CN109304196A - One kind carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon oxidative dehydrogenation processes - Google Patents
One kind carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon oxidative dehydrogenation processes Download PDFInfo
- Publication number
- CN109304196A CN109304196A CN201710625268.8A CN201710625268A CN109304196A CN 109304196 A CN109304196 A CN 109304196A CN 201710625268 A CN201710625268 A CN 201710625268A CN 109304196 A CN109304196 A CN 109304196A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- hetero atom
- weight
- content
- containing hetero
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of carbon material containing hetero atom and preparation method and application and hydrocarbon oxidative dehydrogenation processes, this contains hetero atom carbon material and contains oxygen element, nitrogen, protium and carbon, in the X ray diffracting spectrum of the carbon material containing hetero atom, disperse peak is respectively present between 2 angles θ is 20 ° -30 ° and between 40 ° -50 °, the content of the Surface Oxygen determined by x-ray photoelectron spectroscopy is a, the content of the body phase oxygen determined by elemental microanalysis method is b, a/b >=2.Catalyst of the carbon material containing hetero atom as hydrocarbon oxidative dehydrogenation can obtain the olefine selective significantly improved, reduce the material quantity to burn in vain, improve raw material availability and reaction safety.Also, the cost of the carbon material according to the present invention containing hetero atom is low and is easily obtained.
Description
Technical field
The present invention relates to a kind of carbon material containing hetero atom and its preparation method and application, the invention further relates to using this contain it is miscellaneous
Hydrocarbon oxidative dehydrogenation processes of the atom carbon material as catalyst.
Background technique
There are various forms structures, including carbon nanotube, graphite, graphene, Nano diamond, active carbon, ocean for carbon material
Green onion carbon etc..Carbon material has environmental-friendly, renewable, low power consumption and other advantages, carbon materials compared to INVENTIONConventional metal-oxide catalyst
Material also has good heating conduction, therefore energy utilization rate is high, advantageously reduces reaction temperature, improves selectivity of product.
It is had been reported in the catalysis reaction such as alkane activation and oxidative dehydrogenation currently, having a plurality of types of carbon materials.Example
Such as, six the seventies of last century, researcher have found that coke can be catalyzed alkanes oxidative dehydrogenation reaction (Journal of
Catalysis,31:444-449,1973)；Document (ACTA PHYSICA POLONIC A, 118 (2010) 459-464) report
Using active carbon as catalyst, butylene and butadiene are converted by normal butane.
The catalytic activity of simple carbon material is not high, but since the controllability of carbon material surface structure is strong, it can be with people
To be surface modified, such as incorporation oxygen heteroatom functional group, thus regulate and control the electron density distribution and acid-base property on its surface,
Improve the catalytic activity of carbon material.It is taken off for example, carbon nanotube progress phosphorous-nitrogen modified can be greatlyd improve it in butane oxidation
Performance (Catalysis Today, 102:248-253,2005 in hydrogen；Science Vol.322(3),73-77,2008).
However, carbon nanotube is sufficiently expensive and is not easy to prepare.Also, the obtained carbon material of method of prior art report
Overall selectivity in alkanes oxidative dehydrogenation reaction is difficult to reach 60% or more, namely in the reaction, have nearly half with
On charging invalid combustion reaction has occurred, excessive combustion reaction not only reduces raw material availability, and reduces anti-
The safety answered causes carbon material to be difficult to functionization when being applied to alkanes oxidative dehydrogenation reaction.
Therefore, there is an urgent need to improve selectivity of product of the carbon material in alkanes oxidative dehydrogenation reaction, to improve raw material
Utilization rate and reaction safety.
Summary of the invention
It is an object of the invention to overcome existing carbon material in the catalyst as hydrocarbon oxidative dehydrogenation, product choosing
The low technical problem of selecting property provides a kind of carbon material containing hetero atom, this contains hetero atom carbon material and shows in hydrocarbon oxidative dehydrogenation
The selectivity of product significantly improved is shown.
According to the first aspect of the invention, the present invention provides a kind of carbon material containing hetero atom, this contains hetero atom carbon materials
Material contains oxygen element, nitrogen, protium and carbon, on the basis of the total amount of the carbon material containing hetero atom and based on the element,
The content of the oxygen element is 1-10 weight %, and the content of the nitrogen is 0.01-4 weight %, the content of the protium
For 0.1-3 weight %, the content of the carbon is 83-98.89 weight %,
It is between 20 ° -30 ° and between 40 ° -50 ° at 2 angles θ in the X ray diffracting spectrum of the carbon material containing hetero atom
It is respectively present disperse peak；
This contains in hetero atom carbon material, and the content of the Surface Oxygen determined by x-ray photoelectron spectroscopy is a, by elemental analysis
The content for the body phase oxygen that method determines is b, a/b >=2.
According to the second aspect of the invention, the present invention provides a kind of preparation method of carbon material containing hetero atom, the party
Method include: by raw material carbon material in a kind of atmosphere reactive, roasted at a temperature of 400-1200 DEG C, the reactivity
Atmosphere contains ammonia, optional carrier gas and optional vapor；
The raw material carbon material contains oxygen element, protium and carbon, on the basis of the total amount of the raw material carbon material
And based on the element, the content of the oxygen element is 0.2-12 weight %, and the content of the protium is 0.05-3 weight %, described
The content of carbon is 85-99.75 weight %；
In the X ray diffracting spectrum of the raw material carbon material, divide between 2 angles θ is 20 ° -30 ° and between 40 ° -50 °
Not there is disperse peak；
In the raw material carbon material, the content of the Surface Oxygen determined by x-ray photoelectron spectroscopy is a, by elemental microanalysis method
The content of determining body phase oxygen is b, a/b < 2.
According to the third aspect of the present invention, the present invention provides a kind of method systems as described in the second aspect of the present invention
Standby carbon material containing hetero atom.
According to the fourth aspect of the present invention, the present invention provides described in first aspect of the present invention or third aspect
Carbon material containing hetero atom as hydrocarbon oxidative dehydrogenation catalyst application.
According to the fifth aspect of the present invention, the present invention provides a kind of hydrocarbon oxidative dehydrogenation processes, this method is included in oxygen
Under fluidized dehydrogenation reaction condition, hydrocarbon and carbon material containing hetero atom described in first aspect of the present invention or third aspect are connect
Touching.
Catalyst of the carbon material containing hetero atom according to the present invention as hydrocarbon oxidative dehydrogenation can be obtained and be significantly improved
Olefine selective reduces the material quantity to burn in vain, improves raw material availability and reaction safety.Also, it is according to the present invention
Carbon material containing hetero atom as raw material, but uses the amorphous carbon material of relative moderate to make without expensive carbon pipe
For raw material, thus the cost of the carbon material according to the present invention containing hetero atom is low and be easily obtained.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectrogram for the raw material carbon material that embodiment 1 uses.
Fig. 2 is the X-ray diffraction spectrogram of the carbon material containing hetero atom prepared by embodiment 1.
Fig. 3 is the X-ray diffraction spectrogram for the carbon nanotube as raw material that comparative example 1 uses.
Fig. 4 is the X-ray diffraction spectrogram of the carbon nanotube containing hetero atom prepared by comparative example 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of carbon material containing hetero atom, this contains hetero atom carbon materials
Material contains oxygen element, nitrogen, protium and carbon.
Carbon material containing hetero atom according to the present invention, on the basis of the total amount of the carbon material containing hetero atom and based on the element,
The content of the oxygen element is 1-10 weight %, preferably 1.2-8 weight %, more preferably 1.5-6 weight %；The nitrogen
Content be 0.01-4 weight %, preferably 0.03-3 weight %, more preferably 0.05-2 weight %；The content of the protium
For 0.1-3 weight %, preferably 0.2-2.5 weight %, more preferably 0.4-2 weight %；The content of the carbon is 83-
98.89 weight %, preferably 86.5-98.57 weight %, more preferably 90-98.05 weight %.
In the present invention, the content of each element is measured using elemental microanalysis method in carbon material containing hetero atom and raw material carbon material.
In the present invention, elemental analysis carries out on Elementar Micro Cube elemental analyser, and concrete operation method and condition are such as
Under: sample weighs 1-2mg in tin can, is put into automatic sampling disk, enters combustion tube burning, ignition temperature 1000 by ball valve
DEG C (when in order to remove sample introduction atmospheric interference, using helium purge) then restores the gas after burning with going back native copper, shape
At nitrogen, carbon dioxide and water.Mixed gas is separated by three desorption columns, is successively detected into thermal conductivity detector (TCD) (TCD).
The analysis of oxygen element is to convert CO under the action of C catalyst using pyrolytic for the oxygen in sample, then use
TCD detects CO.
Carbon material containing hetero atom according to the present invention, this contains in the X ray diffracting spectrum of hetero atom carbon material, is at 2 angles θ
Disperse peak is respectively present between 20 ° -30 ° and between 40 ° -50 °.Carbon material containing hetero atom according to the present invention is in other positions
There is usually no disperse peaks.Scanning range (5 ° -70 °) of the carbon material containing hetero atom according to the present invention in X-ray diffraction analysis
The interior bright and sharp peak there is no corresponding to carbon, i.e., carbon material containing hetero atom according to the present invention are amorphous state.
In the present invention, disperse peak refers to that half-peak breadth is not less than 3 ° of diffraction maximum, generally, the half-peak breadth at disperse peak is 3 °-
10°；Bright and sharp peak refers to diffraction maximum of the half-peak breadth less than 3 °.In the present invention, X-ray diffraction analysis is in Rigaku D/MAX-2500
It is carried out on type X-ray diffractometer, using CuK alpha ray, operating voltage 20kV, tube current 10mA, scanning range is 5 °-
70°.In the present invention, in X ray diffracting spectrum, 2 angles θ as corresponding to the peak value of diffraction maximum determine the position of the diffraction maximum.
Carbon material containing hetero atom according to the present invention, this contains in hetero atom carbon material, is determined by x-ray photoelectron spectroscopy
The content of Surface Oxygen is a, and the content of the body phase oxygen determined by elemental microanalysis method is b, a/b >=2.Contain miscellaneous original from this is further increased
The angle of selectivity of product of the sub- carbon material in the catalyst as hydrocarbon oxidative dehydrogenation is set out, and a/b is preferably 2-5, more
Preferably 2.1-4.5.
In the present invention, X-ray photoelectron spectroscopic analysis is in Thermo Scientific company equipped with Thermo
It is tested on the ESCALab250 type x-ray photoelectron spectroscopy of Avantage V5.926 software, excitaton source is monochromatization Al
K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, base vacuum when analysis test
It is 6.5 × 10-10Mbar, the peak C1s (284.6eV) correction of electron binding energy simple substance carbon, in Thermo Avantage software
Upper carry out data processing carries out quantitative analysis using sensitivity factor method in analysis module.In 150 DEG C of temperature before sample test
Degree and the pressure of 1 normal atmosphere are 3 hours dry in helium atmosphere.
Carbon material containing hetero atom according to the present invention, which is >=100m2/ g, preferably
For >=500m2/ g, more preferably >=600m2/ g, further preferably 700-1500m2/ g, such as can be 750-1300m2/g。
In the present invention, specific surface area is measured by nitrogen adsorption BET method.
Carbon material containing hetero atom according to the present invention, the carbon material containing hetero atom are made using amorphous carbon as raw material
, volume average particle size generally can be 20-850 μm, preferably 50-400 μm, more preferably 60-260 μm.In the present invention,
Volume average particle size is measured using laser particle analyzer.
Carbon material containing hetero atom according to the present invention, such as sulphur atom and the other nonmetallic heteroatoms contents of phosphorus atoms can be with
For customary amount.Generally, in carbon material containing hetero atom according to the present invention, its outside oxygen atom, hydrogen atom and nitrogen-atoms
The total amount of its nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) can be 1 weight % hereinafter, preferably 0.5 weight % or less.
Carbon material containing hetero atom according to the present invention, can also be containing the remaining metallic atom in carbon material preparation process on a small quantity, this
A little remaining metallic atoms are typically derived from the catalyst used when preparing carbon material, the content one of these remaining metallic atoms
As for 1 weight % hereinafter, preferably 0.5 weight % or less.
According to the second aspect of the invention, the present invention provides a kind of preparation method of carbon material containing hetero atom, the party
Method include: by raw material carbon material in a kind of atmosphere reactive, roasted at a temperature of 400-1200 DEG C.
Method described in the second aspect according to the present invention, the raw material carbon material contain oxygen element, protium and carbon member
Element, on the basis of the total amount of the raw material carbon material and based on the element, the content of the oxygen element is 0.2-12 weight %, described
The content of protium is 0.05-3 weight %, and the content of the carbon is 85-99.75 weight %.It is final from further increasing
The angle of selectivity of product when catalyst of the carbon material containing hetero atom as hydrocarbon oxidative dehydrogenation of preparation is set out, with described
On the basis of the total amount of raw material carbon material and based on the element, the content of the oxygen element is preferably 0.5-10 weight %, more preferably
1-9.5 weight, further preferably 2-9 weight %；The content of the protium is preferably 0.1-3 weight %, more preferably
0.5-2.8 weight %, further preferably 1-2.6 weight %；The content of the carbon is preferably 87-99.4 weight %, more
Preferably 87.7-98.5 weight %, further preferably 88.4-97 weight %.
Remaining nonmetallic heteroatoms (such as sulphur atom and phosphorus member in the raw material carbon material outside oxygen atom and hydrogen atom
Element) total amount (based on the element) can be customary amount.Generally, in the raw material carbon material outside oxygen atom and hydrogen atom
The total amount of remaining nonmetallic heteroatoms is not higher than 1 weight %, preferably not higher than 0.5 weight %.According to the method for the present invention,
The raw material carbon material can also contain some metallic elements according to the difference in source, these metallic elements are typically derived from system
The catalyst used when standby raw material carbon material, content is generally in 1 weight % hereinafter, it is preferred that below 0.5 weight %.
In the X ray diffracting spectrum of the raw material carbon material, the raw material carbon material 2 angles θ be 20 ° -30 ° between and
Disperse peak is respectively present between 40 ° -50 °.Method described in the second aspect according to the present invention, the raw material carbon material is other
There is usually no disperse peaks for position.Method described in the second aspect according to the present invention, the raw material carbon material is in X-ray diffraction
Bright and sharp peak is not present in the scanning range (5 ° -70 °) of analysis, i.e., the described raw material carbon material is amorphous state, such as can be work
The combination of one or more of property charcoal, coke, charcoal and carbon black, preferably active carbon.
In the raw material carbon material, the content of the Surface Oxygen determined by x-ray photoelectron spectroscopy is a, by elemental microanalysis method
The content of determining body phase oxygen is b, a/b < 2.From the carbon material containing hetero atom finally prepared is further increased in hydrocarbon oxidative dehydrogenation
The angle of selectivity of product in reaction is set out, and a/b is preferably 0.9-1.95, more preferably 1.2-1.9.
The specific surface area of the raw material carbon material can be 400-1400m2/ g, preferably 600-1300m2/ g, more preferably
800-1200m2/g。
The volume average particle size of the raw material carbon material generally can be 25-850 μm, preferably 50-400 μm, more preferably
It is 80-200 μm.In the present invention, volume average particle size is measured using laser particle analyzer.
Method described in the second aspect according to the present invention, raw material carbon material can use commonly used in the art before use
Method is pre-processed (as washed), to remove some impurity of raw material carbon material surface；It can also be without pretreatment, directly
It uses, in embodiment disclosed by the invention, raw material carbon material is not pre-processed using preceding.
Method described in the second aspect according to the present invention, the atmosphere reactive contain ammonia, optional carrier gas and
Optional vapor.The carrier gas can be non-active gas.The non-active gas refers to chemically inert gas, Ke Yiwei
Nitrogen and/or zero group gas, such as the combination of one or more of nitrogen, neon, argon gas and helium.
On the basis of the dosage of the ammonia in raw material carbon material can introduce enough nitrogen-atoms.Generally, described anti-
In answering property atmosphere, the content of ammonia can be 0.01-5 volume %, preferably 0.1-4 volume %, more preferably 0.5-3 body
Product %.
Method described in the second aspect according to the present invention, in one embodiment, the atmosphere reactive be not aqueous
Steam, remaining condition under the same conditions, according to the embodiment preparation nano-carbon material containing hetero atom hydrocarbon oxidation take off
Higher olefine selective is shown in hydrogen reaction.
Method described in the second aspect according to the present invention, in another embodiment, the atmosphere reactive contain
Vapor introduces vapor in the atmosphere reactive, remaining condition under the same conditions, preparation can be further increased
Feed stock conversion of the nano-carbon material containing hetero atom in hydrocarbon oxidative dehydrogenation.In this embodiment, the reactivity
In atmosphere, the content of vapor can be 0.01-10 volume %, preferably 0.1-9 volume %, more preferably 0.2-5 volume %,
Further preferably 0.5-2 volume %.
Method described in the second aspect according to the present invention, the atmosphere reactive can be flowing atmosphere, or
Non-current atmosphere, is not particularly limited.As flowing atmosphere, can continue to introduce into reactor in roasting process described anti-
Atmosphere in answering property atmosphere metathesis reactor；As illiquidity atmosphere, the reactive gas is built before roasting in reactor
Atmosphere, in roasting process, reactor and the external world are without gas exchanges.
Method described in the second aspect according to the present invention, it is described roasting 400-1200 DEG C at a temperature of carry out, preferably
500-1100 DEG C at a temperature of carry out.From the carbon material containing hetero atom finally prepared is further increased in hydrocarbon oxidative dehydrogenation
In the angle of selectivity of product set out, the roasting more preferably 700-1000 DEG C at a temperature of carry out.
The duration of the roasting can be selected according to the temperature roasted.Generally, the roasting is held
The continuous time can be 0.5-24 hours, preferably 1-8 hours, more preferably 2-6 hours.
According to the third aspect of the present invention, the present invention provides one kind is prepared by the second aspect the method for the present invention
Carbon material containing hetero atom.
Carbon material containing hetero atom according to the present invention is had by carbon material containing hetero atom prepared by method of the invention
Good catalytic performance shows the olefine selective significantly improved in hydrocarbons oxidative dehydrogenation, thus effectively
Improve raw material availability and product yield.
Carbon material containing hetero atom according to the present invention or the carbon material containing hetero atom prepared by method of the invention can be with
It is directly used as catalyst, can also be used in the form of preformed catalyst.The preformed catalyst can be containing according to the present invention
Carbon material containing hetero atom or the carbon material containing hetero atom and binder that are prepared by method of the invention.The binder can
It to be selected according to the specifically used occasion of the preformed catalyst, is subject to and can satisfy requirement, such as can be to have
Machine binder and/or inorganic binder.
According to the fourth aspect of the present invention, the present invention provides in terms of first aspect according to the present invention or third
Application of the carbon material containing hetero atom as the catalyst of hydrocarbon oxidative dehydrogenation.
Application according to the present invention, the carbon material containing hetero atom are used directly for hydrocarbon oxidative dehydrogenation, can also be with
Hydrocarbon oxidative dehydrogenation is used for after molding.
According to the fifth aspect of the present invention, the present invention provides a kind of hydrocarbon oxidative dehydrogenation processes, this method is included in oxygen
Under fluidized dehydrogenation reaction condition, hydrocarbon and carbon material containing hetero atom described in first aspect of the present invention or third aspect are connect
Touching.
Hydrocarbon oxidative dehydrogenation method according to the present invention, the carbon material containing hetero atom are used directly for connecing with hydrocarbon
Touching is used to contact with hydrocarbon after can also forming the carbon material containing hetero atom.
Hydrocarbon oxidative dehydrogenation method according to the present invention can carry out dehydrogenation to a plurality of types of hydrocarbon, to obtain insatiable hunger
And hydrocarbon, such as alkene.According to the method for the present invention particularly suitable for carrying out dehydrogenation to alkane, to obtain alkene.
In the present invention, the hydrocarbon is preferably alkane, such as C2-C12Alkane.Specifically, the hydrocarbon can be but be not limited to second
Alkane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene, n-hexane, 2- methylpentane, 3- methylpent
Alkane, 2,3- dimethylbutane, hexamethylene, methyl cyclopentane, normal heptane, 2- methyl hexane, 3- methyl hexane, 2- ethylpentane,
3- ethylpentane, 2,3- dimethyl pentane, 2,4- dimethyl pentane, normal octane, 2- methyl heptane, 3- methyl heptane, 4- methyl
Heptane, 2,3- dimethylhexane, 2,4- dimethylhexane, 2,5- dimethylhexane, 3- ethyl hexane, 2,2,3- trimethyl penta
Alkane, 2,3,3- trimethylpentane, 2,4,4- trimethylpentane, 2- methyl -3- ethylpentane, n -nonane, 2- methyloctane, 3- first
Base octane, 4- methyloctane, 2,3- dimethyl heptane, 2,4- dimethyl heptane, 3- ethyl heptane, 4- ethyl heptane, 2,3,4-
Trimethyl cyclohexane, 2,3,5- trimethyl cyclohexane, 2,4,5- trimethyl cyclohexane, 2,2,3- trimethyl cyclohexane, 2,2,4- trimethyl oneself
Alkane, 2,2,5- trimethyl cyclohexane, 2,3,3- trimethyl cyclohexane, 2,4,4- trimethyl cyclohexane, 2- methyl -3- ethyl hexane, 2- first
Base -4- ethyl hexane, 3- methyl -3- ethyl hexane, 3- methyl -4- ethyl hexane, 3,3- diethylpentane, 1- methyl -2- second
Butylcyclohexane, 1- methyl -3- ethyl cyclohexane, 1- methyl -4- ethyl cyclohexane, n-propyl hexamethylene, isopropyl cyclohexane, three
Hexahydrotoluene (the various isomers including trimethyl-cyclohexane, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- 3-methyl cyclohexanols
Alkane, 1,2,5- trimethyl-cyclohexane, 1,3,5- trimethyl-cyclohexane), n-decane, 2- methylnonane, 3- methylnonane, 4- methyl
Nonane, 5- methylnonane, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyl octane, 4- ethyl octane, 2,3,4- tri-
Methyl heptane, 2,3,5- trimethylheptane, 2,3,6- trimethylheptane, 2,4,5- trimethylheptane, 2,4,6- trimethylheptane,
2,2,3- trimethylheptane, 2,2,4- trimethylheptane, 2,2,5- trimethylheptane, 2,2,6- trimethylheptane, 2,3,3- tri-
Methyl heptane, 2,4,4- trimethylheptane, 2- methyl -3- ethyl heptane, 2- methyl -4- ethyl heptane, 2- methyl -5- ethyl heptan
Alkane, 3- methyl -3- ethyl heptane, 4- methyl -3- ethyl heptane, 5- methyl -3- ethyl heptane, 4- methyl -4- ethyl heptane, 4-
Propyl heptane, 3,3- diethylhexane, 3,4- diethylhexane, 2- methyl -3,3- diethylpentane, vinylbenzene, 1- phenyl third
One of alkane, 2- phenyl-propane, 1- phenyl butane, 2- phenyl butane, 1- phenyl pentane, 2- phenyl pentane and 3- phenyl pentane
Or two or more combination.It is highly preferred that the hydrocarbon be one or both of propane, normal butane, iso-butane and vinylbenzene with
On.It is further preferred that the hydrocarbon is normal butane.
Hydrocarbon oxidative dehydrogenation method according to the present invention, the dosage of oxygen can be conventional selection.Generally, hydrocarbon and oxygen
The molar ratio of gas can be 0.2-3:1, preferably 0.5-2.5:1, more preferably 1-2:1.
Hydrocarbon and optional oxygen can be sent into reactor by carrier gas by hydrocarbon oxidative dehydrogenation method according to the present invention
In with the haptoreaction of carbon material containing hetero atom.The carrier gas can for it is common at reaction conditions will not with reactant and react
The gas that product occurs chemical interaction and will not decompose, such as nitrogen, carbon dioxide, rare gas and vapor
One or more of combination.The dosage of the carrier gas can be conventional selection.Generally, the content of carrier gas can be
30-99.5 volume %, preferably 50-99 volume %, more preferably 70-98 volume %.
The temperature of hydrocarbon oxidative dehydrogenation method according to the present invention, the contact can be conventional selection, to be enough to make
Hydrocarbon occurs subject to dehydrogenation reaction.Generally, the contact can 200-650 DEG C at a temperature of carry out, preferably at 300-600 DEG C
At a temperature of carry out, more preferably 350-550 DEG C at a temperature of carry out, further preferably 400-450 DEG C at a temperature of carry out.
Hydrocarbon oxidative dehydrogenation method according to the present invention, the contact can carry out in fixed bed reactors, can also
To carry out in a fluidized bed reactor, it is not particularly limited.Preferably, the contact carries out in fixed bed reactors.
Hydrocarbon oxidative dehydrogenation method according to the present invention, duration of the contact can according to the temperature of contact into
Row selection can indicate contact when such as described contact carries out in fixed bed reactors with volume space velocity when the gas of charging
Duration.Generally, volume space velocity can be 500-2000h when the gas of charging-1, preferably 800-1200h-1。
The present invention will be described in detail with reference to embodiments, but does not therefore limit the scope of the invention.
In following embodiment and comparative example, outfit of the X-ray photoelectron spectroscopic analysis in Thermo Scientific company
It is tested on the ESCALab250 type x-ray photoelectron spectroscopy for having Thermo Avantage V5.926 software, excitaton source
For monochromatization Al K α X-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, analysis test
When base vacuum be 6.5 × 10-10Mbar, the peak C1s (284.6eV) correction of electron binding energy simple substance carbon, in Thermo
Data processing is carried out on Avantage software, and quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is being surveyed
It is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before examination.
In following embodiment and comparative example, using the ASAP2000 type N of Micromertrics company of the U.S.2Physical absorption
Instrument measurement the specific area, volume average particle size measure on laser particle analyzer.
In following embodiment and comparative example, elemental analysis carries out on Elementar Micro Cube elemental analyser,
Concrete operation method and condition are as follows: sample weighs 1-2mg in tin can, is put into automatic sampling disk, enters burning by ball valve
Pipe burning, ignition temperature are 1000 DEG C (when in order to remove sample introduction atmospheric interference, using helium purge), then with going back native copper to combustion
Gas after burning is restored, and nitrogen, carbon dioxide and water are formed.Mixed gas is separated by three desorption columns, successively
It is detected into TCD detector.The analysis of oxygen element is that under the action of C catalyst, the oxygen in sample is turned using pyrolytic
CO is turned to, CO is then detected using TCD.
In following embodiment and comparative example, X-ray diffraction analysis is on Rigaku D/MAX-2500 type X-ray diffractometer
It carries out, using CuK alpha ray, operating voltage 20kV, tube current 10mA, scanning range is 5 ° -70 °.
Embodiment 1-9 is for illustrating the present invention.
Embodiment 1
(it will be purchased from green World Activated Carbon Co., Ltd, volume average particle size is 200 μ as the active carbon of raw material carbon material
M, nature parameters are listed in table 1, in the X-ray diffraction spectrogram of the raw material carbon material, 2 angles θ be 20 ° -30 ° between and
Disperse peak is respectively present between 40 ° -50 °, there is no diffraction maximum and bright and sharp peaks in remaining position) it is placed in tube furnace in 500 DEG C
5h is roasted, continues to be passed through atmosphere reactive (its being made of ammonia, vapor and nitrogen into tube furnace in roasting process
In, the content of ammonia is 3 volume %, and the content of vapor is 2 volume %), after roasting, above-mentioned atmosphere reactive is kept,
By the temperature cooled to room temperature of tube furnace, carbon material containing hetero atom according to the present invention (volume average particle size 205 is obtained
μm), nature parameters are listed in table 1.
Embodiment 2
Carbon material containing hetero atom is prepared using method same as Example 1, unlike, the temperature of roasting is 700 DEG C,
To obtain carbon material containing hetero atom according to the present invention (volume average particle size is 210 μm), nature parameters arrange in table 1
Out, this contains in the X-ray diffraction spectrogram of hetero atom carbon material, is to be respectively present between 40 ° -50 ° between 20 ° -30 ° at 2 angles θ
Disperse peak.
Embodiment 3
Carbon material containing hetero atom is prepared using method same as Example 1, unlike, the temperature of roasting is 900 DEG C,
To obtain carbon material containing hetero atom according to the present invention (volume average particle size is 209 μm), nature parameters arrange in table 1
Out, this contains in the X-ray diffraction spectrogram of hetero atom carbon material, is to be respectively present between 40 ° -50 ° between 20 ° -30 ° at 2 angles θ
Disperse peak.
Embodiment 4
Carbon material containing hetero atom is prepared using method same as Example 1, unlike, the temperature of roasting is 1000
DEG C, to obtain carbon material containing hetero atom according to the present invention (volume average particle size is 202 μm), nature parameters are in table 1
It lists, this contains in the X-ray diffraction spectrogram of hetero atom carbon material, is to deposit respectively between 40 ° -50 ° between 20 ° -30 ° at 2 angles θ
At disperse peak.
Embodiment 5
Carbon material containing hetero atom is prepared using method same as Example 1, unlike, the temperature of roasting is 1200
DEG C, to obtain carbon material containing hetero atom according to the present invention (volume average particle size is 198 μm), nature parameters are in table 1
It lists, this contains in the X-ray diffraction spectrogram of hetero atom carbon material, is to deposit respectively between 40 ° -50 ° between 20 ° -30 ° at 2 angles θ
At disperse peak.
Embodiment 6
Carbon material containing hetero atom is prepared using method same as Example 1, unlike, the temperature of roasting is 400 DEG C,
To obtain carbon material containing hetero atom according to the present invention (volume average particle size is 203 μm), nature parameters arrange in table 1
Out, this contains in the X-ray diffraction spectrogram of hetero atom carbon material, is to be respectively present between 40 ° -50 ° between 20 ° -30 ° at 2 angles θ
Disperse peak.
Embodiment 7
Carbon material containing hetero atom is prepared using method same as Example 1, unlike, the not aqueous steaming of atmosphere reactive
Gas, to obtain carbon material containing hetero atom according to the present invention (volume average particle size is 208 μm), nature parameters are in table 1
It lists, this contains in the X-ray diffraction spectrogram of hetero atom carbon material, is to deposit respectively between 40 ° -50 ° between 20 ° -30 ° at 2 angles θ
At disperse peak.
Comparative example 1
Carbon material containing hetero atom is prepared using method same as Example 2, unlike, raw material carbon material is received using carbon
Mitron (is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences, nature parameters are listed in table 1), and what is obtained contains hetero atom
The nature parameters of carbon pipe are listed in table 1.
Comparative example 2
Carbon material containing hetero atom is prepared using method same as Example 1, unlike, atmosphere reactive is free of ammonia
The nature parameters of gas, obtained product are listed in table 1.
Comparative example 3
Carbon material containing hetero atom is prepared using method same as Example 1, unlike, the temperature of roasting is 300 DEG C,
The nature parameters of obtained product are listed in table 1.
Comparative example 4
Nano-carbon material containing hetero atom is prepared using method same as Example 1, unlike, the temperature of roasting is
1500 DEG C, the nature parameters of obtained product are listed in table 1.
Embodiment 8
By as the active carbon of raw material carbon material (be purchased from Beijing chemical reagents corporation, volume average particle size be 120 μm,
Nature parameters are listed in table 1, in the X-ray diffraction spectrogram of the raw material carbon material, 2 angles θ be 20 ° -30 ° between and 40 ° -
Disperse peak is respectively present between 50 °, there is no diffraction maximum and bright and sharp peaks in remaining position) it is placed in tube furnace in 800 DEG C of roastings
3h continues to be passed through atmosphere reactive (wherein, the ammonia being made of ammonia, vapor and nitrogen into tube furnace in roasting process
The content of gas is 1.5 volume %, and the content of vapor is 1 volume %), after roasting, above-mentioned atmosphere reactive is kept, will be managed
The temperature cooled to room temperature of formula furnace obtains carbon material containing hetero atom according to the present invention (volume average particle size is 123 μm),
Its nature parameters is listed in table 1, this contains in the X-ray diffraction spectrogram of hetero atom carbon material, 2 angles θ be 20 ° -30 ° between and
Disperse peak is respectively present between 40 ° -50 °.
Embodiment 9
(it will be purchased from Beijing chemical reagents corporation, volume average particle size is 80 μm, property as the active carbon of raw material carbon material
Matter parameter is listed in table 1, in the X-ray diffraction spectrogram of the raw material carbon material, 2 angles θ be 20 ° -30 ° between and 40 ° -50 °
Between be respectively present disperse peak, in remaining position, there is no diffraction maximum and bright and sharp peaks) be placed in tube furnace in 800 DEG C of roasting 2h,
Continue to be passed through atmosphere reactive (wherein, the ammonia being made of ammonia, vapor and nitrogen in roasting process into tube furnace
Content is 0.5 volume %, and the content of vapor is 0.5 volume %), after roasting, above-mentioned atmosphere reactive is kept, by tubular type
The temperature cooled to room temperature of furnace obtains carbon material containing hetero atom according to the present invention (volume average particle size is 87 μm),
Nature parameters are listed in table 1, this contains in the X-ray diffraction spectrogram of hetero atom carbon material, 2 angles θ be 20 ° -30 ° between and
Disperse peak is respectively present between 40 ° -50 °.
Table 1
1: the raw material carbon material that embodiment 1 uses
2: the carbon nanotube as raw material that comparative example 1 uses
3: the raw material carbon material that embodiment 8 uses
4: the raw material carbon material that embodiment 9 uses
5: the content of the oxygen determined by x-ray photoelectron spectroscopy is a, and the content of the oxygen determined by elemental microanalysis method is b.
Fig. 1 shows the X-ray diffraction spectrogram of the raw material carbon material of the use of embodiment 1, and Fig. 2 shows the preparations of embodiment 1
The carbon material containing hetero atom X-ray diffraction spectrogram.Figure it is seen that carbon material containing hetero atom prepared by embodiment 1 is in 2 θ
Angle is that disperse peak is respectively present between 40 ° -50 ° between 20 ° -30 °.Fig. 3 and Fig. 4 respectively illustrates the work of the use of comparative example 1
It, can from Fig. 4 for the X-ray diffraction spectrogram of the carbon nanotube containing hetero atom prepared by the carbon nanotube and comparative example 1 of raw material
The nano-carbon material containing hetero atom that out prepared by comparative example 1 has still maintained the ordered structure of carbon nanotube.
EXPERIMENTAL EXAMPLE 1-9
The carbon material containing hetero atom respectively prepared by embodiment 1-9 is used as the catalyst of n butane oxidation dehydrogenation, and carries out
N butane oxidation dehydrogenation reaction, the specific method is as follows.
The carbon material containing hetero atom of 0.2g (admission space 0.5mL) embodiment 1-9 preparation is filled as catalyst respectively
It fills out in universal fixed bed miniature quartz pipe reactor, two end seal of miniature quartz pipe reactor has quartz sand, in normal pressure (that is, 1
Standard atmospheric pressure) and 400 DEG C under conditions of, by containing normal butane and oxygen gas (concentration of normal butane be 1.0 volume %,
The molar ratio of normal butane and oxygen is 1:2, and surplus is nitrogen as carrier gas) it with total volume air speed is 1200h-1It is passed through reactor
In reacted, continuously monitor the composition of the reaction mixture exported from reactor, and calculate n-butane conversion, total olefin
Selectivity and n-butene selectivity, the results are shown in Table 2 within 5 hours for reaction.
Experimental comparison's example 1-4
Butane oxidation dehydrogenation reaction is carried out using method identical with EXPERIMENTAL EXAMPLE 1-9, unlike, the catalysis of use
Agent is the product of comparative example 1-4 preparation, and the results are shown in Table 2 within 5 hours for reaction.
Control experiment example 1-4
Butane oxidation dehydrogenation reaction is carried out using method identical with EXPERIMENTAL EXAMPLE 1-9, unlike, the catalysis of use
Agent is the raw material carbon material in embodiment 1,8 and 9 and the raw material carbon nanotube in comparative example 1, the result column of reaction 5 hours
In table 2.
Table 2
1: using the raw material carbon material that embodiment 1 uses as catalyst2: the carbon as raw material used using comparative example 1 is received
Mitron is as catalyst
3: using the raw material carbon material that embodiment 8 uses as catalyst4: using embodiment 9 use raw material carbon material as
Catalyst
Table 2 as a result, it was confirmed that catalyst using carbon material containing hetero atom of the invention as hydrocarbon oxidative dehydrogenation, energy
The selectivity for alkene is greatly improved.Existing catalyst is although higher n-butane conversion can be obtained, alkene choosing
Selecting property is lower, thus most of normal butane burns in vain, anti-as hydrocarbon oxidative dehydrogenation using carbon material containing hetero atom of the invention
The catalyst answered, although n-butane conversion is declined, unconverted normal butane can separate recycling, mention
The high overall utilization of raw material.Also, carbon material containing hetero atom according to the present invention is made using cheap amorphous carbon
For raw material, preparation process is succinct, significantly reduces manufacturing cost.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (18)
1. a kind of carbon material containing hetero atom, this contains hetero atom carbon material and contains oxygen element, nitrogen, protium and carbon, with
On the basis of the total amount of the carbon material containing hetero atom and based on the element, the content of the oxygen element is 1-10 weight %, the nitrogen member
The content of element is 0.01-4 weight %, and the content of the protium is 0.1-3 weight %, and the content of the carbon is 83-
98.89 weight %,
In the X ray diffracting spectrum of the carbon material containing hetero atom, between 2 angles θ is 20 ° -30 ° and between 40 ° -50 ° respectively
There are disperse peaks；
This contains in hetero atom carbon material, and the content of the Surface Oxygen determined by x-ray photoelectron spectroscopy is a, true by elemental microanalysis method
The content of fixed body phase oxygen is b, a/b >=2.
2. carbon material containing hetero atom according to claim 1, wherein a/b 2-5, preferably 2.1-4.5.
3. carbon material containing hetero atom according to claim 1 or 2, wherein using the total amount of the carbon material containing hetero atom as base
Quasi- and based on the element, the content of the oxygen element is 1.2-8 weight %, preferably 1.5-6 weight %；The content of the nitrogen
For 0.03-3 weight %, preferably 0.05-2 weight %；The content of the protium is 0.2-2.5 weight %, preferably 0.4-2
Weight %；The content of the carbon is 86.5-98.57 weight %, preferably 90-98.05 weight %.
4. carbon material containing hetero atom described in any one of -3 according to claim 1, wherein this contains the ratio of hetero atom carbon material
Surface area is >=100m2/ g, preferably >=500m2/ g, more preferably >=600m2/ g, further preferably 700-1500m2/g。
5. a kind of preparation method of carbon material containing hetero atom, this method comprises: by raw material carbon material in a kind of atmosphere reactive,
It is roasted at a temperature of 400-1200 DEG C, the atmosphere reactive contains ammonia, optional carrier gas and optional water and steams
Gas；
The raw material carbon material contains oxygen element, protium and carbon, on the basis of the total amount of the raw material carbon material and with
Element meter, the content of the oxygen element are 0.2-12 weight %, and the content of the protium is 0.05-3 weight %, the carbon member
The content of element is 85-99.75 weight %；
In the X ray diffracting spectrum of the raw material carbon material, deposited respectively between 2 angles θ is 20 ° -30 ° and between 40 ° -50 °
At disperse peak；
In the raw material carbon material, the content of the Surface Oxygen determined by x-ray photoelectron spectroscopy is a, is determined by elemental microanalysis method
Body phase oxygen content be b, a/b < 2.
6. according to the method described in claim 5, wherein, the atmosphere reactive contains vapor, in the atmosphere reactive,
The content of vapor be 0.01-10 volume %, preferably 0.1-9 volume %, more preferably 0.2-5 volume %, further preferably
For 0.5-2 volume %.
7. method according to claim 5 or 6, wherein in the atmosphere reactive, the content of ammonia is 0.01-5 body
Product %, preferably 0.1-4 volume %, more preferably 0.5-3 volume %.
8. the method according to any one of claim 6-7, wherein a/b 0.9-1.95, preferably 1.2-
1.9。
9. the method according to any one of claim 6-8, wherein on the basis of the total amount of the raw material carbon material simultaneously
Based on the element, the content of the oxygen element is 0.5-10 weight %, preferably 1-9.5 weight, more preferably 2-9 weight %；Institute
The content for stating protium is 0.1-3 weight %, preferably 0.5-2.8 weight %, more preferably 1-2.6 weight %；The carbon member
The content of element is 87-99.4 weight %, preferably 87.7-98.5 weight %, more preferably 88.4-97 weight %.
10. the method according to any one of claim 6-9, wherein the specific surface area of the raw material carbon material is
400-1400m2/ g, preferably 600-1300m2/ g, more preferably 800-1200m2/g。
11. the method according to any one of claim 6-10, wherein the raw material carbon material is active carbon.
12. the method according to any one of claim 6-11, wherein it is described roasting 500-1100 DEG C at a temperature of
Carry out, preferably 700-1000 DEG C at a temperature of carry out.
13. the method according to any one of claim 6-12, wherein the duration of the roasting is that 0.5-24 is small
When, preferably 1-8 hours, more preferably 2-6 hours.
14. a kind of carbon material containing hetero atom of the preparation of the method as described in any one of claim 6-13.
15. catalysis of the carbon material containing hetero atom as hydrocarbon oxidative dehydrogenation described in any one of claim 1-5 and 14
The application of agent.
16. application according to claim 15, wherein the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably
Butane, further preferably normal butane.
17. a kind of hydrocarbon oxidative dehydrogenation processes, this method are included under the conditions of oxidative dehydrogenation, by hydrocarbon and claim 1-5 and
The contact of carbon material containing hetero atom described in any one of 14.
18. according to the method for claim 17, wherein the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably
Butane, further preferably normal butane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710625268.8A CN109304196B (en) | 2017-07-27 | 2017-07-27 | Heteroatom-containing carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710625268.8A CN109304196B (en) | 2017-07-27 | 2017-07-27 | Heteroatom-containing carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109304196A true CN109304196A (en) | 2019-02-05 |
| CN109304196B CN109304196B (en) | 2021-05-14 |
Family
ID=65202619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710625268.8A Active CN109304196B (en) | 2017-07-27 | 2017-07-27 | Heteroatom-containing carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109304196B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461486A (en) * | 2020-03-31 | 2021-10-01 | 中国石油化工股份有限公司 | Catalytic oxidation method of naphthenic hydrocarbon |
| WO2024082309A1 (en) * | 2022-10-21 | 2024-04-25 | 宁德时代新能源科技股份有限公司 | Carbonaceous material and preparation method therefor, and secondary battery and electrical device comprising same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105817242A (en) * | 2015-01-27 | 2016-08-03 | 中国石油化工股份有限公司 | Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons |
| CN105905895A (en) * | 2016-04-15 | 2016-08-31 | 中国科学院理化技术研究所 | Preparation device of nitrogen-containing activated carbon and preparation method |
-
2017
- 2017-07-27 CN CN201710625268.8A patent/CN109304196B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105817242A (en) * | 2015-01-27 | 2016-08-03 | 中国石油化工股份有限公司 | Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons |
| CN105817249A (en) * | 2015-01-27 | 2016-08-03 | 中国石油化工股份有限公司 | Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons |
| CN105817247A (en) * | 2015-01-27 | 2016-08-03 | 中国石油化工股份有限公司 | Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons |
| CN105905895A (en) * | 2016-04-15 | 2016-08-31 | 中国科学院理化技术研究所 | Preparation device of nitrogen-containing activated carbon and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| JIAN ZHANG等: "Surface-Modified Carbon Nanotubes Catalyze Oxidative Dehydrogenation of n-Butane", 《SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461486A (en) * | 2020-03-31 | 2021-10-01 | 中国石油化工股份有限公司 | Catalytic oxidation method of naphthenic hydrocarbon |
| CN113461486B (en) * | 2020-03-31 | 2023-08-08 | 中国石油化工股份有限公司 | Catalytic oxidation method of cycloalkane |
| WO2024082309A1 (en) * | 2022-10-21 | 2024-04-25 | 宁德时代新能源科技股份有限公司 | Carbonaceous material and preparation method therefor, and secondary battery and electrical device comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109304196B (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | MOF-derived hierarchical hollow spheres composed of carbon-confined Ni nanoparticles for efficient CO 2 methanation | |
| US9981845B2 (en) | Catalyst for producing hydrogen and method for producing hydrogen | |
| Zhou et al. | Two-dimensional molybdenum carbide 2D-Mo2C as a superior catalyst for CO2 hydrogenation | |
| Dai et al. | Single Ni sites distributed on N-doped carbon for selective hydrogenation of acetylene | |
| Liu et al. | Methane reforming with carbon dioxide over a Ni/ZiO2–SiO2 catalyst: Influence of pretreatment gas atmospheres | |
| Kovalskii et al. | (Ni, Cu)/hexagonal BN nanohybrids–New efficient catalysts for methanol steam reforming and carbon monoxide oxidation | |
| Valentini et al. | Role of vanadium in Ni: Al2O3 catalysts for carbon dioxide reforming of methane | |
| Xu et al. | Ultrafine NiO–La2O3–Al2O3 aerogel: a promising catalyst for CH4/CO2 reforming | |
| Cheng et al. | Molybdenum phosphide, a new hydrazine decomposition catalyst: Microcalorimetry and FTIR studies | |
| Li et al. | Unveiling the origin of enhanced catalytic performance of NiCu alloy for semi-hydrogenation of acetylene | |
| CN106607018B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method and application | |
| Jung et al. | The surfactant-assisted Ni–Al2O3 catalyst prepared by a homogeneous precipitation method for CH4 steam reforming | |
| Seo et al. | Hydrogen production by steam reforming of simulated liquefied natural gas (LNG) over mesoporous nickel–M–alumina (M= Ni, Ce, La, Y, Cs, Fe, Co, and Mg) aerogel catalysts | |
| CN109304196A (en) | One kind carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon oxidative dehydrogenation processes | |
| Wu et al. | Dynamic nanoscale imaging of enriched CO adlayer on Pt (111) confined under h-BN monolayer in ambient pressure atmospheres | |
| Zhang et al. | Low-temperature dry reforming of methane tuned by chemical speciations of active sites on the SiO2 and γ-Al2O3 supported Ni and Ni-Ce catalysts | |
| Wan et al. | Promotive effect of boron oxide on the iron-based catalysts for Fischer-Tropsch synthesis | |
| Habimana et al. | Effect of Cu promoter on Ni-based SBA-15 catalysts for partial oxidation of methane to syngas | |
| Sorcar et al. | Design of coke-free methane dry reforming catalysts by molecular tuning of nitrogen-rich combustion precursors | |
| Bian et al. | Enhanced metal-support interaction on NiSi-P catalyst for improved COx methanation performance | |
| CN106925326B (en) | One kind nano-carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method | |
| CN109304197A (en) | One kind carbon material containing metallic atom and its preparation method and application and a kind of hydrocarbon oxidative dehydrogenation processes | |
| Liu et al. | The key points of highly stable catalysts for methane reforming with carbon dioxide | |
| CN109305683A (en) | One kind carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon oxidative dehydrogenation processes | |
| Hwu et al. | Potential application of tungsten carbides as electrocatalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |