CN106925327B - One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method - Google Patents

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

Info

Publication number
CN106925327B
CN106925327B CN201511032434.0A CN201511032434A CN106925327B CN 106925327 B CN106925327 B CN 106925327B CN 201511032434 A CN201511032434 A CN 201511032434A CN 106925327 B CN106925327 B CN 106925327B
Authority
CN
China
Prior art keywords
nano
carbon material
weight
range
metallic atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201511032434.0A
Other languages
Chinese (zh)
Other versions
CN106925327A (en
Inventor
史春风
于鹏
荣峻峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201511032434.0A priority Critical patent/CN106925327B/en
Publication of CN106925327A publication Critical patent/CN106925327A/en
Application granted granted Critical
Publication of CN106925327B publication Critical patent/CN106925327B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a kind of nano-carbon material containing metallic atom and preparation method and application, the nano-carbon material contains the O element of 1-10 weight %, the N element of 0.2-5 weight % and the metallic element selected from Group IA and HA of 0.1-10 weight %, in XPS, the content of the O element determined by the peak within the scope of 529.5-530.8eV is 0.02-0.3 weight %, the ratio of the amount of the O element determined by the peak of 531.0-532.5eV and the amount of the O element determined by the peak of 532.6-533.5eV is 0.8-2.5, the ratio of the total amount of the amount and N element of the N element determined by the peak within the scope of 398.5-400.1eV is 0.7-1.The hydrocarbon dehydrogenation reaction method of the nano-carbon material containing metallic atom as catalyst is used the present invention also provides a kind of.The nano-carbon material containing metallic atom shows good catalytic performance in the dehydrogenation reaction of hydrocarbons, can significantly improve selectivity of product, while can also obtain higher feed stock conversion.

