CN105817252A - Modification method for carbon-based material - Google Patents

Modification method for carbon-based material Download PDF

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Publication number
CN105817252A
CN105817252A CN201510703710.5A CN201510703710A CN105817252A CN 105817252 A CN105817252 A CN 105817252A CN 201510703710 A CN201510703710 A CN 201510703710A CN 105817252 A CN105817252 A CN 105817252A
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carbon
based material
range
peak
determines
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CN105817252B (en
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史春风
荣峻峰
于鹏
谢婧新
林伟国
宗明生
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a modification method for a carbon-based material. The carbon-based material contains 80 to 98.9 wt% of elemental C, 0.1 to 7 wt% of elemental N and 1 to 15 wt% of elemental O. The invention also provides a preparation method for the carbon-based material. The preparation method comprises the following steps: (1) mixing a solid carbon source, a precursor and water so as to obtain a mixed material, wherein the precursor contains an organic amine and/or quaternary ammonium base; (2) subjecting the mixed material obtained in the step (1) to hydro-thermal treatment so as to obtain a material having undergone hydro-thermal treatment, separating solids from the material having undergone hydro-thermal treatment and carrying out drying so as to obtain a dried material; and (3) roasting the dried material obtained in the step (2). The invention also provides application of the carbon-based material in catalysis of oxidation of hydrocarbons. The carbon-based material provided by the invention can improve selectivity and conversion rate of olefins prepared from hydrocarbons through oxidation.

Description

A kind of method of modifying of carbon-based material
Technical field
The present invention relates to technical field of material chemistry, in particular it relates to a kind of carbon-based material, the preparation method of a kind of carbon-based material, the purposes of this carbon-based material and the method for a kind of hydrocarbon oxidation.
Background technology
Carbon-based material includes CNT, activated carbon, graphite, Graphene, fullerene, carbon nano-fiber and Nano diamond etc..Carbon-based material can be as the catalysis material of oxidation of alkanes, such as: have document (AppliedCatalysis, 29 (1987) 311-326) report and utilize activated carbon, for catalyst, oxidative dehydrogenation of ethylbenzene is become styrene, also has document (ACTAPHYSICAPOLONICA, Vol.118, (2010), 459-464) report and utilize activated carbon, for catalyst, normal butane is converted into butylene and butadiene.
Research shows, if modifying the heteroatomic saturated and unsaturation functional groups such as oxygen-containing, nitrogen on nano-carbon material (such as CNT and Graphene) surface, the catalysis activity of nano-carbon material can be changed, as realized introducing oxygen atom in nano-carbon material by nano-carbon material being carried out oxidation processes, thus increase the content of oxygen-containing functional group in nano-carbon material.For example, it is possible to by nano-carbon material at strong acid (such as HNO3、H2SO4) and/or strong oxidizing solution (such as H2O2、KMnO4Carry out back flow reaction in), can also assist while back flow reaction and carry out microwave heating or sonic oscillation, to strengthen the effect of oxidation reaction.
But, carrying out back flow reaction in strong acid and/or strong oxidizing solution may have a negative impact to the framing structure of nano-carbon material, even destroys the framing structure of nano-carbon material.Such as: nano-carbon material nitric acid is aoxidized, although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, but easily cause nano-carbon material cut-off and/or substantially increase the defective bit in graphite network structure, consequently, it is possible to reduce the performance of nano-carbon material, such as heat stability.It addition, by carrying out back flow reaction in strong acid and/or strong oxidizing solution, during to introduce oxygen atom, the introduction volume of oxygen atom is high to the dependency of operation condition, and fluctuation range is wider, is difficult to accurately control.
Alkene particularly alkadienes and aromatic olefin be important industrial chemicals, such as butadiene be produce synthetic rubber (such as butadiene-styrene rubber, butadiene rubber, nitrile rubber, neoprene) primary raw material.Utilize styrene and butadiene copolymer, produce various uses resin widely (such as ABS resin, SBS resin, BS resin and MBS resin), make butadiene gradually occupy critical role in production of resins.In addition, butadiene can be additionally used in production ethylidene norbornene (EP rubbers Third monomer), 1,4-butanediol, adiponitrile (nylon66 fiber monomer), sulfolane, anthraquinone and oxolane etc., therefore butadiene is also important basic chemical industry raw material.Additionally, styrene is also the monomer of important synthetic rubber and plastics, can be used to produce butadiene-styrene rubber, polystyrene and foamed polystyrene etc.；It is also used for manufacturing the engineering plastics of multiple different purposes from other monomer copolymerizations.As prepared ABS resin with acrylonitrile, butadiene copolymer, it is widely used in various household electrical appliance and industrial；The SAN resin prepared with acrylonitrile compolymer is the resin of impact resistance, bright in color；It is a kind of thermoplastic elastomer with the SBS obtained by butadiene copolymer, is widely used as polrvinyl chloride, polyacrylic modifying agent etc..Styrene, mainly for the production of styrene series resin and butadiene-styrene rubber, is also one of raw material producing ion exchange resin and pharmaceuticals, additionally, styrene can be additionally used in the industries such as pharmacy, dyestuff, pesticide and ore dressing.
Oxidative dehydrogenation is the important method preparing alkene, such as can by butane oxidation dehydrogenation generate 1-butylene, 1-butylene can so that oxidative dehydrogenation generate 1,3-butadiene；Vinylbenzene oxidative dehydrogenation can also be generated styrene.The problem that alkene generally there are selectivity and conversion ratio is difficult to improve simultaneously is prepared in oxidative dehydrogenation.
Summary of the invention
It is an object of the invention to overcome oxidative dehydrogenation to prepare the selectivity in the presence of alkene and problem that conversion ratio is typically difficult to improve simultaneously, it is provided that a kind of can prepare alkene and obtain high selectivity and the carbon-based material of conversion ratio, the preparation method of this carbon-based material and the purposes of this carbon-based material simultaneously by catalytic oxidative dehydrogenation.
The inventors found that, use the presoma containing organic amine and/or quaternary ammonium base that carbon source material is carried out hydrothermal treatment consists, solid in material after hydrothermal treatment consists is separated and after drying roasting, can be formed and there is catalytic hydrocarbon oxidation prepare the activity of alkene and obtain the carbon-based material of high selectivity and conversion ratio simultaneously, resulting in the present invention.
On the one hand, the invention provides a kind of carbon-based material, on the basis of the gross weight of this carbon-based material, this carbon-based material contains the carbon of 80-98.9 weight %, the nitrogen element of 0.1-7 weight % and the oxygen element of 1-15 weight %；Wherein, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.2-5.
On the other hand, present invention also offers a kind of method preparing carbon-based material, the method comprises the steps: that solid carbon source, presoma and water are mixed by (1), obtains mixed material；Wherein, described presoma contains organic base, and described organic base includes organic amine and/or quaternary ammonium base；(2) the mixed material that step (1) obtains is carried out hydrothermal treatment consists, obtain the material after hydrothermal treatment consists；And separate the solid in the material after hydrothermal treatment consists；(3) solid in the material after hydrothermal treatment consists step (2) obtained carries out roasting.
On the other hand, present invention also offers the carbon-based material that method as above prepares.
Another further aspect, present invention also offers carbon-based material as above and carbon-based material that method as defined above the prepares purposes in catalytic hydrocarbon oxidation reaction.
Another further aspect, the method that present invention also offers the oxidation of a kind of hydrocarbon, the method includes: under hydrocarbon catalysis oxidizing condition, will contact with catalyst with the gas of oxygen containing hydrocarbon；Described catalyst includes carbon-based material as above.
By technique scheme, the present invention can improve oxidation simultaneously and prepare selectivity and the conversion ratio of alkene.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The invention provides a kind of carbon-based material, on the basis of the gross weight of this carbon-based material, this carbon-based material contains the carbon of 80-98.9 weight %, the nitrogen element of 0.1-7 weight % and the oxygen element of 1-15 weight %；Wherein, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.2-5.
Wherein it is preferred to, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.5-2.It is further preferred that in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.6-1.8.Usually, the area of the O1s spectral peak in x-ray photoelectron power spectrum may determine that the total amount of O element in carbon-based material.Wherein, the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines may indicate that the Relative mole content of C-O group in carbon-based material, and the amount of the oxygen element that the peak in the range of 531.8-532.2eV determines may indicate that the Relative mole content of C=O group in carbon-based material.
In the present invention, in carbon-based material, the content of each element is that after process 3h, carbon-based material is used the numerical value that X-ray photoelectron spectroscopy measures at a temperature of 300 DEG C in helium atmosphere, and its assay method is well known to those skilled in the art, and does not repeats.
In the present invention, x-ray photoelectron power spectrum collection of illustrative plates refers to XPS collection of illustrative plates, XPS collection of illustrative plates can measure according to the method that Instrumental Analysis field is conventional and obtain, in x-ray photoelectron power spectrum, the calculating of the amount of the element that the peak in particular range determines can calculate according to the method that Instrumental Analysis field is conventional, the data software such as can being measured according to the description of x-ray photoelectron spectroscopy and use x-ray photoelectron spectroscopy to carry carries out quantitative Analysis, and the present invention does not has particular/special requirement to this.In the present invention, x-ray photoelectron gamma-spectrometric data is what sample measured after process 3h at a temperature of 300 DEG C in helium atmosphere.Wherein, when the content value of mensuration is less than 0.1 weight %, the content of this element is designated as 0.
In the present invention, from the point of view of the catalytic capability improving described carbon-based material further, preferably, on the basis of the gross weight of this carbon-based material, this carbon-based material contains the carbon of 85-97 weight %, the nitrogen element of 0.2-5 weight % and the oxygen element of 2-10 weight %.It is highly preferred that on the basis of the gross weight of this carbon-based material, this carbon-based material contains the carbon of 90-95 weight %, the nitrogen element of 0.5-4 weight % and the oxygen element of 4-8 weight %.
According to the carbon-based material of the present invention, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 398.0-400.5eV determines and 395.0-405.0eV determines is in the range of 0.5-1；More preferably in the range of 0.6-0.9.The total amount of N element in carbon-based material is may determine that by the area of the N1s spectral peak in x-ray photoelectron power spectrum, usually, the amount of the nitrogen element that the peak in the range of 395.0-405.0eV determines may indicate that the Relative mole content of whole nitrogen contained by nitrogen-containing group in carbon-based material substantially.Wherein, the amount of the nitrogen element that the peak in the range of 398.0-400.5eV determines may indicate that the Relative mole content of the nitrogen (nitrogen as in pyrroles, pyridine, amide and surface amino groups) in carbon-based material contained by NH group substantially.
According to the carbon-based material of the present invention, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 400.6-401.5eV determines and 395.0-405.0eV determines is in the range of 0-0.5；More preferably in the range of 0.1-0.4.Wherein, the amount of the nitrogen element that the peak in the range of 400.6-401.5eV determines may indicate that the Relative mole content of contained graphite mould nitrogen in carbon-based material substantially, and the amount of the nitrogen element that the peak in the range of 395.0-405.0eV determines may indicate that the Relative mole content of the nitrogen contained by whole nitrogen-containing groups of carbon-based material substantially.
According to the carbon-based material of the present invention, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 283.8-284.2eV determines and 280.0-294.0eV determines is in the range of 0.6-1；More preferably in the range of 0.7-0.9.The total amount of C element in carbon-based material is may determine that by the area of the C1s spectral peak in x-ray photoelectron power spectrum, usually, the amount of the carbon that the peak in the range of 280.0-294.0eV determines may indicate that the Relative mole content of the carbon contained by whole carbon-containing groups of carbon-based material substantially.Wherein, the amount of the carbon that the peak in the range of 283.8-284.2eV determines may indicate that the Relative mole content of contained graphitic carbon in carbon-based material substantially.
Carbon-based material according to the present invention, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the carbon that the peak in the range of the amount sum of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines and 280.0-294.0eV determines is in the range of 0.01-0.2；More preferably in the range of 0.05-0.15.The total amount of C element in carbon-based material is may determine that by the area of the C1s spectral peak in x-ray photoelectron power spectrum, usually, the amount of the carbon that the peak in the range of 280.0-294.0eV determines may indicate that the Relative mole content of the carbon contained by whole carbon-containing groups of carbon-based material substantially.Wherein, the amount of the carbon that the peak in the range of 286.2-286.6eV determines may indicate that the Relative mole content of the carbon (carbon as in carboxyl, acid anhydride and ester) in carbon-based material contained by C-O group substantially, and the amount of the carbon that the peak in the range of 288.6-289.0eV determines may indicate that the Relative mole content of the carbon (carbon as in hydroxyl and ether) in carbon-based material contained by C=O group substantially.
According to the carbon-based material of the present invention, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines is in the range of 0.2-2；More preferably in the range of 0.6-1.7.
In the present invention, the position at above-mentioned each peak be can determine that by the combination corresponding to the summit at this peak, the peak that scope determines by mentioned earlier refer to the combination corresponding to summit can peak in such range, a peak can be included within the range, it is also possible to include plural peak.Such as: the peak in the range of 288.6-289.0eV refers to that the combination corresponding to summit can be in the whole peaks in the range of 288.6-289.0eV.
According to the carbon-based material of the present invention, wherein, the W of described carbon-based material500/W800Can be in the range of 0.02-0.5；The W of the most described carbon-based material500/W800In the range of 0.05-0.25.Under this preferable case, described carbon-based material is obtained in that more preferable catalytic effect when as catalyst, during in particular as the catalyst of hydrocarbons dehydrogenation reaction, can obtain higher feed stock conversion and selectivity of product.Wherein, W800Refer under the Elevated Temperature Conditions of air atmosphere and the initial temperature of 25 DEG C and 10 DEG C/min, described carbon-based material weight at 800 DEG C is relative to the slip of the weight at 400 DEG C, i.e. (described carbon-based material weight at 400 DEG C and described carbon-based material weight difference at 800 DEG C)/described carbon-based material weight at 400 DEG C, W500Refer under the Elevated Temperature Conditions of air atmosphere and the initial temperature of 25 DEG C and 10 DEG C/min, described carbon-based material weight at 500 DEG C relative to the slip of the weight at 400 DEG C, i.e. (described carbon-based material weight at 400 DEG C with described carbon-based material weight difference at 500 DEG C)/described carbon-based material weight at 400 DEG C.
