CN105820023B - A kind of method of hydrocarbon oxidation - Google Patents
A kind of method of hydrocarbon oxidation Download PDFInfo
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- CN105820023B CN105820023B CN201510703667.2A CN201510703667A CN105820023B CN 105820023 B CN105820023 B CN 105820023B CN 201510703667 A CN201510703667 A CN 201510703667A CN 105820023 B CN105820023 B CN 105820023B
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 97
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 97
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000007254 oxidation reaction Methods 0.000 title abstract description 20
- 230000003647 oxidation Effects 0.000 title abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 211
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 158
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 153
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000001301 oxygen Substances 0.000 claims abstract description 112
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 112
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims description 71
- 239000007787 solid Substances 0.000 claims description 68
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- 238000005119 centrifugation Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229940047889 isobutyramide Drugs 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
Abstract
本发明公开了一种烃催化脱氢的方法，该方法包括：在烃催化脱氢条件下，将含有烃的气体与催化剂接触；所述催化剂含有碳基材料；以所述碳基材料的总重量为基准，该碳基材料含有70‑99.75重量％的碳元素、0.05‑10重量％的氮元素和0.2‑20重量％的氧元素。本发明能够同时提高烃氧化制备烯烃的选择性和转化率。The invention discloses a method for catalytic dehydrogenation of hydrocarbons. The method comprises: contacting a gas containing hydrocarbons with a catalyst under the conditions of catalytic dehydrogenation of hydrocarbons; the catalyst contains carbon-based materials; On a weight basis, the carbon-based material contains 70-99.75 wt % of carbon element, 0.05-10 wt % of nitrogen element and 0.2-20 wt % of oxygen element. The present invention can simultaneously improve the selectivity and conversion rate of hydrocarbon oxidation to prepare olefins.
Description
Technical field
The present invention relates to technical field of material chemistry, and in particular, to a kind of method of hydrocarbon catalytic dehydrogenation.
Background technique
Carbon-based material includes carbon nanotube, graphene, fullerene, carbon nano-fiber and Nano diamond etc..Carbon substrate
Material can be used as the catalysis material of oxidizing hydrocarbons especially alkane, such as: there are document (Applied Catalysis, 29 (1987)
311-326) reporting becomes styrene for oxidative dehydrogenation of ethylbenzene for catalyst using active carbon, and there are also document (ACTA
PHYSICA POLONIC A, Vol.118, (2010), 459-464) to report using active carbon be that catalyst converts normal butane
For butylene and butadiene.
Studies have shown that miscellaneous if modifying oxygen-containing, nitrogen etc. on nano-carbon material (such as carbon nanotubes and graphene) surface
The saturation of atom and unsaturation functional group, thus it is possible to vary the catalytic activity of nano-carbon material, it such as can be by nano-carbon material
It carries out oxidation processes realization and introduces oxygen atom in nano-carbon material, to increase containing for oxygen-containing functional group in nano-carbon material
Amount.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or strong oxidizing solution (such as H2O2、KMnO4) in into
Row back flow reaction can also assist carrying out microwave heating or sonic oscillation while back flow reaction, to enhance oxidation reaction
Effect.
It may skeleton knot to nano-carbon material but carry out back flow reaction in strong acid and/or strong oxidizing solution
Structure has an adverse effect, or even destroys the skeleton structure of nano-carbon material.Such as: nano-carbon material is aoxidized with nitric acid,
Although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, easily cause nano-carbon material be cut off and/or
The defects of graphite network structure position is obviously increased, so as to reduce the performance of nano-carbon material, such as thermal stability.In addition,
By carrying out back flow reaction in strong acid and/or strong oxidizing solution, when introducing oxygen atom, the introduction volume of oxygen atom is to reaction
The dependence of operating condition is high, and fluctuation range is wider, is not easy accurately to control.
Alkene especially alkadienes and aromatic olefin are important industrial chemicals, such as butadiene is production synthetic rubber
The primary raw material of (such as butadiene-styrene rubber, butadiene rubber, nitrile rubber, neoprene).It is raw using styrene and butadiene copolymer
It produces the extensive resin of various uses (such as ABS resin, SBS resin, BS resin and MBS resin), makes butadiene in production of resins
Gradually occupy an important position.In addition, butadiene can also be used to produce ethylidene norbornene (EP rubbers Third monomer), Isosorbide-5-Nitrae-fourth
Glycol, adiponitrile (nylon66 fiber monomer), sulfolane, anthraquinone and tetrahydrofuran etc., therefore butadiene is also important basic chemical industry
Raw material.In addition, styrene is also important the monomer of synthetic rubber and plastics, can be used to produce butadiene-styrene rubber, polystyrene
With foamed polystyrene etc.；It is also used for being copolymerized the engineering plastics for manufacturing a variety of different purposes from other monomers.Such as with acrylonitrile, fourth
Diene, which is copolymerized, is made ABS resin, is widely used in various household electrical appliance and industrial；It is with SAN resin made from acrylonitrile compolymer
Impact resistance, bright in color resin；It is a kind of thermoplastic elastomer with SBS obtained by butadiene copolymer, is widely used as polychlorostyrene second
Alkene, polyacrylic modifying agent etc..Styrene is handed over mainly for the production of styrene series resin and butadiene-styrene rubber, and production ion
One of the raw material of resin and pharmaceuticals is changed, in addition, styrene can also be used in the industries such as pharmacy, dyestuff, pesticide and ore dressing.
Hydrocarbon oxidative dehydrogenation is to prepare the important method of alkene, such as butane oxidation dehydrogenation can be generated 1- butylene, 1- fourth
Alkene oxidative dehydrogenation can generate 1,3- butadiene in turn；Vinylbenzene oxidative dehydrogenation can also be generated into styrene.Hydrocarbon oxidative dehydrogenation
When preparing alkene, there is selectivity and conversion ratio to be generally difficult to the problem of improving simultaneously.
Summary of the invention
The purpose of the present invention is in the presence of overcoming hydrocarbon oxidative dehydrogenation to prepare alkene selectivity and conversion ratio be generally difficult to
The problem of improving simultaneously, provide it is a kind of can catalytic hydrocarbon oxidative dehydrogenation prepare alkene and obtain simultaneously highly selective and conversion ratio
The purposes of carbon-based material, the preparation method of the carbon-based material and the carbon-based material.
It was found by the inventors of the present invention that using presoma and aqueous hydrogen peroxide solution containing organic amine and/or quaternary ammonium base
Hydro-thermal process is carried out to carbon source material, by the solid separation in the material after hydro-thermal process and after drying and roasting, is capable of forming
The activity of alkene is prepared with catalytic hydrocarbon oxidation and obtains highly selective and conversion ratio carbon-based material simultaneously, results in this
Invention.
The present invention provides the methods of hydrocarbon catalytic dehydrogenation, this method comprises: will contain hydrocarbon under the conditions of hydrocarbon catalytic dehydrogenation
Gas is contacted with catalyst；Wherein, the catalyst contains carbon-based material；On the basis of the total weight of the carbon-based material, institute
State the oxygen that carbon-based material contains the carbon of 70-99.75 weight %, the nitrogen of 0.05-10 weight % and 0.2-20 weight %
Element；Wherein, in the x-ray photoelectron spectroscopy of the carbon-based material, the oxygen element of the peak determination within the scope of 533.1-533.5eV
The ratio of the amount for the oxygen element that amount is determined with the peak within the scope of 531.8-532.2eV is in the range of 0.2-5.
Through the above technical solutions, the present invention can improve the selectivity and conversion ratio that hydrocarbon oxidation prepares alkene simultaneously.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of methods of hydrocarbon catalytic dehydrogenation, this method comprises: will contain under the conditions of hydrocarbon catalytic dehydrogenation
The gas of hydrocarbon is contacted with catalyst；Wherein, the catalyst contains carbon-based material；Using the total weight of the carbon-based material as base
Standard, the carbon-based material contain the carbon of 70-99.75 weight %, the nitrogen of 0.05-10 weight % and 0.2-20 weight %
Oxygen element；Wherein, in the x-ray photoelectron spectroscopy of the carbon-based material, the oxygen that the peak within the scope of 533.1-533.5eV determines is first
The ratio of the amount for the oxygen element that the amount of element and the peak within the scope of 531.8-532.2eV determine is in the range of 0.2-5.
In the present invention, from the point of view of the catalytic capability for further increasing the carbon-based material, it is preferable that the carbon substrate
In the x-ray photoelectron spectroscopy of material, the amount and 531.8-532.2eV of the oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak in range determines is in the range of 0.5-2.It is further preferred that the X in the carbon-based material
In X-ray photoelectron spectroscopy X, within the scope of the amount and 531.8-532.2eV of the oxygen element that the peak within the scope of 533.1-533.5eV determines
Peak determine oxygen element amount ratio in the range of 0.6-1.8.By the face of the O1s spectral peak in x-ray photoelectron spectroscopy
Product can determine the total amount of O element in carbon-based material.Wherein, the amount for the oxygen element that the peak within the scope of 533.1-533.5eV determines
It can indicate the Relative mole content of C-O group in carbon-based material, the oxygen element that the peak within the scope of 531.8-532.2eV determines
Amount can indicate 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 be by carbon-based material 300 DEG C at a temperature of in helium atmosphere
After middle processing 3h, the numerical value measured using X-ray photoelectron spectroscopy, measuring method for known to those skilled in the art, this
Place does not repeat.
In the present invention, x-ray photoelectron spectroscopy map refers to that XPS map, XPS map can be normal according to instrument analysis field
The method of rule measures to obtain, and the calculating of the amount for the element that peak in x-ray photoelectron spectroscopy in particular range determines can be according to
The method of instrument analysis field routine is calculated, such as can be measured according to the specification of x-ray photoelectron spectroscopy
And quantitative calculating is carried out using the data software that x-ray photoelectron spectroscopy carries, the present invention does not have particular/special requirement to this.This hair
In bright, x-ray photoelectron spectroscopy data be sample 300 DEG C at a temperature of handle 3h in helium atmosphere after measure.Its
In, when the content value of measurement is lower than 0.1 weight %, the content of the element is denoted as 0.
In the present invention, from the point of view of the catalytic capability for further increasing the carbon-based material, it is preferable that carbon-based with this
On the basis of the total weight of material, the carbon-based material contain the carbon of 80-97 weight %, 0.2-8 weight % nitrogen and
The oxygen element of 0.5-15 weight %.In order to further improve the catalytic capability of the carbon-based material, it is highly preferred that the carbon substrate
Expect the carbon containing 85-95 weight %, the nitrogen of 0.5-5 weight % and the oxygen element of 2-10 weight %.
Method in accordance with the invention it is preferred that in the x-ray photoelectron spectroscopy of the carbon-based material, 398.0-400.5eV
The ratio of the amount for the nitrogen that the amount for the nitrogen that peak in range determines and the peak within the scope of 395.0-405.0eV determine exists
In the range of 0.5-1；More preferably in the range of 0.6-0.9.It can be with by the area of the N1s spectral peak in x-ray photoelectron spectroscopy
Determine the total amount of N element in carbon-based material, generally, the amount for the nitrogen that the peak within the scope of 395.0-405.0eV determines is basic
It can indicate the Relative mole content of nitrogen contained by whole nitrogen-containing groups in carbon-based material.Wherein, within the scope of 398.0-400.5eV
The amount of nitrogen that determines of peak can indicate (such as pyrroles, pyridine, amide and the table of nitrogen contained by NH group in carbon-based material substantially
Nitrogen in the amino of face) Relative mole content.
Method in accordance with the invention it is preferred that in the x-ray photoelectron spectroscopy of the carbon-based material, 400.6-401.5eV
The ratio of the amount for the nitrogen that the amount for the nitrogen that peak in range determines and the peak within the scope of 395.0-405.0eV determine is in 0-
In the range of 0.5；More preferably in the range of 0.1-0.4.Wherein, the nitrogen that the peak within the scope of 400.6-401.5eV determines
Amount can indicate the Relative mole content of contained graphite mould nitrogen in carbon-based material, the peak within the scope of 395.0-405.0eV substantially
The amount of determining nitrogen can indicate the Relative mole content of nitrogen contained by whole nitrogen-containing groups of carbon-based material substantially.
Method in accordance with the invention it is preferred that in the x-ray photoelectron spectroscopy of the carbon-based material, 283.8-284.2eV
The ratio of the amount for the carbon that the amount for the carbon that peak in range determines and the peak within the scope of 280.0-294.0eV determine exists
In the range of 0.6-1；More preferably in the range of 0.7-0.9.It can be with by the area of the C1s spectral peak in x-ray photoelectron spectroscopy
Determine the total amount of C element in carbon-based material, generally, the amount for the carbon that the peak within the scope of 280.0-294.0eV determines is basic
It can indicate the Relative mole content of carbon contained by whole carbon-containing groups of carbon-based material.Wherein, within the scope of 283.8-284.2eV
The amount of carbon that determines of peak can indicate the Relative mole content of contained graphitic carbon in carbon-based material substantially.
Method in accordance with the invention it is preferred that in the x-ray photoelectron spectroscopy of the carbon-based material, 286.2-286.6eV
The sum of amount of carbon that the amount for the carbon that peak in range determines and the peak within the scope of 288.6-289.0eV determine with
The ratio of the amount for the carbon that peak within the scope of 280.0-294.0eV determines is in the range of 0.02-0.2；More preferably in 0.05-
In the range of 0.15.The total amount of C element in carbon-based material can be determined by the area of the C1s spectral peak in x-ray photoelectron spectroscopy,
Generally, the amount for the carbon that the peak within the scope of 280.0-294.0eV determines can indicate that the whole of carbon-based material is carbon containing substantially
The Relative mole content of carbon contained by group.Wherein, the amount for the carbon that the peak within the scope of 286.2-286.6eV determines substantially may be used
To indicate the Relative mole content of carbon contained by C-O group in carbon-based material (carbon in such as carboxyl, acid anhydride and ester), 288.6-
The amount for the carbon that peak within the scope of 289.0eV determines can indicate carbon (such as hydroxyl contained by C=O group in carbon-based material substantially
Carbon in base and ether) Relative mole content.
Method in accordance with the invention it is preferred that in the x-ray photoelectron spectroscopy of the carbon-based material, 286.2-286.6eV
The ratio of the amount for the carbon that the amount for the carbon that peak in range determines and the peak within the scope of 288.6-289.0eV determine exists
In the range of 0.3-2；More preferably in the range of 0.6-1.7.
In the present invention, position combination as corresponding to the summit at the peak at above-mentioned each peak be can determine that, by mentioned earlier range
Determining peak refer to combination corresponding to summit can peak within that range, in the range may include a peak, can also
To include more than two peaks.Such as: the peak within the scope of 288.6-289.0eV refers to that combination corresponding to summit can be in
Peak in the range of 288.6-289.0eV.