Description

One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon Dehydrogenation reaction method
Technical field
The present invention relates to a kind of nano-carbon materials containing metallic atom, and the invention further relates to a kind of nano carbon materials containing metallic atom The preparation method of material and the nano-carbon material containing metallic atom prepared by this method, the present invention further relates to a kind of pass through will be above-mentioned Nano-carbon material containing metallic atom is roasted and the nano-carbon material containing metallic atom for preparing, and the invention further relates to bases Application and a kind of hydrocarbon dehydrogenation reaction side of the nano-carbon material containing metallic atom of the invention as the catalyst of hydrocarbon dehydrogenation reaction Method.
Background technique
The dehydrogenation reaction of hydrocarbons is a kind of important reaction type, such as most of low-carbon olefine is to pass through low-carbon The dehydrogenation reaction of alkane and obtain.Whether dehydrogenation reaction participates in be divided into direct dehydrogenation reaction (that is, oxygen according to oxygen Gas is not involved in) and oxidative dehydrogenation (that is, oxygen participation) two classes.
A plurality of types of nano-carbon materials have been demonstrated equal to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation With catalytic effect, its catalytic activity can then be improved by introducing oxygen atom and/or nitrogen-atoms in nano-carbon material.
Oxygen atom is introduced in nano-carbon material, can form hydroxyl, carbonyl, carboxyl, ester group on nano-carbon material surface With the oxygen-containing functional groups such as acid anhydrides.
Oxygen atom can be introduced in nano-carbon material by carrying out oxidation processes realization to nano-carbon material, to increase The content of oxygen-containing functional group in nano-carbon material.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or it is strong Oxidizing solution (such as H2O2、KMnO4) in carry out back flow reaction, can also be assisted while back flow reaction carry out microwave heating Or sonic oscillation, to enhance the effect of oxidation reaction.It can but carry out back flow reaction in strong acid and/or strong oxidizing solution Can have an adverse effect to the skeleton structure of nano-carbon material, or even destroy the skeleton structure of nano-carbon material.Such as: it will receive Rice carbon material carries out back flow reaction in nitric acid, although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, Nano-carbon material is easily caused to be cut off and/or obviously increase the defects of graphite network structure position, to reduce nano carbon material The performance of material, such as thermal stability.In addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, to introduce oxygen original The introduction volume of the period of the day from 11 p.m. to 1 a.m, oxygen atom is high to the dependence of operation condition, and fluctuation range is wider.
When introducing nitrogen-atoms in nano-carbon material, according to nitrogen-atoms, locating chemical environment is not in nano-carbon material Together, nitrogen-atoms is usually divided into chemical nitrogen and structure nitrogen.Chemical nitrogen mainly appears in material in the form of surface functional group Surface, such as amino or nitrosyl radical surface nitrogen-containing functional group.Structure nitrogen refer to skeleton structure into nano-carbon material with The nitrogen-atoms of carbon atom bonding.Structure nitrogen mainly include graphite mould nitrogen (that is,), pyridine type nitrogen (that is,) and Pyrroles's type nitrogen (that is,).Graphite mould nitrogen directly replaces the carbon atom in graphite lattice, forms saturation nitrogen-atoms；Pyridine type nitrogen It is unsaturated nitrogen atom with pyrroles's type nitrogen, while replacing carbon atom, often will cause the missing for closing on carbon atom, form defect Position.
Can by introduced in nano-carbon material synthesis process nitrogenous functional atmosphere (such as ammonia, nitrogen, urea, Melamine), nitrogen is introduced into nano carbon material simultaneously in the synthesis process of nano-carbon material using high temperature and/or high pressure In the skeleton structure of material and/or surface；It can also be by the way that nano-carbon material to be placed in nitrogenous functional atmosphere (such as ammonia, nitrogen Gas, urea, melamine) in, nitrogen is introduced into the surface of nano-carbon material using high temperature and/or high pressure.High temperature and/or For high pressure although can form structure nitrogen in nano-carbon material, the type of nitrogen containing species depends on reaction condition, not easily-controllable System；Also, the different types of nitrogen containing species so generated are unevenly distributed on the surface of nano-carbon material, lead to nitrogenous nanometer The performance of carbon material is unstable.It then can also be reacted with amine, by the way that nano-carbon material is carried out oxidation processes thus in nanometer Carbon material surface introduces nitrogen-atoms, and the nitrogen-atoms so introduced is essentially chemical nitrogen.
Although the research of doping vario-property and its catalytic performance in relation to nano-carbon material achieves many progress, for Some of which basic problem is not built consensus yet, is still needed to doping vario-property nano-carbon material and preparation method thereof and catalysis Performance is furtherd investigate.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of nano-carbon material containing metallic atom, using this method Metallic atom can not only be introduced on nano-carbon material surface, and can steadily improve heteroatomic content in nano-carbon material, The structure of nano-carbon material itself is influenced simultaneously little.It is another object of the present invention to provide one kind to receive containing metallic atom Rice carbon material when this contains dehydrogenation reaction of the metallic atom nano-carbon material for hydrocarbons, can obtain higher raw material conversion Rate and selectivity of product.Another object of the present invention is to provide a kind of hydrocarbon dehydrogenation reaction method, this method can obtain higher Feed stock conversion and selectivity of product.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material contains C element, O element, N element and at least one metallic element, the metallic element and is selected from group ia Metallic element and group iia metallic element, on the basis of the total amount of the nano-carbon material containing metallic atom and based on the element, O member The content of element is 1-10 weight %, and the content of N element is 0.2-5 weight %, and the total amount of the metallic element is 0.1-10 weight % is measured, the content of C element is 75-98.7 weight %；
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron spectroscopy is IO t, by The content for the O element that peak in x-ray photoelectron spectroscopy within the scope of 529.5-530.8eV determines is IO m, IO m/IO tIn 0.02- In the range of 0.3；This contains in metallic atom nano-carbon material, by within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy The amount for the O element that peak determines is IO c, the O element that is determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy Amount is IO e, IO c/IO eIn the range of 0.8-2.5；This contains in metallic atom nano-carbon material, is determined by x-ray photoelectron spectroscopy The total amount of N element in the nano-carbon material containing metallic atom is IN t, by 398.5-400.1eV model in x-ray photoelectron spectroscopy The amount for the N element that peak in enclosing determines is IN c, IN c/IN tIn the range of 0.7-1.
According to the second aspect of the invention, the present invention provides a kind of preparation sides of nano-carbon material containing metallic atom Method, this method include that one kind is dispersed with to raw material nano carbon material, at least one nitrogenous compound and at least one metallization The aqueous dispersions for closing object are reacted in closed container, and the nitrogenous compound is selected from NH3, hydrazine and urea, the metallization The metallic element in object is closed in group ia metal element and group iia metallic element, reaction process, the aqueous dispersions Temperature is maintained in the range of 60-300 DEG C.
According to the third aspect of the present invention, the present invention provides a kind of method systems by the second aspect according to the present invention Standby nano-carbon material containing metallic atom.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material be by the nano-carbon material containing metallic atom in terms of first aspect according to the present invention or third into Prepared by row roasting.
According to the fifth aspect of the present invention, receiving containing metallic atom the present invention provides first aspect according to the present invention Rice carbon material, the according to the present invention nano-carbon material containing metallic atom of third aspect or according to the present invention the 4th aspect Nano-carbon material containing metallic atom as hydrocarbon dehydrogenation reaction catalyst application.
According to the sixth aspect of the invention, the present invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, is deposited Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with first aspect according to the present invention containing metal Atom nano-carbon material, the according to the present invention nano-carbon material containing metallic atom in terms of third or according to the present invention the 4th The nano-carbon material containing metallic atom of a aspect contacts.
The preparation method of the nano-carbon material according to the present invention containing metallic atom steadily can not only regulate and control and/or improve Metallic atom and heteroatomic content in nano-carbon material, at the same it is small on the influence of the structure of nano-carbon material itself, and preparation contains Metallic atom nano-carbon material has stable performance.
Nano-carbon material containing metallic atom according to the present invention shows good urge in the dehydrogenation reaction of hydrocarbons Change performance, feed stock conversion and selectivity of product can be significantly improved.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing metallic atom prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo for the raw material nano carbon material that embodiment 1 uses.
Specific embodiment
In the present invention, nano-carbon material refers to that dispersed phase scale at least one dimension is less than the carbon material of 100nm.
According to the first aspect of the invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material contains C element, O element, N element and at least one metallic element.In the present invention, "at least one" table Show one or more.
Nano-carbon material containing metallic atom according to the present invention, the metallic element are selected from group ia metal element and the Group IIA metal element, specific example can include but is not limited to one of lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium or two Kind or more.Preferably, the metallic element is one or more of sodium, potassium, magnesium, calcium and barium, this is being contained gold in this way When belonging to catalyst of the atom nano-carbon material as hydrocarbon dehydrogenation reaction, better catalytic performance can be obtained.
Nano-carbon material containing metallic atom according to the present invention, on the basis of the total amount of the nano-carbon material containing metallic atom And based on the element, the content of O element be 1-10 weight %, preferably 1.2-8 weight %, more preferably 1.3-7.5 weight %, into One step is preferably 2-6 weight %；The content of N element is 0.2-5 weight %, preferably 0.5-4.5 weight %, more preferably 0.8- 4 weight %, further preferably 1-3.5 weight %；The total amount of metallic element is 0.1-10 weight %, preferably 0.2-8 weight Measure %, more preferably 0.5-5 weight %, further preferably 2.5-4 weight %；The content of C element is 75-98.7 weight %, Preferably 79.5-98.1 weight %, more preferably 83.5-97.4 weight %, further preferably 86.5-94.5 weight %.Its In, the content of each element is measured using X-ray photoelectron spectroscopy.Sample before testing 150 DEG C at a temperature of in helium gas It is 3 hours dry in atmosphere.
In the present invention, X-ray photoelectron spectroscopic analysis is in Thermo Scientific company equipped with Thermo It is tested on the ESCALab250 type x-ray photoelectron spectroscopy of Avantage V5.926 software, excitaton source is monochromatization Al K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, base vacuum when analysis test It is 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage software Upper carry out data processing carries out quantitative analysis using sensitivity factor method in analysis module.
Nano-carbon material containing metallic atom according to the present invention, the oxygen element determined by x-ray photoelectron spectroscopy always contain Amount is IO t, the content of the O element determined by the peak within the scope of 529.5-530.8eV in x-ray photoelectron spectroscopy is IO m, IO m/IO t It is further excellent more preferably in the range of 0.06-0.2 preferably in the range of 0.05-0.25 in the range of 0.02-0.3 It is selected in the range of 0.09-0.18.Nano-carbon material containing metallic atom according to the present invention, by x-ray photoelectron spectroscopy The content for the O element that peak within the scope of 531.0-533.5eV determines is IO nm, IO nm/IO tIn the range of 0.7-0.98, preferably exist In the range of 0.75-0.95, more preferably in the range of 0.8-0.94, further preferably in the range of 0.82-0.91.This hair In bright, when indicating numberical range, " ×-× in the range of " it include two binary values.
In the present invention, the area of the O1s spectral peak in x-ray photoelectron spectroscopy is denoted as AO 1, O1s spectral peak is divided into two groups The area of spectral peak (corresponding to the oxygen species being connected with metallic atom) within the scope of 529.5-530.8eV is denoted as A by peakO 2, will The area of spectral peak (corresponding to the oxygen species not being connected with metallic atom) within the scope of 531.0-533.5eV is denoted as AO 3, wherein IO m/IO t=AO 2/AO 1, IO nm/IO t=AO 3/AO 1。
Nano-carbon material containing metallic atom according to the present invention, by 531.0-532.5eV range in x-ray photoelectron spectroscopy The amount for the O element (that is, C=O) that interior peak determines is IO c, by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy The amount of determining O element (that is, C-O) is IO e, IO c/IO eIn the range of 0.8-2.5, preferably in the range of 1-2, more preferably In the range of 1.2-1.7.It is in the present invention, the spectral peak in x-ray photoelectron spectroscopy within the scope of 531.0-533.5eV is (right The oxygen species that Ying Yu is not connected with metallic atom) it is further separated into two groups of peaks, i.e., the spectral peak within the scope of 531.0-532.5eV (corresponding to C=O species) and the spectral peak (corresponding to C-O species) within the scope of 532.6-533.5eV, will be in 531.0- The area of spectral peak within the scope of 532.5eV is denoted as AO 4, the area of the spectral peak within the scope of 532.6-533.5eV is denoted as AO 5, IO c/IO e=AO 4/AO 5。
Nano-carbon material containing metallic atom according to the present invention, in the nano-carbon material containing metallic atom by X-ray light It is true by the peak within the scope of 284.7-284.9eV in x-ray photoelectron spectroscopy on the basis of the total amount for the C element that electron spectrum determines The content of fixed C element (that is, graphite mould carbon) can be 60-98 weight %, preferably 65-95 weight %, more preferably 70-92 Weight %, further preferably 80-92 weight %；It is determined by the peak within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy C element total content can be 2-40 weight %, preferably 5-35 weight %, more preferably 8-30 weight %, further it is excellent It is selected as 8-20 weight %.In the present invention, by the area A of the C1s spectral peak in x-ray photoelectron spectroscopyC 1Determine the total amount of C element, C1s spectral peak in x-ray photoelectron spectroscopy is divided into two groups of peaks, i.e., the spectral peak within the scope of 284.7-284.9eV (corresponds to stone Black type carbon species) and spectral peak (correspond to non-graphite type carbon species) within the scope of 286.0-288.8eV, it will be in 284.7- The area of spectral peak within the scope of 284.9eV is denoted as AC 2, the area of the spectral peak within the scope of 286.0-288.8eV is denoted as AC 3, by Content=the A for the C element that peak in x-ray photoelectron spectroscopy within the scope of 284.7-284.9eV determinesC 2/AC 1, by X-ray photoelectricity Total content=the A for the C element that peak in sub- power spectrum within the scope of 286.0-288.8eV determinesC 3/AC 1。
Nano-carbon material containing metallic atom according to the present invention, this contains in metallic atom nano-carbon material, by X-ray photoelectricity The amount for the C element that peak in sub- power spectrum within the scope of 288.6-288.8eV determines is IC c, by 286.0- in x-ray photoelectron spectroscopy The amount for the C element that peak within the scope of 286.2eV determines is IC e, IC c/IC eIn the range of 0.5-2, preferably in the model of 0.5-1.5 In enclosing, more preferably in the range of 0.7-1.In the present invention, by x-ray photoelectron spectroscopy within the scope of 286.0-288.8eV Spectral peak (correspond to agraphitic carbon species) be further divided into two groups of peaks, i.e., the spectral peak within the scope of 286.0-286.2eV is (right Should be in hydroxyl and ether type carbon species) and within the scope of 288.6-288.8eV spectral peak (correspond to carboxyl, acid anhydride and ester type carbon object Kind), the area of the spectral peak within the scope of 286.0-286.2eV is denoted as AC 4, by the spectral peak within the scope of 288.6-288.8eV Area is denoted as AC 5, IC c/IC e=AC 5/AC 4。
Nano-carbon material containing metallic atom according to the present invention determines that this contains metallic atom and receives by x-ray photoelectron spectroscopy The total amount of N element in rice carbon material is IN t, the N that is determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy The amount of element is IN c, IN c/IN tIn the range of 0.7-1, preferably in the range of 0.8-1, more preferably in the range of 0.9-0.96 It is interior.
Nano-carbon material containing metallic atom according to the present invention, by 400.6-401.5eV range in x-ray photoelectron spectroscopy Content is lower or even is free of for the N element (that is, graphite mould nitrogen) that interior peak determines.Generally, according to the present invention to contain metallic atom In nano-carbon material, the amount of the N element determined by the peak within the scope of 400.6-401.5eV in x-ray photoelectron spectroscopy is IN g, IN g/IN tFor not higher than 0.3, generally in the range of 0-0.2, preferably in the range of 0.04-0.1.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peak in x-ray photoelectron spectroscopyN 1, by X-ray N1s spectral peak in photoelectron spectroscopy is divided into two groups of peaks, i.e., the spectral peak within the scope of 400.6-401.5eV (corresponds to graphite mould nitrogen Species) and 398.5-400.1eV within the scope of spectral peak (nitrogen species in addition to graphite mould nitrogen), will be in 400.6-401.5eV model The area of spectral peak in enclosing is denoted as AN 2, the area of the spectral peak within the scope of 398.5-400.1eV is denoted as AN 3, IN c/IN t=AN 3/ AN 1, IN g/IN t=AN 2/AN 1, when obtained ratio is lower than 0.01, it is believed that be free of such species, and containing such species Amount is denoted as 0.
In the present invention, position combination as corresponding to the summit at the peak at each peak be can determine that, range determines by mentioned earlier Peak refer to combination corresponding to summit can peak within that range, in the range may include a peak, also can wrap Include more than two peaks.Such as: the peak within the scope of 398.5-400.1eV refers to that combination corresponding to summit can be in 398.5- Whole peaks in the range of 400.1eV.
Nano-carbon material containing metallic atom according to the present invention can exist with common various forms, be specifically as follows but It is not limited to carbon nanotube containing metallic atom, graphene containing metallic atom, thin layer graphite containing metallic atom, nano-sized carbon containing metallic atom One of particle, carbon nano-fiber containing metallic atom, Nano diamond containing metallic atom and fullerene containing metallic atom or two Kind or more combination.The carbon nanotube containing metallic atom can be single-walled carbon nanotube containing metallic atom, contain metallic atom The combination of one or more of double-walled carbon nano-tube and multi-walled carbon nanotube containing metallic atom.It is according to the present invention to contain gold Belong to atom nano-carbon material, preferably multi-walled carbon nanotube containing metallic atom.
Nano-carbon material containing metallic atom according to the present invention, it is preferable that the multi-walled carbon nanotube containing metallic atom Specific surface area is 50-500m2/ g can be further improved the catalytic performance of the nano-carbon material containing metallic atom, especially in this way The catalytic performance of catalyst as hydrocarbons dehydrogenation reaction.It is highly preferred that this contains the ratio of metallic atom multi-walled carbon nanotube Surface area is 80-300m2/g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nanotube is 90-280m2/ g.It is further preferred that the specific surface area for containing metallic atom multi-walled carbon nanotube is 100-200m2/g.In the present invention, institute Specific surface area is stated to be measured by nitrogen adsorption BET method.
Nano-carbon material containing metallic atom according to the present invention, the multi-walled carbon nanotube containing metallic atom is in 400-800 DEG C temperature range in weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that In the range of 0.01-0.5, better catalytic effect, especially urging as hydrocarbons dehydrogenation reaction can be obtained in this way When agent, preferably catalysis reaction effect can be obtained.It is highly preferred that w500/w800In the range of 0.02-0.4.Further preferably Ground, w500/w800In the range of 0.05-0.25.It is further preferred that w500/w800In the range of 0.06-0.15.This hair In bright, w800=W800- W400, w500=W500- W400, W400For in 400 DEG C of the at a temperature of mass loss rate that measures, W800For The mass loss rate measured at a temperature of 800 DEG C, W500For in 500 DEG C of the at a temperature of mass loss rate that measures；The weight-loss ratio It is measured in air atmosphere using thermogravimetric analyzer, test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample is being surveyed It is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before examination.
In a preferred embodiment of the invention, the nano-carbon material containing metallic atom preferably contains metal original Sub- multi-walled carbon nanotube, which is 50-500m2/ g, preferably 80-300m2/ G, more preferably 90-280m2/ g, further preferably 100-200m2/g；Also, w500/w800It is excellent in the range of 0.01-0.5 It is selected in the range of 0.02-0.4, more preferably in the range of 0.05-0.25, further preferably in the range of 0.06-0.15.
Nano-carbon material containing metallic atom according to the present invention, for oxygen atom and nitrogen-atoms outside it is other nonmetallic miscellaneous Atom, such as sulphur atom and phosphorus atoms, content can be customary amount.Generally, nanometer containing metallic atom according to the present invention In carbon material, the total amount of other nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) outside oxygen atom and nitrogen-atoms can be 0.5 weight % hereinafter, preferably 0.2 weight % hereinafter, more preferably 0.1 weight % hereinafter, further preferably 0.05 weight Measure % or less.Nano-carbon material containing metallic atom according to the present invention can also contain other metals in addition to aforesaid metal elements Atom, other metallic atoms for example can be for from the catalyst used when preparing nano-carbon material.Other gold The content for belonging to atom is generally 2.5 weight % hereinafter, preferably 2 weight % are hereinafter, further preferably 1 weight % is hereinafter, more Further preferably 0.5 weight % is hereinafter, particularly preferably 0.2 weight % or less.
According to the second aspect of the invention, the present invention provides a kind of preparation sides of nano-carbon material containing metallic atom Method, this method include that one kind is dispersed with to raw material nano carbon material, at least one nitrogenous compound and at least one metallization The aqueous dispersions for closing object are reacted in closed container.
The nitrogenous compound is selected from NH3, hydrazine and urea.
Metallic element in the metallic compound is selected from group ia metal element and group iia metallic element, specific Example can include but is not limited to lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, the metallic element be selected from sodium, potassium, magnesium, Calcium and barium can obtain more preferable in this way when the nano-carbon material containing metallic atom that will be prepared is used as the catalyst of hydrocarbon dehydrogenation reaction Catalytic performance.
Preferably, the metallic compound is selected from the hydroxide containing metallic element and the alkalinity containing the metallic element Salt.It is highly preferred that the metallic compound is selected from the hydroxide containing metallic element, the carbonate containing the metallic element and contains The bicarbonate of the metallic element.The specific example of the metallic compound can include but is not limited to: lithium hydroxide, hydrogen-oxygen Change sodium, potassium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, carbonic acid One or more of calcium, barium carbonate, sodium bicarbonate, calcium bicarbonate, saleratus and barium bicarbonate.From further increasing The angle of catalytic activity of the nano-carbon material containing metallic atom finally prepared in hydrocarbon dehydrogenation reaction is set out, the metal compound Object is preferably sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, carbon One or more of sour barium, sodium bicarbonate, calcium bicarbonate, saleratus and barium bicarbonate.
According to the method for the present invention, the dosage of the nitrogenous compound and the metallic compound can be according to it is contemplated that former The content and type of the nitrogen, oxygen element and the metallic element that introduce in material nano-carbon material are selected.Finally making Standby nano-carbon material containing metallic atom is when being used as the catalyst of hydrocarbon dehydrogenation reaction, it is preferable that raw material nano carbon material: nitrogenous Compound: the weight ratio of metallic compound is in the range of 1:0.01-20:0.01-20, the nanometer containing metallic atom that thus prepares Carbon material can obtain the catalysis reaction effect further increased when being used as the catalyst of hydrocarbon dehydrogenation reaction.It is highly preferred that raw material Nano-carbon material: nitrogenous compound: the weight ratio of metallic compound is in the range of 1:0.02-10:0.02-15.It is further excellent Selection of land, raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in the range of 1:0.05-5:0.05-12. It is further preferred that raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in 1:0.05-2.5:0.1- In the range of 10.It is particularly preferred that raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in 1:0.05-1: In the range of 0.5-5.
According to the method for the present invention, the molar ratio of the nitrogenous compound and the metallic compound can be in 1:0.2-50 In the range of.Preferably, the molar ratio of the nitrogenous compound and the metallic compound is in the range of 1:0.3-30.It is more excellent For the molar ratio of selection of land, the nitrogenous compound and the metallic compound in the range of 1:0.6-6, what is thus prepared contains metal Atom nano-carbon material has more excellent catalytic activity when being used as the catalyst of hydrocarbon dehydrogenation reaction.
Method according to the invention it is possible to be selected according to dosage of the amount of raw material nano carbon material to water.Preferably, Raw material nano carbon material: H2The weight ratio of O is in the range of 1:2-500, when within the scope of the dosage of water being in this, nano-sized carbon The structural form retentivity of material during processing is more preferable, such as: for carbon nanotube, during processing substantially not It is cut off.It is highly preferred that raw material nano carbon material: H2The weight ratio of O is in the range of 1:5-250.It is further preferred that former Expect nano-carbon material: H2The weight ratio of O is in the range of 1:20-200.It is further preferred that raw material nano carbon material: H2O's Weight ratio is in the range of 1:50-160.
According to the method for the present invention, in a preferred embodiment, the nitrogenous compound is ammonia, the metallization The metallic element closed in object is selected from group iia metallic element, is more preferably selected from magnesium, calcium and barium, the metallic compound is preferably Carbonate and/or bicarbonate, the nano-carbon material containing metallic atom thus prepared is when being used as the catalyst of hydrocarbon dehydrogenation reaction Preferably catalysis reaction effect can be obtained.In the preferred embodiment, raw material nano carbon material: nitrogenous compound: metal The weight ratio of compound is preferably in the range of 1:0.02-10:0.05-8, more preferably in the range of 1:0.05-5:0.1-6, Further preferably in the range of 1:0.05-0.5:1-5, still more preferably in the range of 1:0.05-0.2:4-5.At this In preferred embodiment, nitrogenous compound: the molar ratio of metallic compound preferably in the range of 1:0.5-8, more preferably exists In the range of 1:2-7, further preferably in the range of 1:2.5-6.In the preferred embodiment, raw material nano carbon materials Material: H2The weight ratio of O is preferably in the range of 1:5-200, more preferably in the range of 1:50-150, further preferably 1: In the range of 100-120.
According to the method for the present invention, in another preferred embodiment, the nitrogenous compound is hydrazine, the metal Metallic element in compound is selected from group iia metallic element, is preferably selected from magnesium, calcium and barium, the metallic compound is preferably Hydroxide, the nano-carbon material containing metallic atom thus prepared can obtain preferably when being used as the catalyst of hydrocarbon dehydrogenation reaction It is catalyzed reaction effect.Preferably, raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in 1:0.02-5: In the range of 0.02-15.It is highly preferred that raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in 1:0.1- In the range of 2:0.1-10.It is further preferred that raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound exists In the range of 1:0.1-1:0.5-4.In the preferred embodiment, nitrogenous compound: the molar ratio of metallic compound is preferred In the range of 1:0.1-5, more preferably in the range of 1:0.5-2.5.In the preferred embodiment, raw material nano carbon materials Material: H2The weight ratio of O is preferably in the range of 1:10-200, more preferably in the range of 1:50-150.
According to the method for the present invention, in another preferred embodiment, the nitrogenous compound is urea, the gold The metallic element belonged in compound is selected from group ia metal element, is preferably selected from lithium, sodium and potassium, the metallic compound is preferably Carbonate, the nano-carbon material containing metallic atom thus prepared can be obtained when being used as the catalyst of hydrocarbon dehydrogenation reaction and preferably be urged Change reaction effect.Preferably, raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in 1:0.02-5: In the range of 0.05-5.It is highly preferred that raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is in 1:0.2- In the range of 2:0.1-3.It is further preferred that raw material nano carbon material: nitrogenous compound: the weight ratio of metallic compound is 1: In the range of 0.2-1:1-2.In the preferred embodiment, nitrogenous compound: the molar ratio of metallic compound is preferably 1: In the range of 0.2-10, more preferably in the range of 1:0.7-6.In the preferred embodiment, raw material nano carbon material: H2The weight ratio of O is preferably in the range of 1:5-200, more preferably in the range of 1:50-180, further preferably in 1:100- In the range of 160.
According to the method for the present invention, the condition of the reaction is to be enough to improve oxygen atom, nitrogen in raw material nano carbon material Subject to the content of atom and metallic atom.Preferably, in reaction process, range of the temperature of the aqueous dispersions at 60-300 DEG C It is interior.When the temperature of the aqueous dispersions is within above range, can not only effectively improve in raw material nano carbon material Oxygen atom, nitrogen-atoms and metal atom content, and the structural form of raw material nano carbon material will not be generated and be significantly affected.More Preferably, in reaction process, the temperature of the aqueous dispersions is in the range of 100-260 DEG C.It is further preferred that reaction process In, the temperature of the aqueous dispersions is in the range of 120-180 DEG C.
According to the method for the present invention, the duration of the reaction can be selected according to the temperature of reaction, with can It is introduced in raw material nano carbon material subject to enough oxygen atoms, nitrogen-atoms and metallic atom.Generally, the reaction continues Time can be in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably in 12-48 hours ranges It is interior, further preferably in the range of 24-36 hours.
Method according to the invention it is possible to form the aqueous dispersions using common various methods, such as can incite somebody to action Raw material nano carbon material is dispersed in water (preferably deionized water), and the nitrogenous compound and the metal compound is then added Object is uniformly mixed, to obtain the aqueous dispersions.In order to further increase the dispersion effect of raw material nano carbon material, contract simultaneously The time of short dispersion, raw material nano carbon material can be dispersed in containing the nitrogenous compound using the method for sonic oscillation and In the water of the metallic compound.The condition of the sonic oscillation can be conventional selection, generally, the frequency of the sonic oscillation Rate can be 10-150kHz, preferably 10-90kHz；The duration of the sonic oscillation can be 0.1-6 hours, preferably 0.5-2 hours.According to the method for the present invention, the nitrogenous compound and the metallic compound respectively can be with according to specific type The form of dispersion liquid (preferably aqueous dispersions) provides, and can also be not particularly limited by respectively being provided in the form of pure material.
According to the method for the present invention, the content of oxygen element and nitrogen does not limit especially in the raw material nano carbon material It is fixed, it can be conventional selection.Generally, in the raw material nano carbon material content of oxygen element be not higher than 1.5 weight %, it is excellent It is selected as further preferably being not higher than 0.3 weight % not higher than 1.2 weight %, more preferably not above 0.5 weight %；Nitrogen member The content of element is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably not above 0.1 weight %, into one Step is preferably not higher than 0.05 weight %, still more preferably for not higher than 0.02 weight %.According to the method for the present invention, described The total amount of oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms in raw material nano carbon material It (based on the element) can be customary amount.Generally, remaining in the raw material nano carbon material in addition to oxygen element and nitrogen The total amount (based on the element) of nonmetallic heteroatoms is not higher than 0.5 weight %, preferably not higher than 0.2 weight %, more preferably Not higher than 0.1 weight %, it is further preferably not higher than 0.05 weight %.According to the method for the present invention, the raw material nano carbon Material may contain some metallic elements according to the difference in source, such as from using when preparing raw material nano carbon material Metallic atom in catalyst.The content (based on the element) of metallic atom is generally 2.5 weights in the raw material nano carbon material Measure % hereinafter, preferably 1.8 weight % hereinafter, further preferably 0.5 weight % hereinafter, still more preferably be 0.1 weight Measure % or less.
According to the method for the present invention, raw material nano carbon material can be carried out pre- before use using method commonly used in the art Processing (as washed), to remove some impurity of raw material nano carbon material surface；It can also directly be used without pretreatment. In embodiment disclosed by the invention, raw material nano carbon material is not pre-processed using preceding.
Method according to the invention it is possible to handle the nano-carbon material of various existing forms, received to improve this Oxygen atom, nitrogen-atoms and metal element content in rice carbon material.The raw material nano carbon material can be but be not limited to carbon and receive One or both of mitron, graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene with On combination.The carbon nanotube can for one of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube or Two or more combinations.Preferably, the raw material nano carbon material is carbon nanotube, more preferably multi-walled carbon nanotube.
According to the method for the present invention, in a preferred embodiment, the raw material nano carbon material is that multi wall carbon is received Mitron, the specific surface area of the multi-walled carbon nanotube can be 50-500m2/ g, preferably 80-300m2/ g, more preferably 100- 260m2/ g, further preferably 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nanotube, temperature of the multi-walled carbon nanotube at 400-800 DEG C The weight-loss ratio spent in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It can be in 0.01- In the range of 0.5, preferably in the range of 0.02-0.4, more preferably in the range of 0.05-0.35, further preferably exist In the range of 0.05-0.15.
In a kind of more preferably embodiment of the invention, the raw material nano carbon material is multi-walled carbon nanotube, The specific surface area of the multi-walled carbon nanotube is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, into One step is preferably 120-190m2/g；Weight-loss ratio of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, Weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, preferably 0.02-0.4's In range, more preferably in the range of 0.05-0.35, further preferably in the range of 0.05-0.15.
According to the method for the present invention, the reaction carries out in closed container.The reaction can self-generated pressure (that is, Do not apply pressure additionally) under carry out, can also carry out under pressure.Preferably, it is described reaction at autogenous pressures into Row.The closed container can be the common reactor for being able to achieve sealing and heating, such as autoclave.
It according to the method for the present invention, can also include solid matter being isolated from the mixture that reaction obtains, and will divide The solid matter separated out is dried, to obtain the nano-carbon material containing metallic atom.
Solid matter can be isolated from the mixture that reaction obtains using common solid-liquid separating method, such as centrifugation, Filtering and decantation one or more of combination.
The condition of the drying can be conventional selection, be can remove the volatile materials in the solid matter isolated It is quasi-.Generally, the drying can 50-200 DEG C at a temperature of carry out, preferably 80-180 DEG C at a temperature of carry out, it is more excellent It is carried out at a temperature of being selected in 120-160 DEG C.The duration of the drying can be selected according to dry temperature and mode. Generally, the duration of the drying can be 0.5-48 hours, preferably 2-24 hours, more preferably 6-12 hours.Institute Stating drying can carry out under normal pressure (that is, 1 standard atmospheric pressure), can also carry out at reduced pressure.From further increasing The angle of dry efficiency is set out, and the drying preferably carries out at reduced pressure.
According to the method for the present invention, oxygen atom, nitrogen-atoms and the metal that can be effectively improved in raw material nano carbon material are former Sub- content, while the structural form of raw material nano carbon material will not be generated and be significantly affected.
According to the third aspect of the present invention, the present invention provides one kind contains metal by prepared according to the methods of the invention Atom nano-carbon material.
According to the fourth aspect of the present invention, the present invention provides a kind of nano-carbon material containing metallic atom, this contains metal Atom nano-carbon material is by the nano-carbon material containing metallic atom of first aspect according to the present invention and according to the present invention Prepared by the nano-carbon material containing metallic atom of three aspects is roasted.
The roasting can carry out under normal conditions.Preferably, it is described roasting 250-500 DEG C at a temperature of carry out. It is highly preferred that it is described roasting 300-450 DEG C at a temperature of carry out.The duration of the roasting can be according to the temperature of roasting It is selected.Generally, the duration of the roasting can be 1-24 hours, preferably 2-12 hours.The roasting can be with It carries out, can also be carried out in the atmosphere formed by inert gas in oxygen-containing atmosphere.The oxygen-containing atmosphere can be air gas Atmosphere；It can also be the mixed atmosphere that oxygen and inert gas are mixed to form, in the mixed atmosphere, the content of oxygen can be 0.1-22 volume %.The inert gas can include but is not limited to nitrogen and/or rare gas, and the rare gas can be Argon gas and/or helium.Consider from convenience and cost angle, it is preferable that the roasting is in oxygen-containing atmosphere (such as air atmosphere) It carries out.
Nano-carbon material containing metallic atom according to the present invention is received by prepared by method of the invention containing metallic atom Rice carbon material has good catalytic performance, and higher catalytic activity is especially shown in hydrocarbons dehydrogenation reaction.
Nano-carbon material containing metallic atom according to the present invention is received by prepared by method of the invention containing metallic atom Rice carbon material can be directly used as catalyst, can also be used in the form of preformed catalyst.The preformed catalyst can contain With good grounds nano-carbon material containing metallic atom of the invention or the nano carbon material containing metallic atom prepared by method of the invention Material and binder.The binder can be selected according to the specifically used occasion of the preformed catalyst, can satisfy It subject to requirement, such as can be organic binder and/or inorganic binder.The organic binder can be common each Kind polymer-type binder, the inorganic binder can be common various heat-resistant inorganic oxides, such as aluminium oxide and/or oxygen SiClx.It is to hydrocarbon dehydrogenation reaction (such as direct dehydrogenation reaction and oxidative dehydrogenation), particularly to oxygen in the preformed catalyst When fluidized dehydrogenation reaction has the preformed catalyst of catalytic action, the binder is preferably inorganic binder.The shaped catalyst In agent, the content of the nano-carbon material containing metallic atom can be selected according to specifically used requirement, be not particularly limited, generally Ground, on the basis of the total amount of the preformed catalyst, the content of the nano-carbon material containing metallic atom can be 5-95 weight Measure %.
According to the fifth aspect of the present invention, receiving containing metallic atom the present invention provides first aspect according to the present invention Rice carbon material, nano-carbon material containing metallic atom according to the third aspect of the present invention or the 4th side according to the present invention Application of the nano-carbon material containing metallic atom in face as the catalyst of hydrocarbon dehydrogenation reaction.
Application according to the present invention, the nano-carbon material containing metallic atom are used directly for hydrocarbon dehydrogenation reaction, can also To be used for hydrocarbon dehydrogenation reaction after molding.The dehydrogenation reaction can carry out in the presence of oxygen, can not also be in the presence of oxygen It carries out.Preferably, the dehydrogenation reaction carries out in the presence of oxygen, can obtain better catalytic effect in this way.
According to the sixth aspect of the invention, the present invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, is deposited Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with first aspect according to the present invention containing metal Atom nano-carbon material, nano-carbon material containing metallic atom according to the third aspect of the present invention or according to the present invention The contact of nano-carbon material containing metallic atom of four aspects.
Hydrocarbon dehydrogenation reaction method according to the present invention, the nano-carbon material containing metallic atom are used directly for connecing with hydrocarbon Touching is used to contact with hydrocarbon after can also forming the nano-carbon material containing metallic atom.
Hydrocarbon dehydrogenation reaction method according to the present invention can carry out dehydrogenation to a plurality of types of hydrocarbon, to obtain unsaturation Hydrocarbon, such as alkene.According to the method for the present invention particularly suitable for carrying out dehydrogenation to alkane, to obtain unsaturated hydrocarbons, such as alkene.
According to the method for the present invention, the hydrocarbon is preferably alkane, such as C2-C12Alkane.Specifically, the hydrocarbon can be but Be not limited to ethane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentane, 3- methylpentane, 2,3- dimethylbutane, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- second Base pentane, 3- ethylpentane, 2,3- dimethyl pentane, 2,4- dimethyl pentane, normal octane, 2- methyl heptane, 3- methyl heptane, 4- methyl heptane, 2,3- dimethylhexane, 2,4- dimethylhexane, 2,5- dimethylhexane, 3- ethyl hexane, 2,2,3- front three Base pentane, 2,3,3- trimethylpentane, 2,4,4- trimethylpentane, 2- methyl -3- ethylpentane, n -nonane, 2- methyloctane, 3- methyloctane, 4- methyloctane, 2,3- dimethyl heptane, 2,4- dimethyl heptane, 3- ethyl heptane, 4- ethyl heptane, 2, 3,4- trimethyl cyclohexane, 2,3,5- trimethyl cyclohexane, 2,4,5- trimethyl cyclohexane, 2,2,3- trimethyl cyclohexane, 2,2,4- front three Base hexane, 2,2,5- trimethyl cyclohexane, 2,3,3- trimethyl cyclohexane, 2,4,4- trimethyl cyclohexane, 2- methyl -3- ethyl hexane, 2- methyl -4- ethyl hexane, 3- methyl -3- ethyl hexane, 3- methyl -4- ethyl hexane, 3,3- diethylpentane, 1- methyl - 2- ethyl cyclohexane, 1- methyl -3- ethyl cyclohexane, 1- methyl -4- ethyl cyclohexane, n-propyl hexamethylene, isopropyl hexamethylene Alkane, trimethyl-cyclohexane (the various isomers including trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- front threes Butylcyclohexane, 1,2,5- trimethyl-cyclohexane, 1,3,5- trimethyl-cyclohexane), n-decane, 2- methylnonane, 3- methylnonane, 4- methylnonane, 5- methylnonane, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyl octane, 4- ethyl octane, 2, 3,4- trimethylheptane, 2,3,5- trimethylheptane, 2,3,6- trimethylheptane, 2,4,5- trimethylheptane, 2,4,6- front three Base heptane, 2,2,3- trimethylheptane, 2,2,4- trimethylheptane, 2,2,5- trimethylheptane, 2,2,6- trimethylheptane, 2, 3,3- trimethylheptane, 2,4,4- trimethylheptane, 2- methyl -3- ethyl heptane, 2- methyl -4- ethyl heptane, 2- methyl -5- Ethyl heptane, 3- methyl -3- ethyl heptane, 4- methyl -3- ethyl heptane, 5- methyl -3- ethyl heptane, 4- methyl -4- ethyl Heptane, 4- propyl heptane, 3,3- diethylhexane, 3,4- diethylhexane, 2- methyl -3,3- diethylpentane, vinylbenzene, 1- In phenyl-propane, 2- phenyl-propane, 1- phenyl butane, 2- phenyl butane, 1- phenyl pentane, 2- phenyl pentane and 3- phenyl pentane A combination of one or more.It is highly preferred that the hydrocarbon be one of propane, normal butane, iso-butane and vinylbenzene or It is two or more.It is further preferred that the hydrocarbon is normal butane.
Hydrocarbon dehydrogenation reaction method according to the present invention, the reaction can carry out under conditions of there are oxygen, can also be with Under conditions of oxygen is not present.Preferably, it is carried out under conditions of there are oxygen.In method of the invention there are oxygen Under the conditions of when carrying out, the dosage of oxygen can be conventional selection.Generally, the molar ratio of hydrocarbon and oxygen can be 0.01-100: 1, preferably 0.1-10:1, more preferably 0.2-5:1, most preferably 0.5-2:1.
Hydrocarbon and oxygen can be sent into reactor by carrier gas and contain metal by hydrocarbon dehydrogenation reaction method according to the present invention Atom nano-carbon material haptoreaction.The carrier gas can for it is common at reaction conditions will not with reactant and react generation The gas that object occurs chemical interaction and will not decompose, in nitrogen, carbon dioxide, rare gas and water vapour A combination of one or more.The dosage of the carrier gas can be conventional selection.Generally, the content of carrier gas can be with 30- 99.5 volume %, preferably 50-99 volume %, more preferably 70-98 volume %.
The temperature of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be conventional selection, to be enough to send out hydrocarbon Subject to raw dehydrogenation reaction.Generally, the contact can 200-650 DEG C at a temperature of carry out, preferably in 300-600 DEG C of temperature Degree is lower to carry out, more preferably 350-550 DEG C at a temperature of carry out, further preferably 400-450 DEG C at a temperature of carry out.
Hydrocarbon dehydrogenation reaction method according to the present invention, the contact can carry out in fixed bed reactors, can also be It carries out, is not particularly limited in fluidized-bed reactor.Preferably, the contact carries out in fixed bed reactors.
The duration of hydrocarbon dehydrogenation reaction method according to the present invention, the contact can be selected according to the temperature of contact It selects, when such as described contact carries out in fixed bed reactors, holding for contact can be indicated with the volume space velocity of the gas of charging The continuous time.Generally, the volume space velocity of the gas of charging can be 0.1-10000h-1, preferably 1-6000h-1, more preferably 5-5000h-1, further preferably 10-4000h-1, such as 500-800h-1。
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, outfit of the X-ray photoelectron spectroscopic analysis in Thermo Scientific company It is tested on the ESCALab250 type x-ray photoelectron spectroscopy for having Thermo Avantage V5.926 software, excitaton source For monochromatization Al K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, analysis test When base vacuum be 6.5 × 10-10Mbar, the peak C1s (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Data processing is carried out on Avantage software, and quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is being surveyed It is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before examination.
In following embodiment and comparative example, thermogravimetric analysis carries out on TA5000 thermal analyzer, and test condition is air gas Atmosphere, heating rate are 10 DEG C/min, and temperature range is room temperature (25 DEG C) to 1000 DEG C.Sample is before testing in 150 DEG C of temperature It is 3 hours dry in helium atmosphere with the pressure of 1 normal atmosphere.Using the ASAP2000 type N of Micromertrics company, the U.S.2 Physical adsorption appearance measurement the specific area.Raw material nano carbon material is analyzed using the high-resolution-ration transmission electric-lens of FEI Co., U.S. production And the microscopic appearance of the nano-carbon material containing metallic atom.
In following embodiment and comparative example, nitrogenous compound is provided in the form of 25 weight % aqueous solutions, metallic compound It is provided in the form of solid matter.
Embodiment 1-42 is for illustrating nano-carbon material containing metallic atom and preparation method thereof of the invention.
Embodiment 1
(1) using 20g as multi-walled carbon nanotube (the specific surface area 136m of raw material nano carbon material2/ g, oxygen atom content For 0.3 weight %, nitrogen atom content is 0.02 weight %, and (phosphorus is former for remaining nonmetallic heteroatoms in addition to nitrogen-atoms and oxygen atom Son and sulphur atom) total content be 0.01 weight %, metallic atom total content be 0.1 weight %, in 400-800 DEG C of temperature range Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.12, is purchased from Chinese science Chengdu organic chemistry Co., Ltd, institute) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition It include: frequency for 14kHz, the time is 0.5 hour.Then, NH is added3And barium bicarbonate, to obtain aqueous dispersions, wherein By raw material nano carbon material: NH3: barium bicarbonate: H2The weight ratio of O is that the ratio of 1:0.05:4.25:100 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 120 DEG C of temperature Under, it reacts 36 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big Air pressure, similarly hereinafter), after 12 hours dry at a temperature of 120 DEG C, nano-carbon material containing metallic atom is obtained, this contains metallic atom and receives Composition, specific surface area and the w of rice carbon material500/w800It is listed in table 1.
Fig. 1 is the transmission electron microscope photo of the nano-carbon material containing metallic atom of preparation, and Fig. 2 is as the more of raw material The transmission electron microscope photo of wall carbon nano tube.It can be seen that the microcosmic of the nano-carbon material containing metallic atom from Fig. 1 and Fig. 2 Form is good, and it is little to show that reaction process influences the structure of nano-carbon material.
Comparative example 1
Aqueous dispersions same as Example 1 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 120 DEG C, back flow reaction 36 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 At a temperature of DEG C after drying 6 hours, nano-carbon material containing metallic atom is obtained.The group of the nano-carbon material containing metallic atom of preparation At, specific surface area and w500/w800It is listed in table 1.
Comparative example 2
Nano-carbon material is prepared using method same as Example 1, unlike, in step (1), the water dispersion of preparation Liquid is free of barium bicarbonate, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, then NH is added3To obtain aqueous dispersions, wherein press raw material nano carbon material: NH3: barium bicarbonate: H2The weight ratio of O is 1: The ratio of 0.05:0:100 feeds intake.Composition, specific surface area and the w of the nano-carbon material of preparation500/w800It is listed in table 1.
Comparative example 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, step (1) is prepared Aqueous dispersions be free of NH3, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, Then barium bicarbonate is added to obtain aqueous dispersions, wherein NH in the mole and embodiment 1 of barium bicarbonate3And bicarbonate The integral molar quantity of barium is identical, and the dosage of raw material nano carbon material and water is same as Example 1.The nanometer containing metallic atom of preparation Composition, specific surface area and the w of carbon material500/w800It is listed in table 1.
Comparative example 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, step (1) is prepared Aqueous dispersions be free of NH3, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, Then barium bicarbonate is added to obtaining aqueous dispersions, wherein the dosage of raw material nano carbon material, barium bicarbonate and water with Embodiment 1 is identical.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Comparative example 5
It will be dispersed in deionized water using the nano-carbon material containing metallic atom of method identical with comparative example 2 preparation, It is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes: that frequency is 14kHz, and the time is 0.5 hour.Then it is added Barium bicarbonate is to obtain aqueous dispersions, wherein presses raw material nano carbon material: barium bicarbonate: H2The weight ratio of O is 1:0.25: 100 ratio feeds intake.By obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 120 DEG C of temperature Under degree, react 36 hours at autogenous pressures.After reaction, it is cooled to room temperature, opens anti-to the temperature in autoclave Kettle is answered, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C At a temperature of after dry 12 hours, obtain nano-carbon material containing metallic atom, this contains the composition of metallic atom nano-carbon material, compares Surface area and w500/w800It is listed in table 1.
Embodiment 2
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), make Specific surface area for the multi-walled carbon nanotube (be purchased from Shandong great Zhan nano material Co., Ltd) of raw material nano carbon material is 251m2/ g, the weight-loss ratio in 400-800 DEG C of temperature range are w800, weight-loss ratio in 400-500 DEG C of temperature range For w500, w500/w800Be 0.33, oxygen atom content is 0.62 weight %, and nitrogen atom content is 0.01 weight %, except nitrogen-atoms and The total content of remaining nonmetallic heteroatoms (phosphorus atoms and sulphur atom) outside oxygen atom is 0.01 weight %, metallic atom total content For 0.08 weight %.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 3
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, at autogenous pressures Reaction 36 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 4
Nano-carbon material containing metallic atom is prepared using method same as Example 1, unlike, in step (1), NH3With the integral molar quantity of barium bicarbonate it is same as Example 1 under conditions of, make NH3: the molar ratio of barium bicarbonate is 1:10.Preparation The nano-carbon material containing metallic atom composition, specific surface area and w500/w800It is listed in table 1.
Embodiment 5
Using 20g as multi-walled carbon nanotube (the specific surface area 183m of raw material nano carbon material2/ g, oxygen atom content are 0.2 weight %, nitrogen atom content are 0.01 weight %, remaining nonmetallic heteroatoms (phosphorus atoms in addition to nitrogen-atoms and oxygen atom And sulphur atom) total content be 0.04 weight %, metallic atom total content be 0.03 weight %, 400-800 DEG C of humidity province Interior weight-loss ratio is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is 0.07, purchased from China Chengdu organic chemistry Co., Ltd, the academy of sciences) dispersion in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation Condition includes: that frequency is 90kHz, and the time is 2 hours.Then, NH is added3And calcium bicarbonate, so that aqueous dispersions are obtained, In, by raw material nano carbon material: NH3: calcium bicarbonate: H2The weight ratio of O is that the ratio of 1:0.2:5:120 feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 170 DEG C of temperature Under, it reacts 24 hours at autogenous pressures.After reaction, it is cooled to room temperature to the temperature in autoclave, opens reaction Reaction mixture is filtered and washed by kettle, and collects solid matter.By the solid matter being collected into normal pressure, 160 DEG C At a temperature of after dry 6 hours, obtain nano-carbon material containing metallic atom, this contains the composition of metallic atom nano-carbon material, compares table Area and w500/w80It is listed in table 1.
Embodiment 6
Nano-carbon material containing metallic atom is prepared using method same as Example 5, unlike, in step (1), make Specific surface area for the multi-walled carbon nanotube (be purchased from Shandong great Zhan nano material Co., Ltd) of raw material nano carbon material is 103m2/ g, w500/w800Be 0.23, oxygen atom content be 1.1 weight %, nitrogen atom content be 0.03 weight %, denitrogenate with outside oxygen Remaining nonmetallic heteroatoms (p and s) total content be 0.01 weight %, metallic atom total content be 1.6 weight %.Preparation The nano-carbon material containing metallic atom composition, specific surface area and w500/w800It is listed in table 1.
Embodiment 7
Nano-carbon material containing metallic atom is prepared using method same as Example 5, unlike, it, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 220 DEG C, at autogenous pressures Reaction 24 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 1.
Embodiment 8
Nano-carbon material containing metallic atom is prepared using method same as Example 5, unlike, in step (1), press Raw material nano carbon material: NH3: calcium bicarbonate: H2The weight ratio of O is that the ratio of 1:0.5:5:120 feeds intake.Preparation contains metal original Composition, specific surface area and the w of sub- nano-carbon material500/w800It is listed in table 1.
Embodiment 9
Nano-carbon material containing metallic atom is prepared using method same as Example 5, unlike, in step (1), press Raw material nano carbon material: NH3: calcium bicarbonate: H2The weight ratio of O is that the ratio of 1:0.2:1.5:120 feeds intake.Preparation contains metal Composition, specific surface area and the w of atom nano-carbon material500/w800It is listed in table 1.
Embodiment 10
Nano-carbon material containing metallic atom is prepared using method same as Example 5, unlike, in step (1), carbon The potassium hydroxide of sour hydrogen calcium equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and w500/w800It is listed in table 1.
Embodiment 11
Nano-carbon material containing metallic atom is prepared using method same as Example 5, unlike, in step (1), carbon Sour hydrogen calcium is replaced with sodium carbonate, and the mole of sodium carbonate is 0.5 times of the mole of calcium bicarbonate.Preparation is received containing metallic atom Composition, specific surface area and the w of rice carbon material500/w800It is listed in table 1.
Comparative example 6
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 11, unlike, in step (1), For preparing the aqueous solution of aqueous dispersions without NH3, it is, the multi-walled carbon nanotube as raw material nano carbon material is dispersed In deionized water, then with sodium carbonate is added, to obtain aqueous dispersions, the mole of sodium carbonate be in embodiment 11 NH3Identical with the integral molar quantity of sodium carbonate, the dosage of raw material nano carbon material and water is identical as embodiment 11.Preparation contains Composition, specific surface area and the w of metallic atom nano-carbon material500/w800It is listed in table 1.
Embodiment 12
Nano-carbon material containing metallic atom is prepared using method same as Example 5, unlike, in step (1), carbon The sodium bicarbonate of sour hydrogen calcium equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and w500/w800It is listed in table 1.
Embodiment 13
Nano-carbon material containing metallic atom is prepared using method same as Example 5, unlike, in step (1), carbon The magnesium hydroxide of sour hydrogen calcium equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area and w500/w800It is listed in table 1.
Comparative example 7
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 13, unlike, in step (1), For preparing the aqueous solution of aqueous dispersions without NH3, it is, the multi-walled carbon nanotube as raw material nano carbon material is dispersed In deionized water, magnesium hydroxide is then added, to obtain aqueous dispersions, wherein the mole and embodiment of magnesium hydroxide NH in 133Identical with the integral molar quantity of magnesium hydroxide, the dosage of raw material nano carbon material and water is identical as embodiment 13.System Composition, specific surface area and the w of the standby nano-carbon material containing metallic atom500/w800It is listed in table 1.
Embodiment 14
Nano-carbon material containing metallic atom is prepared using method same as Example 1, difference is as follows: step (1) In, in deionized water by the dispersion of raw material nano carbon material, hydrazine and magnesium hydroxide is then added, so that aqueous dispersions are obtained, In, by raw material nano carbon material: hydrazine: magnesium hydroxide: H2The weight ratio of O is that the ratio of 1:1:4:150 feeds intake；It, will in step (2) Obtained aqueous dispersions are in the autoclave with polytetrafluoroethyllining lining, at a temperature of 160 DEG C, at autogenous pressures Reaction 36 hours.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Comparative example 8
Aqueous dispersions identical with embodiment 14 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 160 DEG C, back flow reaction 36 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 At a temperature of DEG C after drying 12 hours, nano-carbon material containing metallic atom is obtained.The nano-carbon material containing metallic atom of preparation Composition, specific surface area and w500/w800It is listed in table 2.