Carbon-based material according to the present invention, it is preferable that nitrogen element therein and the distribution uniform of oxygen element.As when being analyzed by X-ray microregion element, in the different X-ray microcells that the area on the surface of this carbon-based material is identical, the coefficient of variation of the content of nitrogen element and oxygen element is below 20%, more preferably below 15%, particularly preferably below 10%, the most preferably below 5%.Wherein, X-ray microcell refers to the observation area selected when carrying out X-ray microregion element and analyzing.Wherein, the concept of the coefficient of variation refers to the standard deviation of multiple measured value and the percentage ratio of their average, i.e. coefficient of variation CV=(standard deviation SD/ meansigma methods MN) × 100%.Wherein, the method carrying out X-ray microregion element analysis can obtain according to the method mensuration that Instrumental Analysis field is conventional, such as concrete method of testing may include that and is scanned along the length direction of length carbon-based material such as CNT in the range of 25-250nm with energy depressive spectroscopy, determine nitrogen-atoms and the oxygen atom concentration on this length direction or content (measuring 5 concentration or content) respectively, made five effective samples by same nano-carbon material and be scanned Electronic Speculum-energy spectrum analysis respectively, each sample takes 5 different CNTs and is scanned, nitrogen-atoms and oxygen atom each obtain 25 concentration or content data, calculate the coefficient of variation of corresponding nitrogen-atoms and oxygen atom.The coefficient of variation refers to the standard deviation of 25 measured values and the percentage ratio of their average, i.e. coefficient of variation CV=(standard deviation SD/ meansigma methods MN) × 100% herein.In order to preferably reflect the nitrogen element in carbon-based material and the distributing homogeneity of oxygen element, the area on the surface of the carbon-based material that X-ray microregion element is selected in analyzing can be 10-250nm2, preferably 20-200nm2。
Wherein, the structure of at least one during the configuration of described carbon-based material can include the configuration of CNT, Graphene, fullerene, nano carbon particle, activated carbon, thin layer graphite, carbon nano-fiber and Nano diamond.
Wherein, described carbon-based material can be to have the mixture of one or more in the carbon-based material of CNT, Graphene, fullerene, nano carbon particle, activated carbon, thin layer graphite, carbon nano-fiber and nano diamond structure.Wherein, described carbon-based material has the structure selected from CNT, Graphene, fullerene, nano carbon particle, activated carbon, thin layer graphite, carbon nano-fiber and Nano diamond.
Present invention also offers a kind of method preparing carbon-based material, the method comprises the steps: that solid carbon source, presoma and water are mixed by (1), obtains mixed material；Wherein, described presoma contains organic base, and described organic base includes organic amine and/or quaternary ammonium base；(2) the mixed material that step (1) obtains is carried out hydrothermal treatment consists, obtain the material after hydrothermal treatment consists；And separate the solid in the material after hydrothermal treatment consists；(3) solid in the material after hydrothermal treatment consists step (2) obtained carries out roasting.
The method according to the invention, wherein, time and the temperature of mixing do not have particular/special requirement, can change in a big way, and the time such as mixed can be 0.5-72h, and the temperature of mixing can be 20-80 DEG C.
The method according to the invention, wherein, the carbon in described solid carbon source can be 1:(0.001-0.5 with the mol ratio of the nitrogen element in described organic alkali source), preferably 1:(0.01-0.05).
The method according to the invention, wherein, the carbon in described solid carbon source can be 1:(1-100 with the weight ratio of water), preferably 1:(5-20).
The method according to the invention, wherein, hydro-thermal refers to the reaction condition keeping part water to maintain liquid more than 100 DEG C under air-proof condition at autogenous pressures, water heating can be made part water spontaneous vaporization supercharging obtain under air-proof condition by hydro-thermal, preferably, the temperature carrying out hydrothermal treatment consists is 105-200 DEG C；More preferably 120-180 DEG C.Wherein, the time of hydrothermal treatment consists can be 0.5-96h, preferably 2-72h.
Wherein, the operation separating the solid in the material after hydrothermal treatment consists can be carried out by routine separate modes such as centrifugal and/or filtrations.
Wherein, after separating the solid in the material after hydrothermal treatment consists, solid can be dried, the condition of being dried can change in a big way, the present invention is not particularly limited for described dry condition, can be conventional selection, preferably, the temperature being dried is 80-180 DEG C, and the time is 0.5-24h.Described being dried can be carried out at ambient pressure, it is also possible under reduced pressure carries out.
Wherein, described roasting can be carried out in inert atmosphere, can also carry out in oxygen-containing atmosphere, can also carry out in inert atmosphere and oxygen-containing atmosphere successively, wherein, described inert atmosphere refers to the atmosphere formed by non-active gas, described non-active gas such as group 0 element gas (such as argon) and/or nitrogen.Preferably, described roasting is carried out in the gas containing oxygen, and on the basis of the cumulative volume containing the gas of oxygen, the content of the oxygen in the gas containing oxygen is 2-25 volume %.It is highly preferred that described roasting is carried out in atmosphere.
Wherein, the condition carrying out roasting can change in a big way, and the temperature of such as roasting is 200-500 DEG C, preferably 300-450 DEG C, and the time of roasting is 0.5-48h, preferably 2-24h.Carry out temperature that roasting can use the strategy of temperature programming to carry out heat treated, such as roasting when being 200-450 DEG C, first roasting 1-12h at 200-300 DEG C, then roasting 1-12h at 310-450 DEG C；Such as when the temperature of roasting is 300-450 DEG C, first roasting 1-12h at 300-350 DEG C, then roasting 1-12h at 380-450 DEG C.Wherein, room temperature can be cooled to natural cooling after roasting terminates.
The method according to the invention, wherein, the selection of described solid carbon source can be the selection that carbon catalytic field is conventional, as long as having the catalysis of catalytic hydrocarbon oxidation after described solid carbon source hydrothermal treatment, the most described solid carbon source can include at least one in CNT, Graphene, fullerene, nano carbon particle, activated carbon, thin layer graphite, carbon nano-fiber and Nano diamond etc..Preferably, at least one during described solid carbon source includes CNT, Nano diamond and Graphene.
Wherein, described CNT can include SWCN and/or multi-walled carbon nano-tubes.The specific surface area of described CNT can change in a big way, for example, 20-1000m2/ g, preferably 30-500m2/g.Described CNT can be commercially available can also be prepared according to literature method, and this is well known to those skilled in the art, and does not repeats.
In the case of with the method for the invention it is preferred to, when described solid carbon source is multi-walled carbon nano-tubes, the W of described multi-walled carbon nano-tubes500/W800Can be in the range of 0.02-0.5；The W of the most described multi-walled carbon nano-tubes500/W800In the range of 0.05-0.25.Under this preferable case, the carbon-based material that the method for the present invention obtains is obtained in that more preferable catalytic effect when as catalyst, during in particular as the catalyst of hydrocarbons dehydrogenation reaction, can obtain higher feed stock conversion and selectivity of product.Wherein, W800Refer under the Elevated Temperature Conditions of air atmosphere and the initial temperature of 25 DEG C and 10 DEG C/min, described solid carbon source weight at 800 DEG C is relative to the slip of the weight at 400 DEG C, i.e. (described solid carbon source weight at 400 DEG C and described solid carbon source weight difference at 800 DEG C)/described solid carbon source weight at 400 DEG C, W500Refer under the Elevated Temperature Conditions of air atmosphere and the initial temperature of 25 DEG C and 10 DEG C/min, described solid carbon source weight at 500 DEG C relative to the slip of the weight at 400 DEG C, i.e. (described solid carbon source weight at 400 DEG C with described solid carbon source weight difference at 500 DEG C)/described solid carbon source weight at 400 DEG C.
In a kind of embodiment being more highly preferred to of the present invention, described solid carbon source is multi-walled carbon nano-tubes, and the specific surface area of described multi-walled carbon nano-tubes is 50-500m2/ g, preferably 100-400m2/g；The W of described multi-walled carbon nano-tubes500/W800Can be in the range of 0.02-0.5；The W of the most described multi-walled carbon nano-tubes500/W800In the range of 0.05-0.25.
Wherein, described solid carbon source can be possibly together with oxygen element, nitrogen element and remaining nonmetalloid (such as phosphorus atoms and sulphur atom) according to source difference, it is also possible to do not contain oxygen element, nitrogen element and remaining nonmetalloid (such as phosphorus atoms and sulphur atom).
The method according to the invention, when described solid carbon source contains oxygen element, the wherein content of oxygen element the most not higher than 2 weight %, preferably not higher than 0.5 weight %, the most not higher than 0.2 weight %.
The method according to the invention, when described solid carbon source contains nitrogen element, the wherein content of nitrogen element the most not higher than 0.5 weight %, preferably not higher than 0.2 weight %, the most not higher than 0.1 weight %.
The method according to the invention, when described solid carbon source contains remaining nonmetalloid (such as phosphorus atoms and sulphur atom), the total amount (in terms of element) of remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside oxygen atom and nitrogen-atoms the most not higher than 0.5 weight % in wherein said solid carbon source, it is preferably not higher than 0.2 weight %, the most not higher than 0.1 weight %.
The method according to the invention, described organic amine can include one or more of aliphatic amine, hydramine, amide, aliphatic cyclic amine and aromatic amine.
In the present invention, described quaternary ammonium base can be various organic level Four ammonium alkali；Described aliphatic amine can be NH3In at least one hydrogen by aliphatic alkyl (preferably alkyl) replace after formed various compounds；Described hydramine can be NH3In at least one hydrogen by hydroxyl aliphatic alkyl (preferably alkyl) replace after formed various compounds；Described amide can be the compound formed after the hydroxyl in carboxylic acid is replaced by amino (or amido)；Described aliphatic cyclic amine can be NH3In at least one hydrogen replaced by cycloalkyl group after formed various compounds；Described aromatic amine can be NH3In at least one hydrogen replaced by aryl radical after formed various compounds.
Specifically, described quaternary ammonium base can be quaternary ammonium base shown in formula I, and described aliphatic amine can be the aliphatic amine that Formula II represents, described hydramine can be the hydramine represented such as formula III:
In Formulas I, R1、R2、R3And R4It is respectively C1-C4Alkyl, C1-C4Alkyl include C1-C4Straight chained alkyl and C3-C4Branched alkyl, such as: R1、R2、R3And R4Can be each methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
R5(NH2)n(Formula II)
In Formula II, n is the integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6Branched alkyl, such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl or n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub-and C3-C6Branched alkylidene, such as methylene, ethylidene, sub-n-pro-pyl, sub-normal-butyl, sub-n-pentyl or sub-n-hexyl.One or more during more preferably aliphatic amine compound is ethamine, n-butylamine, butanediamine and hexamethylene diamine.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6Identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub-and C3-C4Branched alkylidene, such as methylene, ethylidene, sub-n-pro-pyl and sub-normal-butyl；M is 1,2 or 3.It is highly preferred that described hydramine is one or more in monoethanolamine, diethanolamine and triethanolamine.
Wherein, at least one during the instantiation of described aliphatic amine can include but not limited to ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine and hexamethylene diamine.The instantiation of described hydramine can include but not limited at least one in monoethanolamine, diethanolamine and triethanolamine；The instantiation of described quaternary ammonium base can include but not limited at least one in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH and TBAH.The instantiation of described amide can include but not limited at least one in Methanamide, acetamide, propionic acid amide., butyramide, isobutyramide, acrylamide, polyacrylamide, caprolactam, dimethylformamide and dimethyl acetylamide.The instantiation of described aliphatic cyclic amine can include but not limited at least one in triethylenediamine, diethylenetriamines, hexamethylenetetramine, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine and cyclohexylamine.The instantiation of described aromatic amine can include but not limited to aniline, diphenylamines, benzidine, o-phenylenediamine, m-diaminobenzene., p-phenylenediamine, o-toluidine, m-toluidine, open-chain crown ether, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2, at least one in 4,6-trimethylaniline, o ethyl aniline, N-butylaniline and 2,6-diethylaniline.
On the other hand, present invention also offers the carbon-based material that method as above prepares.
Wherein, the carbon-based material that the method obtains can contain the carbon of 80-98.9 weight %, the nitrogen element of 0.1-7 weight % and the oxygen element of 1-15 weight %；Preferably comprise the carbon of 85-97 weight %, the nitrogen element of 0.2-5 weight % and the oxygen element of 2-10 weight %；More preferably contain the carbon of 90-95 weight %, the nitrogen element of 0.5-4 weight % and the oxygen element of 4-8 weight %.
Wherein, in the x-ray photoelectron power spectrum of the carbon-based material that the method obtains, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.2-5.
Wherein, in the x-ray photoelectron power spectrum of the carbon-based material that the method obtains, the ratio of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 398.0-400.5eV determines and 395.0-405.0eV determines is in the range of 0.5-1.
Wherein, in the x-ray photoelectron power spectrum of the carbon-based material that the method obtains, the ratio of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 400.6-401.5eV determines and 395.0-405.0eV determines is in the range of 0-0.5.
Wherein, in the x-ray photoelectron power spectrum of the carbon-based material that the method obtains, the ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 283.8-284.2eV determines and 280.0-294.0eV determines is in the range of 0.6-1.
Wherein, in the x-ray photoelectron power spectrum of the carbon-based material that the method obtains, the ratio of the amount of the carbon that the peak in the range of the amount sum of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines and 280.0-294.0eV determines is in the range of 0.01-0.2.
Wherein, in the x-ray photoelectron power spectrum of the carbon-based material that the method obtains, the ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines is in the range of 0.2-2.
The carbon-based material obtained according to the inventive method, described carbon-based material weight-loss ratio in the temperature range of 400-800 DEG C is W800, the weight-loss ratio in the temperature range of 400-500 DEG C is W500, W500/W800Preferably in the range of 0.02-0.5, more preferably in the range of 0.05-0.25.So it is obtained in that more preferable catalytic effect, during in particular as the catalyst of hydrocarbons dehydrogenation reaction, higher feed stock conversion and selectivity of product can be obtained.In the present invention, described weight-loss ratio measures in air atmosphere, and initial temperature is 25 DEG C, and heating rate is 10 DEG C/min.