Method in accordance with the invention it is preferred that the W of carbon-based material500/W800It can be in the range of 0.02-0.5；It is preferred that
The W of the ground carbon-based material500/W800In the range of 0.05-0.25.Under the preferable case, the carbon-based material is being used as
Better catalytic effect can be obtained when catalyst can obtain more when being especially used as the catalyst of hydrocarbons dehydrogenation reaction
High feed stock conversion and selectivity of product.Wherein, W800Refer to air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min
Under Elevated Temperature Conditions, slip of the carbon-based material in the weight at 800 DEG C relative to the weight at 400 DEG C is that is, (described carbon-based
Material at 400 DEG C weight and the carbon-based material in the weight difference at 800 DEG C) the weight of/carbon-based material at 400 DEG C
Amount, W500Under the Elevated Temperature Conditions for referring to air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min, the carbon-based material is 500
Slip of the weight relative to the weight at 400 DEG C at DEG C, i.e. (weight of the carbon-based material at 400 DEG C and the carbon
Sill is in the weight difference at 500 DEG C) the weight of/carbon-based material at 400 DEG C.
Method in accordance with the invention it is preferred that the distribution uniform of nitrogen and oxygen element in carbon-based material.Such as logical
When crossing the analysis of X-ray microregion element, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen and oxygen element
Content the coefficient of variation 20% hereinafter, more preferably 15% hereinafter, particularly preferably 10% hereinafter, particularly preferably existing
5% or less.Wherein, X-ray microcell refers to the observation area selected when carrying out the analysis of X-ray microregion element.Wherein, the coefficient of variation
Concept refer to the standard deviation of multiple measured values and the percentage of their average, i.e. (standard deviation SD/ is flat by coefficient of variation CV=
Mean value MN) × 100%.Wherein, the method for carrying out the analysis of X-ray microregion element can be surveyed according to the method for instrument analysis field routine
Surely it obtains, such as specific test method may include: the carbon substrate with energy depressive spectroscopy along length in the range of 25-250nm
The length direction of material such as carbon nanotube is scanned, determine respectively concentration on the length direction of nitrogen-atoms and oxygen atom or
Content (5 concentration of measurement or content), is made five effective samples by same nano-carbon material and is scanned Electronic Speculum-power spectrum respectively
Analysis, each sample take 5 different carbon nanotubes to be scanned, and nitrogen-atoms and oxygen atom respectively obtain 25 concentration or content number
According to calculating the coefficient of variation of corresponding nitrogen-atoms and oxygen atom.Herein the coefficient of variation refer to 25 measured values standard deviation and they
Average percentage, i.e. coefficient of variation CV=(standard deviation SD/ average value MN) × 100%.In order to preferably reflect carbon
The distributing homogeneity of nitrogen and oxygen element in sill, the surface of selected carbon-based material in the analysis of X-ray microregion element
Area can be 10-250nm2, preferably 20-200nm2。
Wherein, the structural form of the carbon-based material may include carbon nanotube, graphene, fullerene, nano carbon particle,
Active carbon, thin layer graphite, carbon nano-fiber and Nano diamond at least one of structural form structure.
Wherein, the carbon-based material can for carbon nanotube, graphene, fullerene, nano carbon particle, active carbon,
One of carbon-based material of thin layer graphite, carbon nano-fiber and nano diamond structure or a variety of mixtures.Wherein, described
Carbon-based material, which has, is selected from carbon nanotube, graphene, fullerene, nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber
With the structure of Nano diamond.
Wherein, the carbon atom number of the hydrocarbon can be 2-15, and the hydrocarbon includes alkane, alkene and the fragrance containing alkyl
At least one of hydrocarbon；The alkyl contains at least two carbon atoms.
Wherein, the hydrocarbon may include ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, 11
At least one of alkane, dodecane, ethylbenzene, phenylpropyl alcohol alkane, benzene butane, benzene pentane and benzene hexane；Preferably include butane, 1- butylene,
At least one of ethylbenzene, propane, ethane and pentane.
Wherein, the gas containing hydrocarbon also contains oxygen, and the molar ratio of hydrocarbon and oxygen can become in a big way
Change, such as can be (0.01-100): 1, preferably (0.1-10): 1, more preferably (0.5-5): 1.
Wherein, the gas containing hydrocarbon can also contain carrier gas, and the carrier gas selects to lead for hydrocarbon oxidative dehydrogenation
The selection of domain routine, such as the carrier gas contain nitrogen, CO2At least one of with vapor.
Wherein, in the gas containing hydrocarbon, the total concentration of hydrocarbon and oxygen can be the choosing of hydrocarbon oxidative dehydrogenation field routine
It selects, such as can be 0.5-70 volume %；It is preferred that the total concentration of hydrocarbon and oxygen is 1-50 body in the gas containing hydrocarbon
Product %, more preferably 3-30 volume %.
Wherein, hydrocarbon catalytic dehydrogenation condition can be the selection of hydrocarbon oxidative dehydrogenation field routine, such as hydrocarbon catalytic dehydrogenation condition
It may include: that Contact Temperature can be for 200-650 DEG C, preferably 300-600 DEG C, more preferably 350-550 DEG C are further excellent
It is selected as 400-450 DEG C；Pressure can be 0.05-80MPa, preferably 0.1-40MPa, more preferably 0.1-20MPa, further
Preferably 0.1-5MPa；It is calculated with the total volume of the gas containing hydrocarbon, the volume space velocity that gas passes through catalyst can be 0.1-
10000h-1, preferably 1-6000h-1, more preferably 5-5000h-1, it is still more preferably 10-4000h-1。
Wherein, the contact of hydrocarbon catalytic dehydrogenation can be carried out in fixed bed reactors and/or fluidized-bed reactor, preferably solid
It carries out in fixed bed reactor, is carried out more preferably in tubular fixed-bed reactor.Preferably, the carbon-based material is as catalyst
It is filled in the tubular fixed-bed reactor, the gas containing hydrocarbon is by the tubular fixed-bed reactor to be connect
Touching.
Wherein, as particularly preferred embodiment of the invention, the hydrocarbon includes butane；With the gross weight of the carbon-based material
On the basis of amount, the carbon-based material contains the carbon of 85-95 weight %, the nitrogen of 0.5-5 weight % and 2-10 weight %
Oxygen element；Contain the structure of carbon nanotube in the structure of the carbon-based material；The gas containing hydrocarbon also contains oxygen, described
The molar ratio of hydrocarbon and oxygen is (0.1-10): 1；In the gas containing hydrocarbon, the total concentration of the hydrocarbon and oxygen is 1-50 body
Product %；Hydrocarbon catalytic dehydrogenation condition includes: that Contact Temperature is 350-500 DEG C, pressure 0.1-5MPa；With the total of the gas containing hydrocarbon
Volume calculates, and the volume space velocity that gas passes through catalyst is 10-2000h-1。
Wherein, as particularly preferred embodiment of the invention, the hydrocarbon includes propane；With the gross weight of the carbon-based material
On the basis of amount, the carbon-based material contains the carbon of 85-95 weight %, the nitrogen of 0.5-5 weight % and 2-10 weight %
Oxygen element；Contain the structure of carbon nanotube in the structure of the carbon-based material；The gas containing hydrocarbon also contains oxygen, described
The molar ratio of hydrocarbon and oxygen is (0.05-2): 1；In the gas containing hydrocarbon, the total concentration of the hydrocarbon and oxygen is 10-30 body
Product %；Hydrocarbon catalytic dehydrogenation condition includes: that Contact Temperature is 400-550 DEG C, pressure 0.1-5MPa；With the total of the gas containing hydrocarbon
Volume calculates, and the volume space velocity that gas passes through catalyst is 5-1000h-1。
Wherein, as particularly preferred embodiment of the invention, the hydrocarbon includes ethylbenzene；The carbon-based material contains 85-
The oxygen element of the carbon of 95 weight %, the nitrogen of 0.5-5 weight % and 2-10 weight %；Contain in the structure of the carbon-based material
There is the structure of carbon nanotube；Hydrocarbon catalytic dehydrogenation condition includes: that Contact Temperature is 300-500 DEG C, pressure 0.1-5MPa；To contain
The total volume of the gas of hydrocarbon calculates, and the volume space velocity that gas passes through catalyst is 10-4000h-1.It is highly preferred that described contain hydrocarbon
Gas also contain oxygen, the molar ratio of the hydrocarbon and oxygen is (0.1-10): 1；In the gas containing hydrocarbon, the hydrocarbon and
The total concentration of oxygen is 1-50 volume %.