Comparative example 9
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 14, unlike, step is matched in (1) The aqueous dispersions of system are free of hydrazine, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, Then magnesium hydroxide is added to obtain aqueous dispersions, wherein hydrazine and hydroxide in the mole and embodiment 14 of magnesium hydroxide The integral molar quantity of magnesium is identical, and the dosage of raw material nano carbon material and water is identical as embodiment 14.Preparation is received containing metallic atom Composition, specific surface area and the w of rice carbon material500/w800It is listed in table 2.
Comparative example 10
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 14, unlike, step is matched in (1) The aqueous dispersions of system are free of hydrazine, it is, in deionized water by the dispersion of the multi-walled carbon nanotube as raw material nano carbon material, Then magnesium hydroxide is added to obtaining aqueous dispersions, wherein the dosage of magnesium hydroxide, raw material nano carbon material and water with Embodiment 14 is identical.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Comparative example 11
Nano-carbon material is prepared using method identical with embodiment 14, unlike, the aqueous dispersions of step (1) preparation Without magnesium hydroxide, it is, by the multi-walled carbon nanotube as raw material nano carbon material dispersion in deionized water, then plus Enter hydrazine, to obtain aqueous dispersions, wherein the dosage of raw material nano carbon material, water and hydrazine is identical as embodiment 14.Preparation Nano-carbon material composition, specific surface area and w500/w800It is listed in table 2.
Embodiment 15
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 14, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 250 DEG C, in spontaneous pressure It is reacted 36 hours under power.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is arranged in table 2 Out.
Embodiment 16
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 14, unlike, it is received as raw material The multi-walled carbon nanotube of rice carbon material is same as Example 2.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area And w500/w800It is listed in table 2.
Embodiment 17
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 14, unlike, in step (1), Under conditions of the integral molar quantity of hydrazine and magnesium hydroxide remains unchanged, make hydrazine: the molar ratio 1:5 of magnesium hydroxide.Preparation contains gold Belong to composition, specific surface area and the w of atom nano-carbon material500/w800It is listed in table 2.
Embodiment 18
Nano-carbon material containing metallic atom is prepared using method same as Example 5, difference is as follows: step (1) In, in deionized water by the dispersion of raw material nano carbon material, hydrazine and barium hydroxide is then added, so that aqueous dispersions are obtained, In, by raw material nano carbon material: hydrazine: barium hydroxide: H2The weight ratio of O is that the ratio of 1:0.1:0.5:50 feeds intake；Step (2) In, obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 140 DEG C, certainly It is reacted 48 hours under raw pressure.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 19
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 18, unlike, in step (1), Multi-walled carbon nanotube as raw material nano carbon material is same as Example 6.The group of the nano-carbon material containing metallic atom of preparation At, specific surface area and w500/w800It is listed in table 2.
Embodiment 20
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 18, unlike, in step (1), By raw material nano carbon material: hydrazine: barium hydroxide: H2The weight ratio of O is that the ratio of 1:0.5:0.5:50 feeds intake.Preparation contains metal Composition, specific surface area and the w of atom nano-carbon material500/w800It is listed in table 2.
Embodiment 21
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 18, unlike, in step (1), By raw material nano carbon material: hydrazine: barium hydroxide: H2The weight ratio of O is that the ratio of 1:0.1:0.2:50 feeds intake.Preparation contains metal Composition, specific surface area and the w of atom nano-carbon material500/w800It is listed in table 2.
Embodiment 22
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 18, unlike, in step (2), By obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in self-generated pressure Lower reaction 48 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 23
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 18, unlike, in step (1), The calcium hydroxide of barium hydroxide equimolar amounts replaces.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area with And w500/w800It is listed in table 2.
Embodiment 24
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 18, unlike, barium hydroxide is used The sodium hydroxide of equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800? It is listed in table 2.
Embodiment 25
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 18, unlike, barium hydroxide is used The barium bicarbonate of equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800? It is listed in table 2.
Embodiment 26
Nano-carbon material containing metallic atom is prepared using method same as Example 1, difference is as follows: step (1) In, in deionized water by the dispersion of raw material nano carbon material, urea and sodium bicarbonate is then added, so that aqueous dispersions are obtained, Wherein, by raw material nano carbon material: urea: sodium bicarbonate: H2The weight ratio of O is that the ratio of 1:1:1:160 feeds intake；Step (2) In, by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, at a temperature of 150 DEG C, spontaneous It is reacted 12 hours under pressure.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Comparative example 12
Aqueous dispersions identical with embodiment 26 are placed in the three-necked flask for being equipped with condenser pipe, which is placed in In the oil bath that temperature is 150 DEG C, back flow reaction 12 hours under normal pressure.After reaction, it is down to the temperature in three-necked flask After room temperature, reaction mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 At a temperature of DEG C after drying 12 hours, nano-carbon material containing metallic atom is obtained.The nano-carbon material containing metallic atom of preparation Composition, specific surface area and w500/w800It is listed in table 2.
Comparative example 13
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 26, unlike, step (1) is prepared Aqueous dispersions be free of urea, it is, by raw material nano carbon material dispersion in deionized water, sodium bicarbonate is then added, To obtain aqueous dispersions, wherein the dosage of raw material nano carbon material, water and sodium bicarbonate is identical as embodiment 26.System Composition, specific surface area and the w of the standby nano-carbon material containing metallic atom500/w800It is listed in table 2.
Comparative example 14
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 26, unlike, step (1) is prepared Aqueous dispersions be free of urea, it is, by raw material nano carbon material dispersion in deionized water, sodium bicarbonate is then added, To obtain aqueous dispersions, wherein the integral molar quantity phase of the mole of sodium bicarbonate and urea in embodiment 26 and sodium bicarbonate Together, the dosage of raw material nano carbon material and water is identical as embodiment 26.The group of the nano-carbon material containing metallic atom of preparation At, specific surface area and w500/w800It is listed in table 2.
Comparative example 15
Nano-carbon material is prepared using method identical with embodiment 26, unlike, the aqueous dispersions of step (1) preparation Without sodium bicarbonate, it is, in deionized water by the dispersion of raw material nano carbon material, urea is then added, to obtain water Dispersion liquid, wherein the dosage of raw material nano carbon material, water and urea is identical as embodiment 26.The nano-carbon material of preparation Composition, specific surface area and w500/w800It is listed in table 2.
Embodiment 27
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 26, unlike, in step (2), By obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, in self-generated pressure Lower reaction 12 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 28
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 26, unlike, it is received as raw material The multi-walled carbon nanotube of rice carbon material is same as Example 2.The composition of the nano-carbon material containing metallic atom of preparation, specific surface area And w500/w800It is listed in table 2.
Embodiment 29
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 26, unlike, in step (1), Under conditions of the integral molar quantity of urea and sodium bicarbonate is constant, make urea: the molar ratio 1:5 of sodium bicarbonate.Preparation contains gold Belong to composition, specific surface area and the w of atom nano-carbon material500/w800It is listed in table 2.
Embodiment 30
Nano-carbon material containing metallic atom is prepared using method same as Example 5, difference is as follows: step (1) In, in deionized water by the dispersion of raw material nano carbon material, urea then is added and saleratus is uniformly dispersed, to obtain water Dispersion liquid, wherein in raw material nano carbon material: urea: the ratio that the weight ratio of saleratus and water is 1:0.2:2:100 is thrown Material；In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 180 DEG C of temperature Under, it reacts 24 hours at autogenous pressures.
Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 31
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 30, unlike, in step (1), Multi-walled carbon nanotube as raw material nano carbon material is same as Example 6.The group of the nano-carbon material containing metallic atom of preparation At, specific surface area and w500/w800It is listed in table 2.
Embodiment 32
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 30, unlike, in step (1), In raw material nano carbon material: urea: the weight ratio of saleratus and water is that the ratio of 1:0.05:2:100 feeds intake.Preparation contains Composition, specific surface area and the w of metallic atom nano-carbon material500/w800It is listed in table 2.
Embodiment 33
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 30, unlike, in step (1), In raw material nano carbon material: urea: the weight ratio of saleratus and water is that the ratio of 1:0.5:0.5:100 feeds intake.Preparation Composition, specific surface area and the w of the nano-carbon material containing metallic atom500/w800It is listed in table 2.
Embodiment 34
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 30, unlike, in step (2), By obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, at a temperature of 210 DEG C, in self-generated pressure Lower reaction 24 hours.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800It is listed in table 2.
Embodiment 35
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 30, unlike, saleratus is used The calcium bicarbonate of equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800? It is listed in table 2.
Embodiment 36
Nano-carbon material containing metallic atom is prepared using method identical with embodiment 30, unlike, saleratus is used The potassium hydroxide of equimolar amounts replaces.Composition, specific surface area and the w of the nano-carbon material containing metallic atom of preparation500/w800? It is listed in table 2.
Embodiment 37
Nano-carbon material containing metallic atom prepared by embodiment 1 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Comparative example 16
Nano-carbon material containing metallic atom prepared by comparative example 1 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Comparative example 17
Nano-carbon material containing metallic atom prepared by comparative example 2 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Comparative example 18
Nano-carbon material containing metallic atom prepared by comparative example 3 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Comparative example 19
Nano-carbon material containing metallic atom prepared by comparative example 4 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Comparative example 20
Nano-carbon material containing metallic atom prepared by comparative example 5 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Embodiment 38
Nano-carbon material containing metallic atom prepared by embodiment 2 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Embodiment 39
Nano-carbon material containing metallic atom prepared by embodiment 3 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Embodiment 40
Nano-carbon material containing metallic atom prepared by embodiment 4 350 DEG C at a temperature of air atmosphere in roasting it is 4 small When.
Embodiment 41
Nano-carbon material containing metallic atom prepared by embodiment 14 450 DEG C at a temperature of air atmosphere in roasting it is 2 small When.
Embodiment 42
Nano-carbon material containing metallic atom prepared by embodiment 30 300 DEG C at a temperature of air atmosphere in roasting it is 12 small When.
Embodiment 43-84 is for illustrating the present invention.
Embodiment 43-78
Respectively using the nano-carbon material containing metallic atom of 0.2g (admission space 1.9mL) embodiment 1-36 preparation as urging Agent is seated in universal fixed bed miniature quartz pipe reactor, and two end seal of miniature quartz pipe reactor has quartz sand, Under the conditions of 0.1MPa and 430 DEG C, by the gas containing hydrocarbon and oxygen, (concentration of normal butane is 1.5 volume %, normal butane and oxygen Molar ratio 0.5:1, surplus are nitrogen as carrier gas) it with total volume air speed is 600h-1It is passed through in reactor and is reacted, continuously The composition of the reaction mixture exported from reactor is monitored, and calculates n-butane conversion, total olefin selectivity and butylene choosing Selecting property (for the overall selectivity of 1- butylene and 2- butylene), the results are shown in Table 3 within 3 hours and 24 hours for reaction.
Comparative example 21-35
It is reacted using method identical with embodiment 43-78, unlike, it is prepared respectively using comparative example 1-15 Nano-carbon material containing metallic atom is as catalyst.Reaction result is listed in table 3.
Comparative example 36
It is reacted using method identical with embodiment 43-78, unlike, use raw material same as Example 1 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Comparative example 37
It is reacted using method identical with embodiment 43-78, unlike, use raw material same as Example 5 Nano-carbon material is as catalyst.Reaction result is listed in table 3.
Embodiment 79-84
It is reacted using method identical with embodiment 43-78, unlike, contained using prepared by embodiment 37-42 Metallic atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 38-42
It is reacted using method identical with embodiment 43-78, unlike, contained using prepared by comparative example 16-20 Metallic atom carbon nanotube is as catalyst.Reaction result is listed in table 4.
Comparative example 43
It is reacted using method identical with embodiment 43-78, unlike, catalyst is will be same as Example 1 Raw material nano carbon material 350 DEG C at a temperature of air atmosphere in roast 4 hours obtained from.Reaction result arranges in table 4 Out.
Comparative example 44
It is reacted using method identical with embodiment 43-78, unlike, catalyst is will be same as Example 5 Raw material nano carbon material 300 DEG C at a temperature of air atmosphere in roast 12 hours obtained from.Reaction result arranges in table 4 Out.
Table 3
Table 4
The preferred embodiment of the present invention has been described above in detail, but the tool during present invention is not limited to the embodiments described above Body details within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, these letters Monotropic type all belongs to the scope of protection of the present invention.It should also be noted that, as described in the above specific embodiments each Particular technique feature can be combined in any appropriate way in the case of no contradiction, in order to avoid unnecessary heavy Multiple, the invention will not be further described in various possible combinations.In addition, between a variety of different embodiments of the invention Any combination can also be carried out, as long as it does not violate the idea of the present invention, it should also be regarded as the disclosure of the present invention.