The carbon-based material obtained according to the inventive method, nitrogen element therein and the distribution uniform of oxygen element.As when being analyzed by X-ray microregion element, in the different X-ray microcells that the area on the surface of this carbon-based material is identical, the coefficient of variation of the content of nitrogen element and oxygen element is below 20%.Wherein, X-ray microcell refers to the observation area selected when carrying out X-ray microregion element and analyzing.Wherein, the concept of the coefficient of variation refers to the standard deviation of multiple measured value and the percentage ratio of their average, i.e. coefficient of variation CV=(standard deviation SD/ meansigma methods MN) × 100%.Wherein, the method carrying out X-ray microregion element analysis can obtain according to the method mensuration that Instrumental Analysis field is conventional, such as concrete method of testing may include that and is scanned along the length direction of length carbon-based material such as CNT in the range of 25-250nm with energy depressive spectroscopy, determine nitrogen-atoms and the oxygen atom concentration on this length direction or content (measuring 5 concentration or content) respectively, made five effective samples by same nano-carbon material and be scanned Electronic Speculum-energy spectrum analysis respectively, each sample takes 5 different CNTs and is scanned, nitrogen-atoms and oxygen atom each obtain 25 concentration or content data, calculate the coefficient of variation of corresponding nitrogen-atoms and oxygen atom.The coefficient of variation refers to the standard deviation of 25 measured values and the percentage ratio of their average, i.e. coefficient of variation CV=(standard deviation SD/ meansigma methods MN) × 100% herein.In order to preferably reflect the nitrogen element in carbon-based material and the distributing homogeneity of oxygen element, the area on the surface of the carbon-based material that X-ray microregion element is selected in analyzing can be 10-250nm2, preferably 20-200nm2。
Wherein, the method for the present invention obtains having the possible cause of the carbon-based material of above-mentioned pathognomonic feature parameter and includes that in the method for the present invention be to combine the processing procedure such as hydro-thermal and roasting under specific material variety and material proportion.
The configuration of the carbon-based material obtained according to the inventive method can include at least one in the configuration of CNT, Graphene, fullerene, nano carbon particle, activated carbon, thin layer graphite, carbon nano-fiber and Nano diamond.
Another further aspect, present invention also offers carbon-based material as above and the carbon-based material that as above method prepares purposes in catalytic hydrocarbon oxidation reaction.
Another further aspect, the method that present invention also offers the oxidation of a kind of hydrocarbon, the method includes: under hydrocarbon catalysis oxidizing condition, will contact with catalyst with the gas of oxygen containing hydrocarbon；Described catalyst includes carbon-based material as above.
Wherein, the carbon number of described hydrocarbon can be 2-15, and described hydrocarbon includes at least one in alkane, alkene and the aromatic hydrocarbon containing alkyl；Described alkyl contains at least two carbon atom.
Wherein, at least one during described hydrocarbon can include ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, ethylbenzene, phenylpropyl alcohol alkane, benzene butane, benzene pentane and benzene hexane；Preferably include at least one in butane, 1-butylene, ethylbenzene, propane, ethane and pentane.
Wherein, hydrocarbon can change with the mol ratio of oxygen in a big way, such as, can be (0.01-100): 1, is preferably (0.1-10): 1, more preferably (0.2-5): 1.
Wherein, the described gas containing hydrocarbon and oxygen can also contain carrier gas, and the selection of described carrier gas can be the selection that hydrocarbon oxidation field is conventional, and the most described carrier gas can contain nitrogen, CO2With at least one in steam.
Wherein, in the described gas containing hydrocarbon and oxygen, the total concentration of hydrocarbon and oxygen can be the selection that hydrocarbon oxidation field is conventional, such as, can be 0.5-70 volume %；In the preferably described gas containing hydrocarbon and oxygen, the total concentration of hydrocarbon and oxygen is 1-50 volume %, more preferably 2-30 volume %.
Wherein, hydrocarbon catalysis oxidizing condition can be that the selection that hydrocarbon oxidation field is conventional, such as hydrocarbon catalysis oxidizing condition may include that Contact Temperature can be 200-650 DEG C, preferably 300-600 DEG C, more preferably 350-550 DEG C, the most preferably 400-450 DEG C；Pressure can be 0.05-80MPa, preferably 0.1-40MPa, more preferably 0.1-20MPa, the most preferably 0.1-5MPa；Calculating with the cumulative volume of the gas containing hydrocarbon and oxygen, gas can be 0.1-10000h by the volume space velocity of catalyst-1, preferably 1-6000h-1, more preferably 5-5000h-1, the most preferably 10-4000h-1。
Wherein, the contact of hydrocarbon catalysis oxidation can be carried out at fixed bed reactors and/or fluidized-bed reactor, preferably carries out in fixed bed reactors, more preferably carries out in tubular fixed-bed reactor.Preferably, described carbon-based material is filled in described tubular fixed-bed reactor as catalyst, described containing hydrocarbon and the gas of oxygen by described tubular fixed-bed reactor to contact.
Further describe the present invention by the following examples.In following example and comparative example, if not otherwise specified, used reagent is commercially available analytical reagent.Wherein, the phosphorus content not containing oxygen element CNT is less than 1.5 weight % more than 96 weight %, ash, and specific surface area is 168m2/ g, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences, the phosphorus content containing oxygen element CNT is more than 95 weight %, and oxygen element content is 1.1 weight %, and ash is less than 1.2 weight %, and specific surface area is 211m2/ g, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.The phosphorus content of Graphene is more than 99 weight %, and ash is less than 0.8 weight %, and specific surface area is 627m2/ g, purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
In following example and comparative example, X-ray photoelectron spectroscopic analysis is carried out on the ESCALab250 type x-ray photoelectron spectroscopy of ThermoScientific company.Excitaton source is monochromatization AlK α X-ray, and energy is 1486.6eV, and power is 150W.Penetrating energy used by narrow scan is 30eV.Base vacuum when analyzing test is 6.5 × 10-10mbar.C1s peak (284.0eV) correction of electron binding energy simple substance carbon.Correlation method for data processing is carried out on the ThermoAvantage software that x-ray photoelectron spectroscopy carries, and version number is V5.926, uses the sensitivity factor method known to industry to carry out quantitatively and wait analysis in analyzing module.
In following example and comparative example, thermogravimetric analysis is carried out on TA5000 thermal analyzer, and test condition is air atmosphere, and programming rate is 10 DEG C/min, and temperature range is that room temperature (25 DEG C) is to 1000 DEG C.
In following example and comparative example, use ASAP2000 type N of Micromertrics company of the U.S.2Physical adsorption appearance measurement the specific area.
In following example and comparative example, employing is furnished with the scanning electron microscope (Holland's PHILIPS company XL30ESEM type scanning electron microscope) of energy depressive spectroscopy (parts) and measures nano-carbon material (as a example by CNT) surface nitrogen atom and the distributing homogeneity of oxygen atom, concrete method of testing is: be scanned along the length direction of length CNT in the range of 25-250nm with energy depressive spectroscopy, determine nitrogen-atoms and the oxygen atom concentration (measuring 5 concentration) on this length direction respectively, made five effective samples by same nano-carbon material and be scanned Electronic Speculum-energy spectrum analysis respectively, each sample takes 5 different CNTs and is scanned, nitrogen-atoms and oxygen atom each obtain 25 concentration datas, calculate the coefficient of variation of corresponding nitrogen-atoms and oxygen atom.The coefficient of variation refers to the standard deviation of 25 measured values and the percentage ratio of their average, i.e. coefficient of variation CV=(standard deviation SD/ meansigma methods MN) × 100% herein.
Embodiment 1
nullUnder room temperature，By solid carbon source (not containing the CNT of oxygen element)、Presoma (TPAOH) and water stirring mixing 2h，Obtain mixed material，Wherein，Carbon in described solid carbon source is 1:0.03 with the mol ratio of the nitrogen element in described presoma，Described solid carbon source is 1:10 with the weight ratio of water，Mixed material obtained above is placed in and seals in autoclave with teflon-lined，In 140 DEG C of hydrothermal treatment consists 24h at autogenous pressures，Solid in material after hydrothermal treatment consists is filtered and separates and be dried，The temperature being dried is 120 DEG C，Until the solid filtering isolated is kept substantially constant weight (the dry time is 6h)，Obtain dried material，Then by the dried material that obtains under the sintering temperature of 330 DEG C，Roasting 2h in atmosphere，Then under the sintering temperature of 430 DEG C，Roasting 2h in atmosphere，Obtain the carbon-based material of the present embodiment.
Embodiment 2
nullUnder room temperature，By solid carbon source (not containing the CNT of oxygen element)、Presoma (caprolactam) and water stirring mixing 1h，Obtain mixed material，Wherein，Carbon in described solid carbon source is 1:0.01 with the mol ratio of the nitrogen element in described presoma，Described solid carbon source is 1:20 with the weight ratio of water，Mixed material obtained above is placed in and seals in autoclave with teflon-lined，In 180 DEG C of hydrothermal treatment consists 24h at autogenous pressures，Solid in material after hydrothermal treatment consists is filtered and separates and be dried，The temperature being dried is 120 DEG C，Until the solid filtering isolated is kept substantially constant weight (the dry time is 6h)，Obtain dried material，Then by the dried material that obtains under the sintering temperature of 300 DEG C，Roasting 2h in atmosphere，Then under the sintering temperature of 400 DEG C，Roasting 2h in atmosphere，Obtain the carbon-based material of the present embodiment.
Embodiment 3
nullUnder room temperature，By solid carbon source (not containing the CNT of oxygen element)、Presoma (tetraethyl ammonium hydroxide) and water stirring mixing 3h，Obtain mixed material，Wherein，Carbon in described solid carbon source is 1:0.05 with the mol ratio of the nitrogen element in described presoma，Described solid carbon source is 1:5 with the weight ratio of water，Mixed material obtained above is placed in and seals in autoclave with teflon-lined，In 120 DEG C of hydrothermal treatment consists 48h at autogenous pressures，Solid in material after hydrothermal treatment consists is filtered and separates and be dried，The temperature being dried is 120 DEG C，Until the solid filtering isolated is kept substantially constant weight (the dry time is 6h)，Obtain dried material，Then by the dried material that obtains under the sintering temperature of 350 DEG C，Roasting 2h in atmosphere，Then under the sintering temperature of 450 DEG C，Roasting 2h in atmosphere，Obtain the carbon-based material of the present embodiment.
Embodiment 4
nullUnder room temperature，By solid carbon source (not containing the CNT of oxygen element)、Presoma (TPAOH) and water stirring mixing 5h，Obtain mixed material，Wherein，Carbon in described solid carbon source is 1:0.001 with the mol ratio of the nitrogen element in described presoma，Described solid carbon source is 1:100 with the weight ratio of water，Mixed material obtained above is placed in and seals in autoclave with teflon-lined，In 160 DEG C of hydrothermal treatment consists 12h at autogenous pressures，Solid in material after hydrothermal treatment consists is filtered and separates and be dried，The temperature being dried is 120 DEG C，Until the solid filtering isolated is kept substantially constant weight (the dry time is 6h)，Obtain dried material，Then by the dried material that obtains under the sintering temperature of 330 DEG C，Roasting 2h in atmosphere，Then under the sintering temperature of 380 DEG C，Roasting 2h in atmosphere，Obtain the carbon-based material of the present embodiment.
Embodiment 5
nullUnder room temperature，By solid carbon source (not containing the CNT of oxygen element)、Presoma (TPAOH) and water stirring mixing 6h，Obtain mixed material，Wherein，Carbon in described solid carbon source is 1:0.45 with the mol ratio of the nitrogen element in described presoma，Described solid carbon source is 1:1 with the weight ratio of water，Mixed material obtained above is placed in and seals in autoclave with teflon-lined，In 150 DEG C of hydrothermal treatment consists 24h at autogenous pressures，Solid in material after hydrothermal treatment consists is filtered and separates and be dried，The temperature being dried is 120 DEG C，Until the solid filtering isolated is kept substantially constant weight (the dry time is 6h)，Obtain dried material，Then by the dried material that obtains under the sintering temperature of 350 DEG C，Roasting 2h in atmosphere，Then under the sintering temperature of 450 DEG C，Roasting 2h in atmosphere，Obtain the carbon-based material of the present embodiment.
Embodiment 6
Using the method with embodiment 1 to prepare carbon-based material, except for the difference that, the temperature of hydrothermal treatment consists is 195 DEG C.
Embodiment 7
Using the method with embodiment 1 to prepare carbon-based material, except for the difference that, the temperature of hydrothermal treatment consists is 105 DEG C.
Embodiment 8
Use and prepare carbon-based material with the method for embodiment 1, except for the difference that, TPAOH is replaced with hexamethylene diamine and n-butylamine etc. weight mixture.
Embodiment 9
Use and prepare carbon-based material with the method for embodiment 1, except for the difference that, TPAOH is replaced with diethanolamine and aniline etc. weight mixture.
Embodiment 10
Use the method with embodiment 1 to prepare carbon-based material, except for the difference that CNT is replaced with Graphene.
Embodiment 11
Use and prepare carbon-based material with the method for embodiment 1, except for the difference that, the dried material obtained under the sintering temperature of 330 DEG C, roasting 4h in atmosphere.
Embodiment 12
Use and prepare carbon-based material with the method for embodiment 1, except for the difference that, the dried material obtained under the sintering temperature of 430 DEG C, roasting 4h in atmosphere.
Embodiment 13
Use and prepare carbon-based material with the method for embodiment 1, except for the difference that, the dried material obtained under the sintering temperature of 500 DEG C, roasting 1h in atmosphere.
Embodiment 14
Use and prepare carbon-based material with the method for embodiment 1, except for the difference that, the dried material obtained under the sintering temperature of 210 DEG C, roasting 4h in atmosphere.
Embodiment 15
Using the method with embodiment 1 to prepare carbon-based material, except for the difference that, solid carbon source is the CNT containing oxygen element, and roasting is carried out in argon.
Embodiment 16
Using the method with embodiment 1 to prepare carbon-based material, except for the difference that, solid carbon source is the CNT containing oxygen element, and roasting is carried out in atmosphere.
Embodiment 17
Using the method with embodiment 1 to prepare carbon-based material, except for the difference that, roasting is carried out in nitrogen.
Comparative example 1
Under room temperature, by solid carbon source (not containing the CNT of oxygen element), presoma (TPAOH) and water stirring mixing 6h, obtain mixed material, wherein, carbon in described solid carbon source is 1:0.03 with the mol ratio of the nitrogen element in described presoma, described solid carbon source is 1:10 with the weight ratio of water, mixed material obtained above is dried, the temperature being dried is 120 DEG C, until the solid filtering isolated is kept substantially constant weight (the dry time is 6h), obtain dried material, then by the dried material that obtains under the sintering temperature of 330 DEG C, roasting 2h in atmosphere, then under the sintering temperature of 430 DEG C, roasting 2h in atmosphere, using the material after roasting as the carbon-based material of this comparative example.
Comparative example 2
Under room temperature, by solid carbon source (not containing the CNT of oxygen element), presoma (TPAOH) and water stirring mixing 6h, obtain mixed material, wherein, carbon in described solid carbon source is 1:0.03 with the mol ratio of the nitrogen element in described presoma, described solid carbon source is 1:10 with the weight ratio of water, mixed material obtained above is placed in and seals in autoclave with teflon-lined, in 140 DEG C of hydrothermal treatment consists 24h at autogenous pressures, solid in material after hydrothermal treatment consists is filtered and separates and be dried, the temperature being dried is 120 DEG C, until the solid filtering isolated is kept substantially constant weight (the dry time is 6h), obtain dried material, then using the dried material that obtains as the carbon-based material of this comparative example.
Testing example 1
Reference literature (JianZhangetal., Science322 (2008), method in 73-77) or the method quoted, the carbon-based material obtaining embodiment 1-17 and comparative example 1-2 and the oxygen element CNT that contain/do not contains bought as mentioned above carry out elementary analysis and XPS atlas analysis.Wherein, x-ray photoelectron power spectrum is at a temperature of 300 DEG C in helium atmosphere and measures after processing 3h.Result is as shown in table 1.
In table 1, the O of XPS collection of illustrative plates row represents the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines；The C1 of XPS collection of illustrative plates row represents ratio × 100 (percent value) of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 283.8-284.2eV determines and 280.0-294.0eV determines；C2 represents amount × 100 (percent value) of the carbon that the peak in the range of the amount sum of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines and 280.0-294.0eV determines；C3 refers to the ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines.The N1 of XPS collection of illustrative plates row refers to ratio × 100 (percent value) of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 398.0-400.5eV determines and 395.0-405.0eV determines；N2 refers to ratio × 100 (percent value) of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 400.6-401.5eV determines and 395.0-405.0eV determines.W represents W500/W800× 100 (percent value).C, N and O of elementary composition row represents the elementary composition of carbon, nitrogen and oxygen respectively.CV represented when X-ray microregion element is analyzed, in the different X-ray microcells that the area on the surface of this carbon-based material is identical, and the coefficient of variation of the content of nitrogen element and oxygen element.
Table 1
Can be seen that according to the analyzing test data of embodiment 1-17 and comparative example 1-2 in table 1, it is likely to be due to add presoma and carried out hydro-thermal and roasting, making in the XPS collection of illustrative plates of carbon-based material, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.2-5；The ratio of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 398.0-400.5eV determines and 395.0-405.0eV determines is in the range of 0.5-0.1；The ratio of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 400.6-401.5eV determines and 395.0-405.0eV determines is in the range of 0-0.5；The ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 283.8-284.2eV determines and 280.0-294.0eV determines is in the range of 0.6-1；The ratio of the amount of the carbon that the peak in the range of the amount sum of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines and 280.0-294.0eV determines is in the range of 0.01-0.2；The ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines is in the range of 0.2-2；W500/W800For 0.02-0.5；In the different X-ray microcells that area is identical, the coefficient of variation of the content of N element and O element is below 20%.
Testing example 2
The carbon-based material respectively embodiment 1-17 and comparative example 1-2 of 0.25g obtained and buy as mentioned above containing oxygen element CNT and do not contain oxygen element CNT as catalyst, it is loaded in universal fixed bed miniature quartz pipe reactor, miniature quartz pipe reactor two end seal has quartz sand, under the conditions of normal pressure and 420 DEG C, by material, (volumetric concentration of butane is 1.98%, butane and oxygen molar ratio 2:3, Balance Air is nitrogen) it is 1000h in cumulative volume air speed-1Under react, according to the method in document (JianZhangetal., Science322 (2008) 73-77) after reaction 8h, measure butanes conversion, butadiene selective and total olefin selectivity, the results are shown in Table 2.
Table 2
Data according to table 2, it is found that the carbon-based material that the present invention obtains can improve hydrocarbon oxidative dehydrogenation as catalyst simultaneously and prepare selectivity and the conversion ratio of alkene.The carbon of 90-95 weight %, the nitrogen element of 0.5-4 weight % and the oxygen element of 4-8 weight % is contained at this carbon-based material of preferred carbon-based material, in x-ray photoelectron power spectrum in this carbon-based material, in the case of the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.6-1.8, it is possible to improve hydrocarbon oxidative dehydrogenation the most simultaneously and prepare selectivity and the conversion ratio of alkene.Further, the temperature in preferred hydrothermal treatment consists is 120-180 DEG C and in the case of sintering temperature is 300-450 DEG C, it is possible to improves oxidative dehydrogenation the most simultaneously and prepares selectivity and the conversion ratio of alkene.
Testing example 3
The carbon-based material respectively embodiment 1-17 and comparative example 1-2 of 0.25g obtained and buy as mentioned above containing oxygen element CNT and do not contain oxygen element CNT as catalyst, it is loaded in universal fixed bed miniature quartz pipe reactor, miniature quartz pipe reactor two end seal has quartz sand, under the conditions of normal pressure and 450 DEG C, by material, (concentration of propane is 5.88 volume %, propane and oxygen molar ratio 1:1, Balance Air is nitrogen, accounts for surplus) it is 100h in cumulative volume air speed-1Under react, according to the method in document (JianZhangetal., Science322 (2008), 73-77) after reaction 8h, measure conversion of propane, Propylene Selectivity and total olefin selectivity, the results are shown in Table 3.
Table 3
Data according to table 3, it is found that the carbon-based material that the present invention obtains can improve hydrocarbon oxidative dehydrogenation as catalyst simultaneously and prepare selectivity and the conversion ratio of alkene.The carbon of 90-95 weight %, the nitrogen element of 0.5-4 weight % and the oxygen element of 4-8 weight % is contained at this carbon-based material of preferred carbon-based material, in x-ray photoelectron power spectrum in this carbon-based material, in the case of the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.6-1.8, it is possible to improve hydrocarbon oxidative dehydrogenation the most simultaneously and prepare selectivity and the conversion ratio of alkene.Further, the temperature in preferred hydrothermal treatment consists is 120-180 DEG C and in the case of sintering temperature is 300-450 DEG C, it is possible to improves oxidative dehydrogenation the most simultaneously and prepares selectivity and the conversion ratio of alkene.
Testing example 4
Respectively the carbon-based material that embodiment 1-17 and comparative example 1-2 of 0.25g obtain is bought as mentioned above containing oxygen element CNT and do not contain oxygen element CNT as catalyst, it is loaded in universal fixed bed miniature quartz pipe reactor, miniature quartz pipe reactor two end seal has quartz sand, under the conditions of normal pressure and 350 DEG C, by material, (concentration of ethylbenzene is 1.98 volume %, ethylbenzene and oxygen molar ratio 0.5:1, Balance Air is nitrogen, accounts for surplus) it is 2000h in cumulative volume air speed-1Under react, after reaction 8h, the method in reference literature (Angew.Chem.Int.Ed.48 (2009) 6913), measures conversion of ethylbenzene and selectivity of styrene, and the results are shown in Table 4.
Table 4
Data according to table 4, it is found that the carbon-based material that the present invention obtains can improve hydrocarbon oxidative dehydrogenation as catalyst simultaneously and prepare selectivity and the conversion ratio of alkene.The carbon of 90-95 weight %, the nitrogen element of 0.5-4 weight % and the oxygen element of 4-8 weight % is contained at this carbon-based material of preferred carbon-based material, in x-ray photoelectron power spectrum in this carbon-based material, in the case of 533.1-533.5eV the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of determines and 531.8-532.2eV determines is in the range of 0.6-1.8, it is possible to improve hydrocarbon oxidative dehydrogenation the most simultaneously and prepare selectivity and the conversion ratio of alkene.Further, the temperature in preferred hydrothermal treatment consists is 120-180 DEG C and in the case of sintering temperature is 300-450 DEG C, it is possible to improves oxidative dehydrogenation the most simultaneously and prepares selectivity and the conversion ratio of alkene.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can be carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary repetition, various possible compound modes are illustrated by the present invention the most separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (23)

1. a carbon-based material, it is characterised in that: on the basis of the gross weight of this carbon-based material, this carbon-based material contains the carbon of 80-98.9 weight %, the nitrogen element of 0.1-7 weight % and the oxygen element of 1-15 weight %；Wherein, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.2-5.
