photoelectron spectrum of the raw nanocarbon material, the molar ratio of the content of nitrogen element determined from the peak corresponding to graphitic nitrogen to the content of nitrogen element determined from the peak corresponding to pyridinium nitrogen is from 0.3 to 0.8: 1.
41. the method according to claim 40, wherein in the X-ray photoelectron spectrum of the raw nanocarbon material, the molar ratio of the content of nitrogen element determined from the peak corresponding to graphitic nitrogen to the content of nitrogen element determined from the peak corresponding to pyridinium nitrogen is from 0.4 to 0.5: 1.
42. the method according to any one of claims 1 to 9 and 15 to 16, wherein in the X-ray photoelectron spectrum of the raw nanocarbon material, a molar ratio of a content of nitrogen element determined from a peak corresponding to graphitic nitrogen to a content of nitrogen element determined from a peak corresponding to a pyridine oxidizing species is 0.1 to 5: 1.
43. the method according to claim 42, wherein in the X-ray photoelectron spectrum of the raw nanocarbon material, the molar ratio of the content of nitrogen element determined from a peak corresponding to graphitic nitrogen to the content of nitrogen element determined from a peak corresponding to a pyridine oxidizing species is 1 to 4.5: 1.
44. the method according to claim 43, wherein in the X-ray photoelectron spectrum of the raw nanocarbon material, the molar ratio of the content of nitrogen element determined from a peak corresponding to graphitic nitrogen to the content of nitrogen element determined from a peak corresponding to a pyridine oxidizing species is 2 to 4: 1.
45. the method according to claim 44, wherein in the X-ray photoelectron spectrum of the raw nanocarbon material, a molar ratio of a content of nitrogen element determined from a peak corresponding to graphitic nitrogen to a content of nitrogen element determined from a peak corresponding to a pyridine oxidizing species is 2.5 to 3.5: 1.
46. the method according to any one of claims 1 to 9 and 15 to 16, wherein the raw nanocarbon material has an X-ray photoelectron spectrum in which the content of nitrogen element determined from a peak corresponding to graphitic nitrogen and the content of nitrogen element determined from a peak corresponding to-NO are present2The molar ratio of the content of nitrogen elements determined by the peak of the group is 0.1-3: 1.
47. the method according to claim 46, wherein the raw nanocarbon material has an X-ray photoelectron spectrum in which the content of nitrogen element determined from a peak corresponding to graphitic nitrogen and the content of nitrogen element determined from a peak corresponding to-NO are present2The molar ratio of the content of nitrogen elements determined by the peak of the group is 1-3: 1.
48. the method according to claim 47, wherein the raw nanocarbon material has an X-ray photoelectron spectrum in which the content of nitrogen element determined from a peak corresponding to graphitic nitrogen and the content of nitrogen element determined from a peak corresponding to-NO are present2The molar ratio of the content of nitrogen elements determined by the peak of the group is 1.5-2.5: 1.
49. the method of claim 48The method of (1), wherein in an X-ray photoelectron spectrum of said raw material nanocarbon material, a content of nitrogen element determined from a peak corresponding to graphite-type nitrogen and a content of nitrogen element determined from a peak corresponding to-NO2The molar ratio of the content of nitrogen elements determined by the peak of the group is 1.8-2.1: 1.
50. the method of claim 1, wherein ID/IGIs 0.1-0.2.
51. The method of claim 50, wherein ID/IGIs 0.15-0.18.
52. The method of any one of claims 1-9, 15-16, and 50-51, wherein the feedstock nanocarbon material is carbon nanotubes.
53. The method of claim 52, wherein the feedstock nanocarbon material is multi-walled carbon nanotubes.
54. The method of claim 53, wherein the multi-walled carbon nanotubes have a specific surface area of 50-500m2/g。
55. The method of claim 54, wherein said multi-walled carbon nanotubes have a specific surface area of 70-300m2/g。
56. The method of claim 55, wherein the multi-walled carbon nanotubes have a specific surface area of 80-160m2/g。
57. The method of claim 53, wherein the weight loss ratio of the multi-walled carbon nanotube within the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800In the range of 0.01-0.3.
58. According to claimThe method of claim 57, wherein w500/w800In the range of 0.02-0.2.
59. The method of claim 58, wherein w500/w800In the range of 0.05-0.15.
60. The method according to claim 1, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectroscopy spectrum in which the content of oxygen element determined from a peak corresponding to a C-O group and the content of oxygen element determined from a peak corresponding to a C-O group are the same
The molar ratio of the content of oxygen element determined by the peak of the group is 1.15-3: 1.
61. the method according to claim 60, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectroscopy spectrum in which the content of oxygen element determined from a peak corresponding to a C-O group and the content of oxygen element determined from a peak corresponding to a C-O group are the same
The molar ratio of the oxygen content determined by the peak of the radical is 1.25-2.8: 1.
62. the method according to claim 1, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectroscopy spectrum corresponding to that of
The content of oxygen determined by the peak of the radical corresponds to
The molar ratio of the content of oxygen element determined by the peak of the group is 0.1-2: 1.
63. the method of claim 62, wherein,in the X-ray photoelectron spectrum of the nano carbon material containing the heteroatom, the molecular weight of the carbon material is determined by
The content of oxygen determined by the peak of the radical corresponds to
The molar ratio of the oxygen content determined by the peak of the radical is 0.2-1.5: 1.
64. the method of claim 63, wherein the heteroatom-containing nanocarbon material exhibits an X-ray photoelectron spectroscopy pattern corresponding to that of
The content of oxygen determined by the peak of the radical corresponds to
The molar ratio of the content of oxygen element determined by the peak of the group is 0.25-1.1: 1.
65. the method of claim 64, wherein the heteroatom-containing nanocarbon material exhibits an X-ray photoelectron spectroscopy spectrum corresponding to that of
The content of oxygen determined by the peak of the radical corresponds to
The molar ratio of the content of oxygen element determined by the peak of the group is 0.35-0.95: 1.
66. the method according to claim 1, wherein the heteroatom-containing nanocarbon material is one having a total amount of surface elements of the heteroatom-containing nanocarbon material determined by X-ray photoelectron spectroscopyIn the X-ray photoelectron spectrum corresponding to
The content of oxygen element determined by the peak of the radical is 0.4-1 mol%.
67. The method according to claim 66, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectroscopy spectrum corresponding to that of the total amount of surface elements of the heteroatom-containing nanocarbon material determined by X-ray photoelectron spectroscopy
The content of oxygen element determined by the peak of the radical is 0.5-1 mol%.
68. The method according to claim 1, wherein in an X-ray photoelectron spectroscopy spectrum of the heteroatom-containing nanocarbon material, a content of an oxygen element determined from a spectral peak corresponding to adsorbed water is 5 mol% or less based on a total amount of surface elements of the heteroatom-containing nanocarbon material determined from X-ray photoelectron spectroscopy.
69. The method of claim 68, wherein the content of elemental oxygen, as determined from a peak corresponding to adsorbed water, is 0.05-3 mole%.
70. The method of claim 69, wherein the elemental oxygen content as determined by the peak corresponding to adsorbed water is 0.08-1.5 mole%.
71. The method of claim 70, wherein the content of elemental oxygen, as determined by a peak corresponding to adsorbed water, is 0.3-1.2 mole%.
72. The method according to claim 71, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectroscopy spectrum in which a molar ratio of a content of nitrogen element determined from a peak corresponding to graphitic nitrogen to a content of nitrogen element determined from a peak corresponding to pyrrole nitrogen is from 1.1 to 4: 1.
73. the method of claim 72, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectroscopy spectrum wherein the molar ratio of the content of nitrogen element determined from a peak corresponding to graphitic nitrogen to the content of nitrogen element determined from a peak corresponding to pyrrole nitrogen is from 1.2 to 3.5: 1.
74. the method according to claim 1, wherein in the X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, the molar ratio of the content of nitrogen element determined from a peak corresponding to graphitic nitrogen to the content of nitrogen element determined from a peak corresponding to pyridinium nitrogen is from 0.5 to 5: 1.
75. the method according to claim 74, wherein in the X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, the molar ratio of the content of nitrogen element determined from the peak corresponding to graphitic nitrogen to the content of nitrogen element determined from the peak corresponding to pyridinium nitrogen is from 0.5 to 2: 1.
76. the method according to claim 75, wherein in the X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, the molar ratio of the content of nitrogen element determined from the peak corresponding to graphitic nitrogen to the content of nitrogen element determined from the peak corresponding to pyridinium nitrogen is from 0.7 to 1.8: 1.
77. the method according to claim 1, wherein in the X-ray photoelectron spectrum of the heteroatom-containing nanocarbon material, the molar ratio of the content of nitrogen element determined from a peak corresponding to graphitic nitrogen to the content of nitrogen element determined from a peak corresponding to a pyridine oxidizing species is 2 to 10: 1.
78. the method of claim 77, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectrum in which the molar ratio of the content of nitrogen element determined from a peak corresponding to graphitic nitrogen to the content of nitrogen element determined from a peak corresponding to a pyridine oxidizing species is from 2.2 to 9: 1.
79. the method of claim 78, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectrum in which the molar ratio of the content of nitrogen element determined from a peak corresponding to graphitic nitrogen to the content of nitrogen element determined from a peak corresponding to a pyridine oxidizing species is from 2.5 to 8: 1.
80. the method according to claim 1, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectrum in which the content of nitrogen element determined from a peak corresponding to graphitic nitrogen and the content of nitrogen element determined from a peak corresponding to-NO are present2The molar ratio of the content of nitrogen elements determined by the peak of the group is 2-10: 1.
81. the method as claimed in claim 80, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectrum in which the content of nitrogen element determined from a peak corresponding to graphitic nitrogen and the content of nitrogen element determined from a peak corresponding to-NO are present2The molar ratio of the content of nitrogen elements determined by the peak of the group is 2.5-6: 1.
82. the method as claimed in claim 81, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectrum in which the content of nitrogen element determined from a peak corresponding to graphitic nitrogen and the content of nitrogen element determined from a peak corresponding to-NO are present2The molar ratio of the content of nitrogen elements determined by the peak of the group is 3.5-5.5: 1.
83. the method according to claim 1, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectroscopy spectrum in which a content of nitrogen element determined from a peak corresponding to graphitic nitrogen is 0.55 to 1 mol% based on a total amount of surface elements of the heteroatom-containing nanocarbon material determined from X-ray photoelectron spectroscopy.
84. The method as claimed in claim 83, wherein the heteroatom-containing nanocarbon material has an X-ray photoelectron spectroscopy spectrum in which a content of nitrogen element determined from a peak corresponding to graphitic nitrogen is 0.55 to 0.95 mol% based on a total amount of surface elements of the heteroatom-containing nanocarbon material determined from X-ray photoelectron spectroscopy.
85. The method of claim 1, wherein ID/IG0.2-0.3: 1.
86. the method according to claim 1, wherein the content of the oxygen element is 0.9 to 8.5% by weight, the content of the nitrogen element is 1 to 6% by weight, the content of the hydrogen element is 0.2 to 1.5% by weight, and the content of the carbon element is 84 to 97.9% by weight, in terms of element, based on the total amount of the heteroatom-containing nanocarbon material.
87. The method according to claim 86, wherein the content of the oxygen element is 1 to 5% by weight, the content of the nitrogen element is 1.5 to 4% by weight, the content of the hydrogen element is 0.3 to 1.2% by weight, and the content of the carbon element is 89.8 to 97.2% by weight, in terms of element, based on the total amount of the heteroatom-containing nanocarbon material.
88. The method according to claim 87, wherein the content of oxygen element is 1.1-4.5 wt%, the content of nitrogen element is 1.6-3 wt%, the content of hydrogen element is 0.4-0.9 wt%, and the content of carbon element is 91.6-96.9 wt% in terms of element, based on the total amount of the heteroatom-containing nanocarbon material.
89. The method according to claim 1, wherein the heteroatom-containing nanocarbon material is a heteroatom-containing carbon nanotube.
90. The method of claim 89, wherein the heteroatom-containing nanocarbon material is a heteroatom-containing multi-walled carbon nanotube.
91. The method of claim 90, wherein the heteroatom-containing multi-walled carbon nanotubes have a specific surface area of 50-500m2/g。
92. The method of claim 91, wherein the heteroatom-containing multi-walled carbon nanotubes have a specific surface area of 70-300m2/g。
93. The method of claim 92, wherein the heteroatom-containing multi-walled carbon nanotubes have a specific surface area of 80-200m2/g。
94. The method as claimed in claim 90, wherein the heteroatom-containing multi-walled carbon nanotube has a weight loss ratio w within a temperature range of 400-800 ℃800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800In the range of 0.01-0.3.
95. The method of claim 94, wherein w500/w800In the range of 0.02-0.2.
96. The method of claim 95, wherein w500/w800In the range of 0.05-0.15.
97. A heteroatom-containing nanocarbon material prepared by the method of any one of claims 1 to 96.
98. Use of the heteroatom-containing nanocarbon material of claim 97 as a catalyst for oxidative dehydrogenation of hydrocarbons.
99. The use of claim 98, wherein the hydrocarbon is an alkane.
100. The use of claim 99, wherein the hydrocarbon is C2-C12Of (a) an alkane.
101. The use of claim 100, wherein the hydrocarbon is n-butane.
102. A process for the dehydrogenation of a hydrocarbon comprising contacting the hydrocarbon with the heteroatom-containing nanocarbon material of claim 97 under hydrocarbon oxidative dehydrogenation reaction conditions.
103. The method of claim 102, wherein the hydrocarbon is an alkane.
104. The method of claim 103, wherein the hydrocarbon is C2-C12Of (a) an alkane.
105. The method of claim 104, wherein the hydrocarbon is n-butane.
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