Claims (85)

1. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material contain C element, O element, N element and At least one metallic element, the metallic element are selected from group ia metal element and group iia metallic element, former containing metal with this On the basis of the total amount of sub- nano-carbon material and based on the element, the content of O element is 1-10 weight %, and the content of N element is 0.2-5 Weight %, the total amount of the metallic element are 0.1-10 weight %, and the content of C element is 75-98.7 weight %；
This contains in metallic atom nano-carbon material, and the total content of the oxygen element determined by x-ray photoelectron spectroscopy is IO t, penetrated by X The content for the O element that peak in photoelectron spectra within the scope of 529.5-530.8eV determines is IO m, IO m/IO t0.02-0.3's In range；
This contains in metallic atom nano-carbon material, is determined by the peak within the scope of 531.0-532.5eV in x-ray photoelectron spectroscopy The amount of O element is IO c, the amount of the O element determined by the peak within the scope of 532.6-533.5eV in x-ray photoelectron spectroscopy is IO e, IO c/IO eIn the range of 0.8-2.5；
This contains in metallic atom nano-carbon material, determines the N in the nano-carbon material containing metallic atom by x-ray photoelectron spectroscopy The total amount of element is IN t, the amount of the N element determined by the peak within the scope of 398.5-400.1eV in x-ray photoelectron spectroscopy is IN c, IN c/IN tIn the range of 0.7-1；
The nano-carbon material containing metallic atom is prepared using method comprising the following steps: one kind being dispersed with raw material nano carbon The aqueous dispersions of material, at least one nitrogenous compound and at least one metallic compound are reacted in closed container, The nitrogenous compound is selected from NH3, hydrazine and urea, the metallic element in the metallic compound be selected from group ia metal element and Group iia metallic element, in reaction process, the temperature of the aqueous dispersions is maintained in the range of 60-300 DEG C.
2. nano-carbon material containing metallic atom according to claim 1, wherein IO m/IO tIn the range of 0.05-0.25； IO c/IO eIn the range of 1-2；IN c/IN tIn the range of 0.8-1.
3. nano-carbon material containing metallic atom according to claim 2, wherein IO m/IO tIn the range of 0.06-0.2； IO c/IO eIn the range of 1.2-1.7；IN c/IN tIn the range of 0.9-0.96.
4. nano-carbon material containing metallic atom according to claim 3, wherein IO m/IO tIn the range of 0.09-0.18.
5. nano-carbon material containing metallic atom described in any one of -4 according to claim 1, wherein this contains metallic atom and receives In rice carbon material, the amount of the C element determined by the peak within the scope of 288.6-288.8eV in x-ray photoelectron spectroscopy is IC c, by X The amount for the C element that peak in X-ray photoelectron spectroscopy X within the scope of 286.0-286.2eV determines is IC e, IC c/IC eIn the model of 0.5-2 In enclosing.
6. nano-carbon material containing metallic atom according to claim 5, wherein IC c/IC eIn the range of 0.5-1.5.
7. nano-carbon material containing metallic atom according to claim 6, wherein IC c/IC eIn the range of 0.7-1.
8. nano-carbon material containing metallic atom described in any one of -4 according to claim 1, wherein contain metallic atom with this On the basis of the total amount of the C element determined in nano-carbon material by x-ray photoelectron spectroscopy, by x-ray photoelectron spectroscopy The content for the C element that peak within the scope of 284.7-284.9eV determines is 60-98 weight %, by x-ray photoelectron spectroscopy The content for the C element that peak within the scope of 286.0-288.8eV determines is 2-40 weight %.
9. nano-carbon material containing metallic atom according to claim 8, wherein in the nano-carbon material containing metallic atom On the basis of the total amount of the C element determined by x-ray photoelectron spectroscopy, by 284.7-284.9eV range in x-ray photoelectron spectroscopy The content for the C element that interior peak determines is 65-95 weight %, by within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy The content for the C element that peak determines is 5-35 weight %.
10. nano-carbon material containing metallic atom according to claim 9, wherein with the nano-carbon material containing metallic atom In on the basis of the total amount of C element that is determined by x-ray photoelectron spectroscopy, by 284.7-284.9eV model in x-ray photoelectron spectroscopy The content for the C element that peak in enclosing determines is 70-92 weight %, by within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy Peak determine C element content be 8-30 weight %.
11. nano-carbon material containing metallic atom according to claim 10, wherein with the nano-carbon material containing metallic atom In on the basis of the total amount of C element that is determined by x-ray photoelectron spectroscopy, by 284.7-284.9eV model in x-ray photoelectron spectroscopy The content for the C element that peak in enclosing determines is 80-92 weight %, by within the scope of 286.0-288.8eV in x-ray photoelectron spectroscopy Peak determine C element content be 8-20 weight %.
12. nano-carbon material containing metallic atom described in any one of -4 according to claim 1, wherein by x-ray photoelectron Power spectrum determines that the total amount of the N element in the nano-carbon material containing metallic atom is IN t, by 400.6- in x-ray photoelectron spectroscopy The amount for the N element that peak within the scope of 401.5eV determines is IN g, IN g/IN tFor not higher than 0.3.
13. nano-carbon material containing metallic atom according to claim 12, wherein IN g/IN tIn the range of 0-0.2.
14. nano-carbon material containing metallic atom according to claim 13, wherein IN g/IN tIn the range of 0.04-0.1.
15. nano-carbon material containing metallic atom described in any one of -3 according to claim 1, wherein former containing metal with this On the basis of the total amount of sub- nano-carbon material and based on the element, the content of O element is 1.2-8 weight %, and the content of N element is 0.5- 4.5 weight %, the content of C element are 79.5-98.1 weight %, and the total amount of the metallic element is 0.2-8 weight %.
16. nano-carbon material containing metallic atom according to claim 15, wherein with the nano-carbon material containing metallic atom Total amount on the basis of and based on the element, the content of O element is 1.3-7.5 weight %, and the content of N element is 0.8-4 weight %, C The content of element is 83.5-97.4 weight %, and the total amount of the metallic element is 0.5-5 weight %.
17. nano-carbon material containing metallic atom according to claim 16, wherein with the nano-carbon material containing metallic atom Total amount on the basis of and based on the element, the content of O element is 2-6 weight %, and the content of N element is 1-3.5 weight %, C element Content be 86.5-94.5 weight %, the total amount of the metallic element is 2.5-4 weight %.
18. nano-carbon material containing metallic atom described in any one of -4 according to claim 1, wherein the metallic element For selected from one or more of sodium, potassium, magnesium, calcium and barium.
19. nano-carbon material containing metallic atom described in any one of -4 according to claim 1, wherein this contains metallic atom Nano-carbon material is carbon nanotube containing metallic atom.
20. nano-carbon material containing metallic atom according to claim 19, wherein this contains metallic atom nano-carbon material and is Multi-walled carbon nanotube containing metallic atom.
21. nano-carbon material containing metallic atom according to claim 20, wherein the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 50-500m2/g。
22. nano-carbon material containing metallic atom according to claim 21, wherein the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 80-300m2/g。
23. nano-carbon material containing metallic atom according to claim 22, wherein the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 90-280m2/g。
24. nano-carbon material containing metallic atom according to claim 23, wherein the multi-wall carbon nano-tube containing metallic atom The specific surface area of pipe is 100-200m2/g。
25. nano-carbon material containing metallic atom according to claim 19, wherein the multi-wall carbon nano-tube containing metallic atom Weight-loss ratio of the pipe in 400-800 DEG C of temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, the weight-loss ratio measures in air atmosphere.
26. nano-carbon material containing metallic atom according to claim 25, wherein w500/w800In the range of 0.02-0.4 It is interior.
27. nano-carbon material containing metallic atom according to claim 26, wherein w500/w800In the range of 0.05-0.25 It is interior.
28. a kind of preparation method of nano-carbon material containing metallic atom, this method includes that one kind is dispersed with to raw material nano carbon materials The aqueous dispersions of material, at least one nitrogenous compound and at least one metallic compound are reacted in closed container, institute It states nitrogenous compound and is selected from NH3, hydrazine and urea, the metallic element in the metallic compound is selected from group ia metal element and the Group IIA metal element, the metallic compound are selected from the hydroxide containing the metallic element, the carbonic acid containing the metallic element Salt and bicarbonate containing the metallic element, in reaction process, the temperature of the aqueous dispersions is maintained at 60-300 DEG C of model In enclosing, the duration of the reaction in the range of 0.5-96 hours, raw material nano carbon material: nitrogenous compound: metallizes The weight ratio of object is closed in the range of 1:0.01-20:0.01-20, raw material nano carbon material: H2The weight ratio of O is 1:2-500, The nitrogenous compound: the molar ratio of metallic compound is in the range of 1:0.2-50.
29. according to the method for claim 28, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound Ratio is measured in the range of 1:0.02-10:0.02-15；
Raw material nano carbon material: H2The weight ratio of O is 1:5-250.
30. according to the method for claim 29, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound Ratio is measured in the range of 1:0.05-5:0.05-12；
Raw material nano carbon material: H2The weight ratio of O is 1:20-200.
31. according to the method for claim 30, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound Ratio is measured in the range of 1:0.05-2.5:0.1-10；
Raw material nano carbon material: H2The weight ratio of O is 1:50-160.
32. according to the method for claim 31, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound Ratio is measured in the range of 1:0.05-1:0.5-5.
33. the method according to any one of claim 28-32, wherein the nitrogenous compound: metallic compound Molar ratio is in the range of 1:0.3-30.
34. according to the method for claim 33, wherein the nitrogenous compound: the molar ratio of metallic compound is 1: In the range of 0.6-6.
35. the method according to any one of claim 28-32, wherein the metallic compound is sodium hydroxide, hydrogen Potassium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, bicarbonate One or more of calcium, saleratus and barium bicarbonate.
36. according to the method for claim 28, wherein the nitrogenous compound is ammonia, the gold in the metallic compound Belong to element be selected from group iia metallic element, the metallic compound be carbonate and/or bicarbonate, raw material nano carbon material: Nitrogenous compound: the weight ratio of metallic compound is in the range of 1:0.02-10:0.05-8, nitrogenous compound: metallic compound Molar ratio in the range of 1:0.5-8, raw material nano carbon material: H2The weight ratio of O is in the range of 1:5-200.
37. according to the method for claim 36, wherein the metallic element in the metallic compound is selected from magnesium, calcium and barium.
38. the method according to claim 36 or 37, wherein raw material nano carbon material: nitrogenous compound: metallic compound Weight ratio in the range of 1:0.05-5:0.1-6, nitrogenous compound: range of the molar ratio of metallic compound in 1:2-7 It is interior, raw material nano carbon material: H2The weight ratio of O is in the range of 1:50-150.
39. according to the method for claim 38, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound Measure ratio in the range of 1:0.05-0.5:1-5, nitrogenous compound: the molar ratio of metallic compound in the range of 1:2.5-6, Raw material nano carbon material: H2The weight ratio of O is in the range of 1:100-120.
40. according to the method for claim 39, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound Ratio is measured in the range of 1:0.05-0.2:4-5.
41. according to the method for claim 28, wherein the nitrogenous compound is hydrazine, the gold in the metallic compound Belong to element be selected from group iia metallic element, the metallic compound be hydroxide, raw material nano carbon material: nitrogenous compound: The weight ratio of metallic compound is in the range of 1:0.02-5:0.02-15, nitrogenous compound: the molar ratio of metallic compound exists In the range of 1:0.1-5, raw material nano carbon material: H2The weight ratio of O is 1:10-200.
42. according to the method for claim 41, wherein the metallic element in the metallic compound is selected from magnesium, calcium and barium.
43. the method according to claim 41 or 42, wherein raw material nano carbon material: nitrogenous compound: metallic compound Weight ratio in the range of 1:0.1-2:0.1-10, nitrogenous compound: model of the molar ratio of metallic compound in 1:0.5-2.5 In enclosing, raw material nano carbon material: H2The weight ratio of O is 1:50-150.
44. according to the method for claim 43, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound Ratio is measured in the range of 1:0.1-1:0.5-4.
45. according to the method for claim 28, wherein the nitrogenous compound is urea, in the metallic compound Metallic element be selected from group ia metal element, the metallic compound be carbonate, raw material nano carbon material: nitrogenous compound: The weight ratio of metallic compound is in the range of 1:0.02-5:0.05-5, nitrogenous compound: the molar ratio of metallic compound is 1: In the range of 0.2-10, raw material nano carbon material: H2The weight ratio of O is in the range of 1:5-200.
46. according to the method for claim 45, wherein the metallic element in the metallic compound is selected from lithium, sodium and potassium.
47. the method according to claim 45 or 46, wherein raw material nano carbon material: nitrogenous compound: metallic compound Weight ratio in the range of 1:0.2-2:0.1-3, nitrogenous compound: range of the molar ratio of metallic compound in 1:0.7-6 It is interior, raw material nano carbon material: H2The weight ratio of O is in the range of 1:50-180.
48. according to the method for claim 47, wherein raw material nano carbon material: nitrogenous compound: the weight of metallic compound Ratio is measured in the range of 1:0.2-1:1-2, raw material nano carbon material: H2The weight ratio of O is in the range of 1:100-160.
49. the method according to any one of claim 28-32,36,37,41,42,45 and 46, wherein reaction process In, the temperature of the aqueous dispersions is maintained in the range of 100-260 DEG C.
50. according to the method for claim 49, wherein in reaction process, the temperature of the aqueous dispersions is maintained at 120- In the range of 180 DEG C.
51. the method according to any one of claim 28-32,36,37,41,42,45 and 46, wherein the reaction Duration in the range of 2-72 hours.
52. method according to claim 51, wherein the duration of the reaction is in the range of 12-48 hours.
53. method according to claim 52, wherein the duration of the reaction is in the range of 24-36 hours.
54. the method according to any one of claim 28-32,36,37,41,42,45 and 46, wherein the raw material The content of N element is not higher than 1.5 weight %, metallic element not higher than the content of 0.5 weight %, O element in nano-carbon material Total amount be not higher than 0.5 weight %.
55. method according to claim 54, wherein the content of N element is not higher than 0.2 in the raw material nano carbon material The content of weight %, O element is not higher than 1.2 weight %, and the total amount of metallic element is not higher than 0.2 weight %.
56. method according to claim 55, wherein the content of N element is not higher than 0.1 in the raw material nano carbon material The content of weight %, O element is 0.5 weight %, and the total amount of metallic element is not higher than 0.1 weight %.
57. method according to claim 56, wherein the content of N element is not higher than in the raw material nano carbon material The content of 0.05 weight %, O element is 0.3 weight %, and the total amount of metallic element is not higher than 0.05 weight %.
58. method according to claim 57, wherein the content of N element is not higher than in the raw material nano carbon material 0.02 weight %.
59. the method according to any one of claim 28-32,36,37,41,42,45 and 46, wherein the raw material Nano-carbon material is carbon nanotube.
60. method according to claim 59, wherein the raw material nano carbon material is multi-walled carbon nanotube.
61. method according to claim 60, wherein the specific surface area of the multi-walled carbon nanotube is 50-500m2/g。
62. method according to claim 61, wherein the specific surface area of the multi-walled carbon nanotube is 80-300m2/g。
63. method according to claim 62, wherein the specific surface area of the multi-walled carbon nanotube is 100-260m2/g。
64. method according to claim 63, wherein the specific surface area of the multi-walled carbon nanotube is 120-190m2/g。
65. method according to claim 60, wherein the multi-walled carbon nanotube is in 400-800 DEG C of temperature range Weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800In the range of 0.01-0.5, The weight-loss ratio measures in air atmosphere.
66. method according to claim 65, wherein w500/w800In the range of 0.02-0.4.
67. method according to claim 66, wherein w500/w800In the range of 0.05-0.35.
68. method according to claim 67, wherein w500/w800In the range of 0.05-0.15.
69. the method according to any one of claim 28-32,36,37,41,42,45 and 46, wherein this method is also Including isolating solid matter from the mixture that reaction obtains, and the solid matter isolated is dried.
70. method according to claim 69, wherein the drying 50-200 DEG C at a temperature of carry out；The drying Duration be 0.5-48 hours.
71. method according to claim 70, wherein the drying 80-180 DEG C at a temperature of carry out；The drying Duration be 2-24 hours.
72. method according to claim 71, wherein the drying 120-160 DEG C at a temperature of carry out；The drying Duration be 6-12 hours.
73. a kind of nano-carbon material containing metallic atom of the preparation of the method as described in any one of claim 28-72.
74. a kind of nano-carbon material containing metallic atom, this contain metallic atom nano-carbon material be will be in claim 1-27 arbitrarily Nano-carbon material containing metallic atom described in nano-carbon material containing metallic atom described in one or claim 73 is roasted Prepared by burning.
75. nano-carbon material containing metallic atom according to claim 74, wherein temperature of the roasting at 250-500 DEG C Degree is lower to carry out, and the duration of the roasting is 1-24 hours.
76. the nano-carbon material containing metallic atom according to claim 75, wherein temperature of the roasting at 300-450 DEG C Degree is lower to carry out；The duration of the roasting is 2-12 hours.
77. nano-carbon material containing metallic atom described in any one of claim 1-27 and 73 or claim 74-76 Any one of described in nano-carbon material containing metallic atom as hydrocarbon dehydrogenation reaction catalyst application.
78. the application according to claim 77, wherein the dehydrogenation reaction carries out in the presence of oxygen.
79. the application according to claim 77 or 78, wherein the hydrocarbon is alkane.
80. the application according to claim 79, wherein the hydrocarbon is C2-C12Alkane.
81. the application according to claim 80, wherein the hydrocarbon is normal butane.
82. a kind of hydrocarbon dehydrogenation reaction method, this method is included under conditions of existence or non-existence oxygen, in hydrocarbon dehydrogenation reaction item Under part, by nano-carbon material containing metallic atom or claim described in any one of hydrocarbon and claim 1-27 and 73 The contact of nano-carbon material containing metallic atom described in any one of 74-76.
83. the method according to claim 82, wherein the hydrocarbon is alkane.
84. the method according to claim 83, wherein the hydrocarbon is C2-C12Alkane.
85. the method according to claim 84, wherein the hydrocarbon is normal butane.
CN201511032434.0A 2015-12-31 2015-12-31 One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method Active CN106925327B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201511032434.0A CN106925327B (en) 2015-12-31 2015-12-31 One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201511032434.0A CN106925327B (en) 2015-12-31 2015-12-31 One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method