Carbon-based material the most according to claim 1, wherein, on the basis of the gross weight of this carbon-based material, this carbon-based material contains the carbon of 85-97 weight %, the nitrogen element of 0.2-5 weight % and the oxygen element of 2-10 weight %, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.5-2.
Carbon-based material the most according to claim 2, wherein, on the basis of the gross weight of this carbon-based material, this carbon-based material contains the carbon of 90-95 weight %, the nitrogen element of 0.5-4 weight % and the oxygen element of 4-8 weight %, in x-ray photoelectron power spectrum in this carbon-based material, the ratio of the amount of the oxygen element that the peak in the range of the amount of the oxygen element that the peak in the range of 533.1-533.5eV determines and 531.8-532.2eV determines is in the range of 0.6-1.8.
4. according to the carbon-based material described in any one in claim 1-3, wherein, in the x-ray photoelectron power spectrum of described carbon-based material, the ratio of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 398.0-400.5eV determines and 395.0-405.0eV determines is in the range of 0.5-1；
The ratio of the amount of the nitrogen element that the peak in the range of the amount of the nitrogen element that the peak in the range of 400.6-401.5eV determines and 395.0-405.0eV determines is in the range of 0-0.5.
5. according to the carbon-based material described in any one in claim 1-3, wherein, in the x-ray photoelectron power spectrum of this carbon-based material, the ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 283.8-284.2eV determines and 280.0-294.0eV determines is in the range of 0.6-1；
The ratio of the amount of the carbon that the peak in the range of the amount sum of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines and 280.0-294.0eV determines is in the range of 0.01-0.2；
The ratio of the amount of the carbon that the peak in the range of the amount of the carbon that the peak in the range of 286.2-286.6eV determines and 288.6-289.0eV determines is in the range of 0.2-2.
6. according to the carbon-based material described in any one in claim 1-3, wherein, in the different X-ray microcells that area on the surface of this carbon-based material is identical, the coefficient of variation each comfortable less than 20% of the content of nitrogen element and oxygen element.
7. according to the carbon-based material described in any one in claim 1-3, wherein, the W of described carbon-based material500/W800In the range of 0.02-0.5；Wherein, W800Referring under the Elevated Temperature Conditions of air atmosphere and the initial temperature of 25 DEG C and 10 DEG C/min, described carbon-based material weight at 800 DEG C is relative to the slip of the weight at 400 DEG C, W500Referring under the Elevated Temperature Conditions of air atmosphere and the initial temperature of 25 DEG C and 10 DEG C/min, described carbon-based material weight at 500 DEG C is relative to the slip of the weight at 400 DEG C.
8. according to the carbon-based material described in any one in claim 1-3, wherein, at least one during the configuration of this carbon-based material includes the configuration of CNT, Graphene, fullerene, nano carbon particle, activated carbon, thin layer graphite, carbon nano-fiber and Nano diamond.
9. the method preparing carbon-based material, it is characterised in that: the method comprises the steps: that solid carbon source, presoma and water are mixed by (1), obtains mixed material；Wherein, described presoma contains organic base, and described organic base includes organic amine and/or quaternary ammonium base；(2) the mixed material that step (1) obtains is carried out hydrothermal treatment consists, obtain the material after hydrothermal treatment consists；And separate the solid in the material after hydrothermal treatment consists；(3) solid in the material after hydrothermal treatment consists step (2) obtained carries out roasting.
Method the most according to claim 9, wherein, the carbon in described solid carbon source is 1:(0.001-0.5 with the mol ratio of the nitrogen element in described organic base)；Carbon in described solid carbon source is 1:(1-100 with the weight ratio of water).
11. methods according to claim 10, wherein, the carbon in described solid carbon source is 1:(0.01-0.05 with the mol ratio of the nitrogen element in described organic base)；Carbon in described solid carbon source is 1:(5-20 with the weight ratio of water).
12. methods according to claim 9, wherein, the temperature carrying out hydrothermal treatment consists is 105-200 DEG C；The time carrying out hydrothermal treatment consists is 0.5-96h；The temperature of roasting is 200-500 DEG C, and the time of roasting is 0.5-48h.
13. methods according to claim 12, wherein, the temperature carrying out hydrothermal treatment consists is 120-180 DEG C；The temperature of roasting is 300-450 DEG C.
14. methods according to claim 9, wherein, roasting is carried out in the gas containing oxygen, and on the basis of the cumulative volume containing the gas of oxygen, the content of the oxygen in the gas containing oxygen is 2-25 volume %.
15. methods according to claim 9, wherein, at least one in CNT, Graphene, fullerene, nano carbon particle, thin layer graphite, activated carbon, carbon nano-fiber and Nano diamond of described carbon source.
16. methods according to claim 9, wherein, described organic amine includes at least one in aliphatic amine, hydramine, amide, aliphatic cyclic amine and aromatic amine；At least one in ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine and hexamethylene diamine of described aliphatic amine；At least one in monoethanolamine, diethanolamine and triethanolamine of described hydramine；At least one in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH and TBAH of described quaternary ammonium base；At least one in Methanamide, acetamide, propionic acid amide., butyramide, isobutyramide, acrylamide, polyacrylamide, caprolactam, dimethylformamide and dimethyl acetylamide of described amide；At least one in triethylenediamine, diethylenetriamines, hexamethylenetetramine, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine and cyclohexylamine of described aliphatic cyclic amine；Described aromatic amine selected from aniline, diphenylamines, benzidine, o-phenylenediamine, m-diaminobenzene., p-phenylenediamine, o-toluidine, m-toluidine, open-chain crown ether, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2, at least one in 4,6-trimethylaniline, o ethyl aniline, N-butylaniline and 2,6-diethylaniline.
The carbon-based material that in 17. claim 9-16, method described in any one prepares.
Carbon-based material described in any one purposes in catalytic hydrocarbon oxidation reaction in 18. claim 1-8 and 17.
The method of 19. 1 kinds of hydrocarbon oxidations, the method includes: under hydrocarbon catalysis oxidizing condition, will contact with catalyst with the gas of oxygen containing hydrocarbon；It is characterized in that: described catalyst includes the carbon-based material in claim 1-8 and 17 described in any one.
20. methods according to claim 19, wherein, the carbon number of described hydrocarbon is 2-15, and described hydrocarbon includes at least one in alkane, alkene and the aromatic hydrocarbon containing alkyl；Described alkyl contains at least two carbon atom.
21. methods according to claim 20, wherein, described hydrocarbon includes at least one in butane, 1-butylene, ethylbenzene, propane, ethane and pentane.
22. methods according to claim 19, wherein, hydrocarbon is (0.1-10) with the mol ratio of oxygen: 1.
23. methods according to claim 19, wherein, hydrocarbon catalysis oxidizing condition includes: Contact Temperature is 300-600 DEG C, and contact pressure is 0.1-40MPa；Calculating with the cumulative volume of the gas containing hydrocarbon and oxygen, gas is 1-6000h by the volume space velocity of catalyst-1。
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