A kind of embodiment according to the present invention, the present invention provides a kind of method of hydrocarbon catalytic dehydrogenation, this method includes
Following steps: (1) solid carbon source, presoma and aqueous hydrogen peroxide solution are mixed, obtains mixed material；Wherein, described
Presoma contains organic alkali source, and organic alkali source includes machine amine and/or quaternary ammonium base；(2) after the mixing for obtaining step (1)
Material carry out hydro-thermal process, the material after obtaining hydro-thermal process；And separate the solid in the material after hydro-thermal process；(3)
Solid in material after hydro-thermal process that step (2) obtains is roasted, carbon-based material is obtained；(4) in hydrocarbon catalytic dehydrogenation
Under the conditions of, the gas containing hydrocarbon is contacted with catalyst；The catalyst contains the carbon-based material that step (3) obtains.
A kind of embodiment according to the present invention, the carbon-based material can be by the preparation method systems that include the following steps
It is standby to obtain: (1) solid carbon source, presoma and aqueous hydrogen peroxide solution to be mixed, obtain mixed material；Wherein, before described
It drives body and contains organic alkali source, organic alkali source includes machine amine and/or quaternary ammonium base；(2) step (1) is obtained mixed
Material carries out hydro-thermal process, the material after obtaining hydro-thermal process；And separate the solid in the material after hydro-thermal process；(3) will
The solid in material after the hydro-thermal process that step (2) obtains is roasted.
According to the method for the present invention, wherein the mixed time and temperature does not have particular/special requirement, can become in a big way
Change, such as the mixed time can be 0.5-72h, mixed temperature can be 20-80 DEG C.
Wherein, the carbon-based material that above-mentioned preparation method obtains can the carbon containing 70-99.75 weight %, 0.05-10
The nitrogen of weight % and the oxygen element of 0.2-20 weight % preferably comprise carbon, the 0.2-8 weight % of 80-97 weight %
Nitrogen and 0.5-15 weight % oxygen element, the further preferably nitrogen of the carbon of 85-95 weight %, 0.5-5 weight %
The oxygen element of element and 2-10 weight %.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that above-mentioned preparation method obtains, 533.1-533.5eV range
The amount for the oxygen element that interior peak determines with the ratio of the amount for the oxygen element that the peak within the scope of 531.8-532.2eV determines is in 0.2-5
In the range of.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that above-mentioned preparation method obtains, 398.0-400.5eV range
The ratio of the amount for the nitrogen that the amount for the nitrogen that interior peak determines and the peak within the scope of 395.0-405.0eV determine is in 0.5-1
In the range of.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that above-mentioned preparation method obtains, 400.6-401.5eV range
The ratio of the amount for the nitrogen that the amount for the nitrogen that interior peak determines and the peak within the scope of 395.0-405.0eV determine is in 0-0.5
In the range of.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that above-mentioned preparation method obtains, 283.8-284.2eV range
The ratio of the amount for the carbon that the amount for the carbon that interior peak determines and the peak within the scope of 280.0-294.0eV determine is in 0.6-1
In the range of.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that above-mentioned preparation method obtains, 286.2-286.6eV range
The sum of amount of carbon that the amount for the carbon that interior peak determines and the peak within the scope of 288.6-289.0eV determine and 280.0-
The ratio of the amount for the carbon that peak within the scope of 294.0eV determines is in the range of 0.02-0.2.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that above-mentioned preparation method obtains, 286.2-286.6eV range
The ratio of the amount for the carbon that the amount for the carbon that interior peak determines and the peak within the scope of 288.6-289.0eV determine is in 0.3-2
In the range of.
The carbon-based material that above-mentioned preparation method obtains, weightlessness of the carbon-based material in 400-800 DEG C of temperature range
Rate is W800, the weight-loss ratio in 400-500 DEG C of temperature range is W500, W500/W800It is preferred that in the range of 0.02-0.5, more
It is preferred that in the range of 0.05-0.25.Better catalytic effect can be obtained in this way, be especially used as hydrocarbons dehydrogenation reaction
Catalyst when, higher feed stock conversion and selectivity of product can be obtained.In the present invention, the weight-loss ratio is in air atmosphere
Measurement, initial temperature are 25 DEG C, and heating rate is 10 DEG C/min.
The carbon-based material that above-mentioned preparation method obtains, the distribution uniform of nitrogen therein and oxygen element.Such as passing through X
When light microregion element is analyzed, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen and oxygen element contain
The coefficient of variation of amount is below 20%.Wherein, X-ray microcell refers to the area of observation coverage selected when carrying out the analysis of X-ray microregion element
Domain.Wherein, the concept of the coefficient of variation refers to the standard deviation of multiple measured values and the percentage of their average, the i.e. coefficient of variation
CV=(standard deviation SD/ average value MN) × 100%.Wherein, the method for carrying out the analysis of X-ray microregion element can be analyzed according to instrument
The method of field routine measures to obtain, such as specific test method may include: along length with energy depressive spectroscopy in 25-250nm
In the range of the length direction of carbon-based material such as carbon nanotube be scanned, determine nitrogen-atoms and oxygen atom in the length respectively
The concentration or content (5 concentration of measurement or content) on direction are spent, five effective samples are made by same nano-carbon material and are distinguished
It is scanned Electronic Speculum-energy spectrum analysis, each sample takes 5 different carbon nanotubes to be scanned, and nitrogen-atoms and oxygen atom are each contented
To 25 concentration or content data, the coefficient of variation of corresponding nitrogen-atoms and oxygen atom is calculated.The coefficient of variation refers to 25 surveys herein
The percentage of the standard deviation of magnitude and their average, i.e. coefficient of variation CV=(standard deviation SD/ average value MN) × 100%.
It is selected in the analysis of X-ray microregion element in order to preferably reflect the distributing homogeneity of nitrogen and oxygen element in carbon-based material
The area on the surface of the carbon-based material taken can be 10-250nm2, preferably 20-200nm2。
Wherein, it includes this hair that above-mentioned preparation method, which obtains having the possible cause of the carbon-based material of above-mentioned pathognomonic feature parameter,
It is that the treatment processes such as hydro-thermal and roasting are combined under specific material variety and material proportion in bright method.
In above-mentioned preparation method, the molar ratio of the nitrogen in carbon and organic alkali source in the solid carbon source
Can be 1:(0.002-50), preferably 1:(0.005-20), more preferably 1:(0.01-10).
The hydrogen peroxide in carbon and the aqueous hydrogen peroxide solution in above-mentioned preparation method, in the solid carbon source
Molar ratio can be 1:(0.01-10), preferably 1:(0.04-5), more preferably 1:(0.1-2).
In above-mentioned preparation method, the content of hydrogen peroxide can be selected in the larger context in the aqueous hydrogen peroxide solution
It selects, the concentration of the aqueous hydrogen peroxide solution can be the normal concentration of this field, such as can be 0.5-80 weight %.Concentration
The aqueous solution for meeting the hydrogen peroxide of above-mentioned requirements can be prepared using conventional method, be also commercially available, such as: it can be with quotient
The hydrogen peroxide of the hydrogen peroxide of the 28-32 weight % bought, the hydrogen peroxide of 48-52 weight % or 68-72 weight %.In order to obtain
Better effect, the concentration of the aqueous solution of hydrogen peroxide are preferably 1-30 weight %.
In above-mentioned preparation method, hydro-thermal refers at 100 DEG C or more under air-proof condition holding part water at autogenous pressures
The reaction condition of liquid is maintained, hydro-thermal can heat water so that part water spontaneous vaporization is pressurized to obtain under air-proof condition, excellent
Selection of land, the temperature for carrying out hydro-thermal process is 105-200 DEG C；More preferably 120-180 DEG C.Wherein, the time of hydro-thermal process can be with
For 0.5-96h, preferably 2-72h.
In above-mentioned preparation method, the operation of the solid in material after separating hydro-thermal process can pass through centrifugation and/or mistake
Filter carries out.
In above-mentioned preparation method, after the solid in material after separating hydro-thermal process, solid can be dried, into
Row drying condition can change in a big way, and the condition of the drying is not particularly limited in the present invention, can be normal
Rule selection, it is preferable that the temperature being dried is 80-180 DEG C, time 0.5-24h.The drying can under normal pressure into
Row, can also carry out under decompression (i.e. negative pressure).
In above-mentioned preparation method, the roasting can carry out in inert atmosphere, can also carry out in oxygen-containing atmosphere,
It can also successively be carried out in inert atmosphere and oxygen-containing atmosphere, wherein the inert atmosphere refers to by non-active gas shape
At atmosphere, the non-active gas such as group 0 element gas (such as argon gas) and/or nitrogen.Preferably, the roasting is containing
Have in the gas of oxygen and carry out, on the basis of the total volume of the gas containing oxygen, oxygen in the gas containing oxygen contains
Amount is 2-25 volume %.In order to more convenient and implement the present invention at low cost, under preferable case, the roasting can be in air
Middle progress.
In above-mentioned preparation method, the condition roasted can change in a big way, such as the temperature of roasting is
200-500 DEG C, preferably 300-450 DEG C, the time of roasting are 0.5-48h, preferably 2-24h.Journey can be used by carrying out roasting
Sequence heating strategy heated, such as roasting temperature be 200-450 DEG C when, roast 1- at 200-300 DEG C first
Then 12h roasts 1-12h at 310-450 DEG C；Such as the temperature of roasting be 300-450 DEG C when, first at 300-350 DEG C
1-12h is roasted, then roasts 1-12h at 380-450 DEG C.Wherein, room temperature can be cooled to natural cooling after roasting.
In above-mentioned preparation method, selecting for the solid carbon source can be the selection of carbon catalytic field routine, as long as described
Catalysis with catalytic hydrocarbon oxidation after solid carbon source hydrothermal treatment, such as the solid carbon source may include that carbon is received
In mitron, graphene, fullerene, nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber and Nano diamond etc. extremely
Few one kind.Preferably, the solid carbon source includes at least one of carbon nanotube, Nano diamond and graphene.
In above-mentioned preparation method, the carbon nanotube may include single-walled carbon nanotube and/or multi-walled carbon nanotube.It is described
The specific surface area of carbon nanotube can change in a big way, for example, 20-1000m2/ g, preferably 30-500m2/g.It is described
Carbon nanotube can be commercially available or prepare according to literature method, this is known to those skilled in the art, herein not
It repeats.
In above-mentioned preparation method, under preferable case, when the solid carbon source is multi-walled carbon nanotube, the multi wall carbon is received
The W of mitron500/W800It can be in the range of 0.02-0.5；The W of the more preferably described multi-walled carbon nanotube500/W800In 0.05-
In the range of 0.25.Under the preferable case, the carbon-based material that method of the invention obtains can be obtained when being used as catalyst
Better catalytic effect, especially be used as hydrocarbons dehydrogenation reaction catalyst when, can obtain higher feed stock conversion with
Selectivity of product.Wherein, W800It is described under the Elevated Temperature Conditions for referring to air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min
Slip of the solid carbon source in the weight at 800 DEG C relative to the weight at 400 DEG C, i.e., (solid carbon source is at 400 DEG C
Weight and the solid carbon source are in the weight difference at 800 DEG C) the weight of/solid carbon source at 400 DEG C, W500Refer to air
Under the Elevated Temperature Conditions of atmosphere and 25 DEG C of initial temperature and 10 DEG C/min, weight of the solid carbon source at 500 DEG C is opposite
The slip of weight at 400 DEG C, i.e., (solid carbon source at 400 DEG C weight and the solid carbon source at 500 DEG C
Weight difference) the weight of/solid carbon source at 400 DEG C.
In the more preferably embodiment of above-mentioned preparation method, the solid carbon source is multi-walled carbon nanotube, described more
The specific surface area of wall carbon nano tube is 50-500m2/ g, preferably 100-400m2/g；The W of the multi-walled carbon nanotube500/W800It can
In the range of 0.02-0.5；The W of the more preferably described multi-walled carbon nanotube500/W800In the range of 0.05-0.25.
In above-mentioned preparation method, the solid carbon source according to source difference can also contain oxygen element, nitrogen and remaining
Nonmetalloid (such as phosphorus atoms and sulphur atom), can also be without containing oxygen element, nitrogen and remaining nonmetalloid (such as phosphorus original
Son and sulphur atom).
In above-mentioned preparation method, when the solid carbon source contains oxygen element, wherein the content of oxygen element is generally not higher than 2
Weight %, preferably not higher than 0.5 weight % are further preferably not higher than 0.2 weight %.
In above-mentioned preparation method, when the solid carbon source contains nitrogen, wherein the content of nitrogen is generally not higher than
0.5 weight %, preferably not higher than 0.2 weight % are further preferably not higher than 0.1 weight %.
In above-mentioned preparation method, when the solid carbon source contains remaining nonmetalloid (such as phosphorus atoms and sulphur atom),
Described in solid carbon source oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms total amount
(based on the element) it is generally not higher than 0.5 weight %, preferably not higher than 0.2 weight %, is further preferably not higher than 0.1 weight
Measure %.
In above-mentioned preparation method, the organic amine may include in aliphatic amine, hydramine, amide, aliphatic cyclic amine and aromatic amine
It is one or more.
In above-mentioned preparation method, the quaternary ammonium base can be various organic level Four ammonium alkali；The aliphatic amine can be NH3
In at least one hydrogen replaced by aliphatic alkyl (preferably alkyl) after the various compounds that are formed；The hydramine can be
NH3In at least one hydrogen replaced by the aliphatic alkyl (preferably alkyl) of hydroxyl after the various compounds that are formed；It is described
The compound that amide is formed after being replaced for the hydroxyl in carboxylic acid by amino (or amido)；The aliphatic cyclic amine can be NH3In
At least one hydrogen replaced by cycloalkyl group after the various compounds that are formed；The aromatic amine can be NH3At least one of
The various compounds that hydrogen is formed after being replaced by aryl radical.
Specifically, the quaternary ammonium base can be quaternary ammonium base shown in formula I, what the aliphatic amine can indicate for Formula II
Aliphatic amine, the aliphatic hydramine can be the aliphatic hydramine such as formula III expression:
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, C1-C4Alkyl include C1-C4Straight chained alkyl and C3-C4
Branched alkyl, such as: R1、R2、R3And R4It can be respectively methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different
Butyl or tert-butyl.
R5(NH2)n(Formula II)
In Formula II, n is an integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, new penta
Base, isopentyl, tertiary pentyl or n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.More preferably fat
Race's amine compounds are one of ethamine, n-butylamine, butanediamine and hexamethylene diamine or a variety of.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-
C4Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is highly preferred that the fat
Race's alcohol amine compound is one of monoethanolamine, diethanol amine and triethanolamine or a variety of.
In above-mentioned preparation method, the specific example of the aliphatic amine can include but is not limited to ethamine, n-propylamine, positive fourth
At least one of amine, di-n-propylamine, butanediamine and hexamethylene diamine.The specific example of the fatty alcohol amine can include but is not limited to
At least one of monoethanolamine, diethanol amine and triethanolamine；The specific example of the quaternary ammonium base can include but is not limited to
At least one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.It is described
The specific example of amide can include but is not limited to formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide,
At least one of polyacrylamide, caprolactam, dimethylformamide and dimethyl acetamide.The specific reality of the aliphatic cyclic amine
Example can include but is not limited to triethylenediamine, diethylenetriamines, hexa, hexamethylene imine, Sanya second
At least one of base diamines, cyclic ethylene imines, morpholine, piperazine and cyclohexylamine.The specific example of the aromatic amine may include
But be not limited to aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, m-toluidine,
Open-chain crown ether, 23 dimethyl aniline, 2,4- dimethylaniline, 2,5- dimethylaniline, 2,6- dimethylaniline, 3,4- bis-
Methylaniline, 3,5- dimethylaniline, 2,4,6- trimethylaniline, o ethyl aniline, N- butylaniline and 2,6- diethylbenzene
At least one of amine.
Present invention be described in more detail by the following examples.In following embodiment and comparative example, if not otherwise specified,
Used reagent is commercially available analytical reagents.Wherein, the phosphorus content without containing oxygen element carbon nanotube is greater than 96 weights
% is measured, ash content is less than 1.5 weight %, specific surface area 168m2/ g is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences,
Phosphorus content containing oxygen element carbon nanotube is greater than 95 weight %, and oxygen element content is 1.1 weight %, and ash content is less than 1.2 weights
Measure %, specific surface area 211m2/ g is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.The phosphorus content of graphene is greater than
99 weight %, ash content is less than 0.8 weight %, specific surface area 627m2/ g is purchased from the limited public affairs of Chinese Academy of Sciences Chengdu organic chemistry
Department.
Hereinafter, ESCALab250 type X-ray of the X-ray photoelectron spectroscopic analysis in Thermo Scientific company
It is carried out on photoelectron spectrograph.Excitaton source is monochromatization Al K α X-ray, energy 1486.6eV, power 150W.Narrow scan
Penetrating energy used is 30eV.Base vacuum when analysis test is 6.5 × 10-10mbar.The C1s of electron binding energy simple substance carbon
Peak (284.0eV) correction.Correlation method for data processing is enterprising in the Thermo Avantage software that x-ray photoelectron spectroscopy carries
Row, version number V5.926 carry out quantitative equal analysis using sensitivity factor method known to industry in analysis module.
Hereinafter, thermogravimetric analysis carries out on TA5000 thermal analyzer, and test condition is air atmosphere, heating rate 10
DEG C/min, temperature range is room temperature (25 DEG C) to 1000 DEG C.
Hereinafter, using the ASAP2000 type N of Micromertrics company of the U.S.2Physical adsorption appearance measurement the specific area.
Hereinafter, using scanning electron microscope (the Dutch PHILIPS company XL 30ESEM type for being furnished with energy depressive spectroscopy (component)
Scanning electron microscope) measurement nano-carbon material (by taking carbon nanotube as an example) surface nitrogen atom and oxygen atom distributing homogeneity,
Specific test method are as follows: the length direction of the carbon nanotube with energy depressive spectroscopy along length in the range of 25-250nm is swept
It retouches, the concentration (5 concentration of measurement) of nitrogen-atoms and oxygen atom on the length direction is determined respectively, by same nano-carbon material system
It is scanned Electronic Speculum-energy spectrum analysis respectively at five effective samples, each sample takes 5 different carbon nanotubes to be scanned, nitrogen
Atom and oxygen atom respectively obtain 25 concentration datas, calculate the coefficient of variation of corresponding nitrogen-atoms and oxygen atom.Variation lines herein
Number refers to the standard deviation of 25 measured values and the percentage of their average, i.e. coefficient of variation CV=(standard deviation SD/ average value
MN) × 100%.
Prepare embodiment 1
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 2 weight %) is stirred 2h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:0.1, the solid carbon source and aquae hydrogenii dioxidi
The molar ratio of hydrogen peroxide in solution is 1:0.5, and mixed material obtained above is placed in in polytetrafluoroethylene (PTFE)
In the sealing autoclave of lining, in 140 DEG C at autogenous pressures hydro-thermal process for 24 hours, by consolidating in the material after hydro-thermal process
Body is separated by filtration and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight
(dry time be 6h), the material after being dried, the then maturing temperature by the material after obtained drying at 330 DEG C
Under, 2h is roasted in air, then under 430 DEG C of maturing temperature, roasts 2h in air, obtains the carbon of this preparation embodiment
Sill.
Prepare embodiment 2
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (caprolactam) and hydrogen peroxide
Aqueous solution (content of hydrogen peroxide is 5 weight %) is stirred 1h, obtains mixed material, wherein in the solid carbon source
Carbon and the presoma in the molar ratio of nitrogen be 1:0.05, in the solid carbon source and aqueous hydrogen peroxide solution
Hydrogen peroxide molar ratio be 1:0.2, mixed material obtained above is placed in the close of polytetrafluoroethyllining lining
Seal autoclave in, in 180 DEG C at autogenous pressures hydro-thermal process for 24 hours, by the material after hydro-thermal process solid filter
It separates and is dried, dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight and (dries
Time is 6h), the material after being dried, then by the material after obtained drying under 300 DEG C of maturing temperature, in air
Middle roasting 2h roasts 2h then under 400 DEG C of maturing temperature in air, obtains the carbon-based material of this preparation embodiment.
Prepare embodiment 3
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetraethyl ammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 30 weight %) is stirred 3h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:5, and the solid carbon source and hydrogen peroxide are water-soluble
The molar ratio of hydrogen peroxide in liquid is 1:0.1, and mixed material obtained above is placed in polytetrafluoroethyllining lining
Sealing autoclave in, in 120 DEG C of hydro-thermal process 48h at autogenous pressures, by the solid in the material after hydro-thermal process
It is separated by filtration and is dried, dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight and (does
The dry time is 6h), the material after being dried, then by the material after obtained drying under 350 DEG C of maturing temperature,
2h is roasted in air, then under 450 DEG C of maturing temperature, roasts 2h in air, obtains the carbon substrate of this preparation embodiment
Material.
Prepare embodiment 4
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 40 weight %) is stirred 5h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:0.008, the solid carbon source and hydrogen peroxide
The molar ratio of hydrogen peroxide in aqueous solution is 1:4, and mixed material obtained above is placed in in polytetrafluoroethylene (PTFE)
In the sealing autoclave of lining, in 160 DEG C of hydro-thermal process 12h at autogenous pressures, by consolidating in the material after hydro-thermal process
Body is separated by filtration and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight
(dry time be 6h), the material after being dried, the then maturing temperature by the material after obtained drying at 330 DEG C
Under, 2h is roasted in air, then under 380 DEG C of maturing temperature, roasts 2h in air, obtains the carbon of this preparation embodiment
Sill.
Prepare embodiment 5
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 0.5 weight %) is stirred 6h, obtains mixed material, wherein described solid
The molar ratio of the nitrogen in carbon and the presoma in body carbon source is 1:15, the solid carbon source and aquae hydrogenii dioxidi
The molar ratio of hydrogen peroxide in solution is 1:0.04, and mixed material obtained above is placed in in polytetrafluoroethylene (PTFE)
In the sealing autoclave of lining, in 150 DEG C at autogenous pressures hydro-thermal process for 24 hours, by consolidating in the material after hydro-thermal process
Body is separated by filtration and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight
(dry time be 6h), the material after being dried, the then maturing temperature by the material after obtained drying at 350 DEG C
Under, 2h is roasted in air, then under 450 DEG C of maturing temperature, roasts 2h in air, obtains the carbon of this preparation embodiment
Sill.
Prepare embodiment 6
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, the temperature of hydro-thermal process is 195 DEG C.
Prepare embodiment 7
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, the temperature of hydro-thermal process is 105 DEG C.
Prepare embodiment 8
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, tetrapropylammonium hydroxide is replaced with oneself
The equal weight mixtures of diamines and n-butylamine.
Prepare embodiment 9
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, tetrapropylammonium hydroxide is replaced with two
The equal weight mixtures of ethanol amine and aniline.
Prepare embodiment 10
Carbon-based material is prepared using the method with preparation embodiment 1, unlike carbon nanotube the weight such as replaced with into
Graphene.
Prepare embodiment 11
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, the material after obtained drying is 330
DEG C maturing temperature under, roast 4h in air.
Prepare embodiment 12
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, the material after obtained drying is 430
DEG C maturing temperature under, roast 4h in air.
Prepare embodiment 13
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, the material after obtained drying is 500
DEG C maturing temperature under, roast 1h in air.
Prepare embodiment 14
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, the material after obtained drying is 210
DEG C maturing temperature under, roast 4h in air.
Prepare embodiment 15
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, solid carbon source is the carbon containing oxygen element
Nanotube, roasting carry out in argon gas.
Prepare embodiment 16
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, solid carbon source is the carbon containing oxygen element
Nanotube, roasting carry out in air.
Prepare embodiment 17
Carbon-based material is prepared using the method with preparation embodiment 1, unlike, roasting carries out in nitrogen.
Prepare comparative example 1
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 2 weight %) is stirred 2h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:0.1, the solid carbon source and aquae hydrogenii dioxidi
The molar ratio of hydrogen peroxide in solution is 1:0.5, mixed material obtained above is dried, dry temperature is
120 DEG C, until the solid being separated by filtration is kept substantially constant weight (the dry time is 6h), the material after being dried,
Then by the material after obtained drying under 330 DEG C of maturing temperature, 2h is roasted in air, then in 430 DEG C of roasting
At a temperature of, 2h is roasted in air, using the material after roasting as the carbon-based material of this comparative example.
Prepare comparative example 2
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 2 weight %) is stirred 2h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:0.1, the solid carbon source and aquae hydrogenii dioxidi
The molar ratio of hydrogen peroxide in solution is 1:0.5, and mixed material obtained above is placed in in polytetrafluoroethylene (PTFE)
It, will be in the material after hydro-thermal process in 140 DEG C of hydro-thermal process 24 hours at autogenous pressures in the sealing autoclave of lining
Solid is separated by filtration and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight
(the dry time is 6h), the material after being dried, then using the material after obtained drying as the carbon-based of this comparative example
Material.
Testing example 1
The side of method or reference in reference literature (Jian Zhang et al., Science 322 (2008), 73-77)
Method, to preparation embodiment 1-17 and prepare the obtained carbon-based material of comparative example 1-2 and buy as described above containing/without aerobic
Elemental carbon nano pipe carries out analysis of chemical elements and XRF elemental analysis and XPS atlas analysis.Wherein, in x-ray photoelectron spectroscopy
Be 300 DEG C at a temperature of in helium atmosphere handle 3h after measure.The results are shown in Table 1.
In table 1, the O of XPS map column indicates the amount and 531.8- for the oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak within the scope of 532.2eV determines；The C1 of XPS map column is indicated within the scope of 283.8-284.2eV
Peak determine carbon amount and 280.0-294.0eV within the scope of peak determination carbon amount ratio × 100 (percentage
Ratio)；The amount and the peak within the scope of 288.6-289.0eV that C2 indicates the carbon that the peak within the scope of 286.2-286.6eV determines
Amount × 100 (percent value) for the carbon that the sum of determining amount of carbon is determined with the peak within the scope of 280.0-294.0eV；
C3 refers to the amount for the carbon that the peak within the scope of 286.2-286.6eV determines and the carbon that the peak within the scope of 288.6-289.0eV determines
The ratio of the amount of element.The N1 of XPS map column refers to the amount and 395.0- for the nitrogen that the peak within the scope of 398.0-400.5eV determines
Ratio × 100 (percent value) of the amount for the nitrogen that peak within the scope of 405.0eV determines；N2 refers to 400.6-401.5eV range
Ratio × 100 (hundred of the amount for the nitrogen that the amount for the nitrogen that interior peak determines and the peak within the scope of 395.0-405.0eV determine
Divide ratio).W indicates W500/W800× 100 (percent values).C, N and the O of element group in column respectively indicate the element of carbon, nitrogen and oxygen
Composition.When CV indicated the analysis of X-ray microregion element, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen member
The coefficient of variation of the content of element and oxygen element.
Table 1
According to preparing embodiment 1-17 in table 1 and prepare the analysis test data of comparative example 1-2 can be seen that may be due to
It joined presoma and hydrogen peroxide and carried out hydro-thermal and roasting, so that in the XPS map of carbon-based material, 533.1-
The amount for the oxygen element that the amount for the oxygen element that peak within the scope of 533.5eV determines and the peak within the scope of 531.8-532.2eV determine
Ratio is in the range of 0.2-5；The amount and 395.0-405.0eV model for the nitrogen that peak within the scope of 398.0-400.5eV determines
The ratio of the amount for the nitrogen that peak in enclosing determines is in the range of 0.5-1；400.6-401.5eV the nitrogen that the peak in range determines
The ratio of the amount for the nitrogen that the amount of element and the peak within the scope of 395.0-405.0eV determine is in the range of 0-0.5；283.8-
The amount for the carbon that the amount for the carbon that peak within the scope of 284.2eV determines and the peak within the scope of 280.0-294.0eV determine
Ratio is in the range of 0.6-1；The amount and 288.6-289.0eV model for the carbon that peak within the scope of 286.2-286.6eV determines
The ratio of the amount for the carbon that the sum of the amount of carbon that peak in enclosing determines is determined with the peak within the scope of 280.0-294.0eV exists
In the range of 0.02-0.2；Within the scope of the amount and 288.6-289.0eV of the carbon that peak within the scope of 286.2-286.6eV determines
Peak determine carbon amount ratio in the range of 0.3-2；W500/W800For 0.05-0.25；The identical difference X of area
In light microcell, the coefficient of variation of the content of N element and O element is below 20%.
Embodiment 1
Respectively by the obtained carbon-based material of the preparation embodiment 1-17 of 0.25g and preparation comparative example 1-2 and purchase as described above
That buys contains oxygen element carbon nanotube and without containing oxygen element carbon nanotube as catalyst, and it is micro- to be loaded into universal fixed bed
In type quartz tube reactor, two end seal of miniature quartz pipe reactor has quartz sand, under the conditions of normal pressure and 420 DEG C, by material (fourth
The volumetric concentration of alkane be 1.98%, butane and oxygen molar ratio 2:3, Balance Air are nitrogen) total volume air speed be 1000h-1Under
It is reacted, is reacted after 8h according to the method in document (322 (2008) 73-77 of Jian Zhang et al., Science),
Butanes conversion, butadiene selective and total olefin selectivity are measured, the results are shown in Table 2.
Table 2
According to the data of table 2, it is found that the present invention can improve the selectivity that butane oxidation dehydrogenation prepares alkene simultaneously
And conversion ratio.Contain the carbon of 85-95 weight %, the nitrogen of 0.5-5 weight % and 2-10 weight in the preferably carbon-based material
The oxygen element for measuring %, in the x-ray photoelectron spectroscopy in the carbon-based material, oxygen that the peak within the scope of 533.1-533.5eV determines
Feelings of the ratio of the amount for the oxygen element that the amount of element and the peak within the scope of 531.8-532.2eV determine in the range of 0.6-1.8
Under condition, selectivity and conversion ratio that butane oxidation dehydrogenation prepares alkene can be further improved simultaneously.Also, at preferred hydro-thermal
In the case that the temperature of reason is 120-180 DEG C and maturing temperature is 300-450 DEG C, it is de- can further to improve simultaneously butane oxidation
Hydrogen prepares the selectivity and conversion ratio of alkene.
Embodiment 2
Respectively by the obtained carbon-based material of the preparation embodiment 1-17 of 0.25g and preparation comparative example 1-2 and purchase as described above
That buys contains oxygen element carbon nanotube and without containing oxygen element carbon nanotube as catalyst, and it is micro- to be loaded into universal fixed bed
In type quartz tube reactor, two end seal of miniature quartz pipe reactor has quartz sand, under the conditions of 0.1MPa and 450 DEG C, by material
(concentration of propane is 5.88 volume %, propane and oxygen molar ratio 1:1, and Balance Air is nitrogen, accounts for surplus) is in total volume air speed
For 100h-1Under reacted, react 8h after according to document (Jian Zhang et al., Science 322 (2008), 73-77)
In method, measurement conversion of propane, Propylene Selectivity and total olefin selectivity, the results are shown in Table 3.
Table 3
According to the data of table 3, it is found that the present invention can improve the selectivity that oxidative dehydrogenation of propane prepares alkene simultaneously
And conversion ratio.Contain the carbon of 85-95 weight %, the nitrogen of 0.5-5 weight % and 2-10 weight in the preferably carbon-based material
The oxygen element for measuring %, in the x-ray photoelectron spectroscopy in the carbon-based material, oxygen that the peak within the scope of 533.1-533.5eV determines
Feelings of the ratio of the amount for the oxygen element that the amount of element and the peak within the scope of 531.8-532.2eV determine in the range of 0.6-1.8
Under condition, selectivity and conversion ratio that oxidative dehydrogenation of propane prepares alkene can be further improved simultaneously.Also, at preferred hydro-thermal
In the case that the temperature of reason is 120-180 DEG C and maturing temperature is 300-450 DEG C, it is de- can further to improve simultaneously oxidation of propane
Hydrogen prepares the selectivity and conversion ratio of alkene.
Embodiment 3
Respectively by the obtained carbon-based material of the preparation embodiment 1-17 of 0.25g and preparation comparative example 1-2 and purchase as described above
That buys contains oxygen element carbon nanotube and without containing oxygen element carbon nanotube as catalyst, and it is micro- to be loaded into universal fixed bed
In type quartz tube reactor, two end seal of miniature quartz pipe reactor has quartz sand, under the conditions of 0.1MPa and 350 DEG C, by material
(concentration of ethylbenzene is 1.98 volume %, ethylbenzene and oxygen molar ratio 0.5:1, and Balance Air is nitrogen, accounts for surplus) is in total volume sky
Speed is 2000h-1Under reacted, react the side after 8h in reference literature (Angew.Chem.Int.Ed.48 (2009) 6913)
Method measures conversion of ethylbenzene and selectivity of styrene, and the results are shown in Table 4.
Table 4
According to the data of table 3, it is found that the present invention can improve the selectivity that oxidative dehydrogenation of ethylbenzene prepares alkene simultaneously
And conversion ratio.Contain the carbon of 85-95 weight %, the nitrogen of 0.5-5 weight % and 2-10 weight in the preferably carbon-based material
The oxygen element for measuring %, in the x-ray photoelectron spectroscopy in the carbon-based material, oxygen that the peak within the scope of 533.1-533.5eV determines
Feelings of the ratio of the amount for the oxygen element that the amount of element and the peak within the scope of 531.8-532.2eV determine in the range of 0.6-1.8
Under condition, selectivity and conversion ratio that oxidative dehydrogenation of ethylbenzene prepares alkene can be further improved simultaneously.Also, at preferred hydro-thermal
In the case that the temperature of reason is 120-180 DEG C and maturing temperature is 300-450 DEG C, it is de- can further to improve simultaneously ethylbenzene oxidation
Hydrogen prepares the selectivity and conversion ratio of alkene.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail 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, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
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| CN109305665B (en) * | 2017-07-28 | 2020-08-18 | 中国石油化工股份有限公司 | A kind of heteroatom-containing nano carbon material and its preparation method and application and a kind of hydrocarbon oxidative dehydrogenation reaction method |
| CN109305666B (en) * | 2017-07-28 | 2020-08-18 | 中国石油化工股份有限公司 | Heteroatom-containing nano carbon material and preparation method thereof, cyclohexane oxidation method and hydrocarbon oxidation dehydrogenation method |
| CN107445787B (en) * | 2017-08-22 | 2020-07-07 | 中国科学院金属研究所 | Application of a graphitized activated carbon material as a catalyst for the oxidative dehydrogenation of n-butane |
| CN108927130B (en) * | 2018-07-17 | 2021-05-18 | 福州大学 | A kind of fluorinated nano-diamond material and its preparation method and application |
| CN111760565B (en) * | 2019-04-01 | 2023-05-05 | 中国石油化工股份有限公司 | Modified nano carbon-based material, preparation method thereof and catalytic oxidation method of cyclic hydrocarbon |
| CN112441958B (en) * | 2019-08-30 | 2022-10-21 | 中国石油化工股份有限公司 | Method for oxidizing tertiary butanol |
| CN112742366B (en) * | 2019-10-29 | 2023-06-09 | 中国石油化工股份有限公司 | Nanocarbon-based material, method for preparing same, and catalytic oxidation method for cycloalkane |
| CN112724053B (en) * | 2019-10-29 | 2023-03-31 | 中国石油化工股份有限公司 | Method for preparing sulfoxide |
| CN115724807B (en) * | 2021-08-31 | 2024-07-09 | 中国石油化工股份有限公司 | Method for preparing styrene oxide |
| CN115724810B (en) * | 2021-08-31 | 2024-05-17 | 中国石油化工股份有限公司 | A method for preparing propylene oxide |
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| 纳米碳纤维催化丙烷氧化脱氢性能的研究;隋志军等;《石油化工》;20051231;第34卷(第7期);612-616 |
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