Publications (2)

Publication Number Publication Date
CN106925327A CN106925327A (en) 2017-07-07
CN106925327B true CN106925327B (en) 2019-05-21

Family

ID=59443626

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201511032434.0A Active CN106925327B (en) 2015-12-31 2015-12-31 One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method

Country Status (1)

Country Link
CN (1) CN106925327B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101718011A (en) * 2009-11-16 2010-06-02 天津工业大学 Method for preparing carbon nanofibers
CN101774573A (en) * 2010-02-08 2010-07-14 哈尔滨工业大学 Method for amination of carbon nano tube
CN103050714A (en) * 2011-10-17 2013-04-17 中国科学院大连化学物理研究所 Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2924362B1 (en) * 2007-11-30 2012-07-13 Centre Nat Rech Scient CHEMICAL REACTOR WITH NANOMETRIC SUPERSTRUCTURE

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101718011A (en) * 2009-11-16 2010-06-02 天津工业大学 Method for preparing carbon nanofibers
CN101774573A (en) * 2010-02-08 2010-07-14 哈尔滨工业大学 Method for amination of carbon nano tube
CN103050714A (en) * 2011-10-17 2013-04-17 中国科学院大连化学物理研究所 Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Oxidative dehydrogenation of n-butane on nano-carbon catalysts having graphitic structures;Da Young Jang et al;《Res Chem Intermed》;20111231;第37卷;第1145-1156页

Also Published As

Publication number Publication date
CN106925327A (en) 2017-07-07

Similar Documents

Publication Publication Date Title
CN105817246B (en) One kind nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN109304476A (en) Carbon coating transition metal nanocomposite and its preparation method and application
CN103949254B (en) Cu @ mSiO2 core-shell nano catalyst for hydrogen production by ammonia borane and hydrazine borane hydrolysis and preparation method thereof
CN106925326B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN113042086A (en) In-situ preparation method and application of amino functionalized carbon nanotube loaded NiAuPd nano-catalyst
CN106925327B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN109305665A (en) One kind nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon oxidative dehydrogenation method
CN106925271B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925318B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925321B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN114082438B (en) Supported nitrogen-doped metal-based mesoporous molecular sieve catalyst and preparation method and application thereof
CN106925325B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925319B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925323B (en) One kind nano-carbon material containing metallic atom and preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925322B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925278B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925311B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106914241A (en) A kind of Rh/VO2Nanocatalyst and its preparation method and application
CN106925324B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925320B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN106925328B (en) One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
CN112007676B (en) Super-hydrophobic high-dispersion supported tungsten carbide catalyst and preparation method and application thereof
CN114308061A (en) NiAu bimetallic alloy nano catalyst and synthesis and application thereof
CN116254553A (en) For electrocatalytic CO 2 Alloy catalyst of (2), preparation method and application thereof
CN115532299A (en) Preparation method and application of palladium-nickel nano catalyst loaded on double carriers

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant