CN109686982A - A method of preparing load type carbon nitride - Google Patents
A method of preparing load type carbon nitride Download PDFInfo
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- CN109686982A CN109686982A CN201910115204.2A CN201910115204A CN109686982A CN 109686982 A CN109686982 A CN 109686982A CN 201910115204 A CN201910115204 A CN 201910115204A CN 109686982 A CN109686982 A CN 109686982A
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- carbon
- carbonitride
- carbon carrier
- load
- nitride
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- 238000000034 method Methods 0.000 title claims abstract description 35
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 88
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 150000001722 carbon compounds Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
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- 206010037660 Pyrexia Diseases 0.000 claims description 2
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
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- 239000005416 organic matter Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 229960004424 carbon dioxide Drugs 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- -1 heating Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
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- 238000012986 modification Methods 0.000 claims 1
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- 230000008569 process Effects 0.000 abstract description 14
- 238000007598 dipping method Methods 0.000 abstract description 4
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- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 229910000765 intermetallic Inorganic materials 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 7
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- 238000002360 preparation method Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 235000019764 Soybean Meal Nutrition 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004455 soybean meal Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of methods for preparing load type carbon nitride, the steps include: s1) one or more kinds of metallic element compounds is prepared into solution, carbon carrier is impregnated with the solution；S2 all or part of solvent therein then) is removed to the carbon carrier heat drying after dipping；S3 300 DEG C or more progress carbon nitridation reactions) are further heated to the carbon carrier after drying under protective atmosphere, obtain the carbonitride of support type；And the heating process in one of step s2 and s3 or both is by being powered to carbon carrier, so that carbon carrier itself is heated as resistance heating.It is an advantage of the invention that prepared carbonitride is evenly distributed on the carbon carrier, good product consistency, process stabilizing, production capacity is big.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, are related to the preparation method of load type carbon nitride.
Background technique
Active carbon have high specific surface area, flourishing pore structure, surface functional group enrich, have partially electronically conductive property etc. it is excellent
Property is widely used in catalyst preparation, water process, air pollution processing, mineral and the extraction of pharmaceuticals industry, battery, secondary electricity
Pond, super capacitor etc. field, application range are very extensive.
Noble metal is as catalyst activity component, in fields such as the energy, fuel cell, photochemistry, chemistry, chemical industry, environmental protection
It has a wide range of applications.Noble metal has that activity is high, selectivity is good, reaction condition is mild, stablizes as catalyst activity component
The advantages that property good service life is long.But the toxicity such as noble metal is at high price, catalyst activity component metal such as cadmium, mercury, lead for having are high
The disadvantages of.Therefore seeking noble metal substitute all the time is all one of the hot spot direction of catalytic chemistry research.By many years
Research, discovery metal carbides, nitride or carbonitride (hereinafter referred to as carbonitride or carbonitride) have
The carbonitride of catalytic activity and stability, especially transition metal with precious metal.But carbonitride directly as
Catalyst material, specific surface area is too low, there is no pore structure, therefore there is no catalytic activity.Must prepare has
The carbonitride of big inner surface and inner hole loads to carbonitride on the carrier of high-specific surface area.
The carbon carriers such as active carbon, graphene, carbon nanotube, large specific surface area or pore structure are flourishing, are chemical necks
The common carrier material in domain.Carbon carrier catalyst generally passes through infusion process and metallic compound active component is loaded to carbon carrier
On, then prepared by chemical modifications processes such as dry or further thermal decompositions.If preparing carbon carrier load
Carbonitride, usually first then load carries out carbon nitridation reaction again.But the general fusing point of carbonitride is high and several
Any solvent is not dissolved in, is difficult directly to load on carbon carrier or other carrier materials carbonitride by infusion process.
Existing research, the preparation method of load type carbon compound is generally by first impregnating soluble metal compound
It onto carbon carrier, is then heated under protective atmosphere again, so that the metallic compound reaction of load generates carbonitride.Also grind
Study carefully by mixing metallic compound with biomass isoreactivity charcoal precursor, then carbonization generates active carbon and carbon at high temperature
Nitride.Existing preparation method has following two disadvantages:
First is that during carbon carrier is dry after dipping or during heating removal solvent, it is general using external heating, heat
Amount passes to carbon carrier by way of dielectric gas convection current or heat transfer, and the evaporation of solvent is occurred mainly in close to heat source
On on the carbon carrier of the part and outer surface of carbon carrier particle, metallic compound will follow solvent to move from the inner surface of carbon carrier particle
Move on to outer surface.This accumulates metallic element in the close outer surface of carbon carrier particle, and dispersion is uneven, and catalysis is brought to live
Property reduce, the problems such as catalyst life is short.
Second is that, using traditional external heating method, heat passes through during higher temperature heats carburizing reagent
The mode of dielectric gas convection current or heat transfer passes to the metallic compound of carbon carrier and load, and the carbon close to heat source is caused to carry
The outer surface part of body or carbon carrier particle overheat, so that the carbonitride particle size generated is excessive, catalytic activity
It is low even without no active (it is, in general, that metal active centres dispersion degree is higher, catalytic activity is better).
In addition, the generation temperature due to many carbonitrides is excessively high, or even to 1000 DEG C or more.Will under protective atmosphere,
Such chemical reaction is carried out, the physical property such as the granularity of the carbonitride of load is also controlled, there is no effective and feasible
Method.
In conclusion the existing method for preparing load type carbon nitride, it is difficult to be prepared and is uniformly dispersed on carrier
Carbonitride.There is no the methods of practical suitable large-scale industrial production load type carbon nitride at present.
Summary of the invention
The purpose of the present invention is to provide a kind of loads to be uniformly dispersed, loaded article granularity is small, low energy consumption, equipment capacity is big,
Product quality consistency is good, stable technical process load type carbon nitride production technology.By being used in electric heating reacting furnace
Carbon carrier (hereafter referred to collectively as material) direct-electrifying that power electrode generates carbon carrier or its precursor during the reaction, according to
Contact resistance between the resistance or feed particles or block of material itself generates heat and heated material under the action of electric current.
The preparation method of the carbon carrier load carbonitride of existing literature report, there is the report using modified carbon carrier more
Road is mainly utilized in active carbon inner surface in-situ polymerization and prepares polyaniline, polyacrylonitrile, polypyrrole (or their derivative
Object) etc. polymer, either directly adopt active carbon, carbon nanotube or the graphene of high nitrogen-containing.Carbon carrier in the present invention
These carbon materials modified can be equally used, and is reacted in subsequent carried metal compound and generates carbonitride
In the process, nitrogenous protective atmosphere can also be used, the nitrogen content in carbon carrier is further increased.
Method disclosed by the invention, it is particularly possible to using conducts such as nitrogen content relatively high biological materials, such as dregs of beans
The presoma of carbon carrier is directly used in the preparation of carbon carrier load type carbon nitride of the invention, by metallic compound and the biology
Matter presoma (or the auxiliary materials such as part bonding agent, release agent are added) directly mixed grind molding, successively dry, carbonization generate carbon and carry
Body, carbon nitridation generate the carbonitride of load.The process can even avoid to avoid the process for the solution for preparing metallic compound
The use of solvent reduces pollution, shortens process, reduces energy consumption and cost.
The object of the present invention is achieved like this:
A method of preparing load type carbon compound, nitride and/or carbonitride, it is characterised in that: by following steps into
Row preparation:
S1 one or more kinds of metallic element compound or its solution are mixed with carbon carrier), form load carbon carrier；
S2) all or part of solvent therein to load carbon carrier heat drying or removal in reacting furnace；
S3) in the reacting furnace same or different from the step s2, to the load carbon carrier after drying under protective atmosphere
Be further heated to 300 DEG C or more progress carbon (and/or nitrogen) and change reaction, obtain the metal carbides of support type, nitride and/or
Carbonitride；
In one of two step of the step s2 and s3 or in two step of s2 and s3, using to load carbon carrier direct-electrifying
Mode heated.
Further, the reacting furnace described in the step s2 or s3 are as follows: burner hearth has the electric heating of bringing-up section
Reacting furnace is provided with heating power supply electrode in the bringing-up section, applied on the material being heated by the electrode voltage from
And to the material feed-in electric current being heated, it is heated using the resistance heating heating for the material being heated accumulated in bringing-up section
Material；
The described method for using the mode to load carbon carrier direct-electrifying to be heated for, by the load carbon carrier into
Expect in the reacting furnace, the load carbon carrier passes through heating process；In the heating process, pass through power electrode
Resulting material is changed in the heating process to the load carbon carrier and/or its that are in the bringing-up section
(hereafter referred to collectively as material) direct-electrifying, by bringing-up section material itself resistance or material particles or block between
Contact resistance fever and heated material, and the maximum temperature that the material passes through in the reacting furnace is not less than
300℃。
Further, the protective atmosphere are as follows: helium, nitrogen, argon gas, ammonia, hydrogen, air, oxygen, natural gas,
One of carbon monoxide, gaseous state or volatile organic matter or more than one mixture vacuumize.
Further, the carbon carrier is graphite, graphene, carbon nanotube, active carbon, activated carbon fibre, process
Modified graphite, graphene modified, carbon nanotube modified, active carbon modified, work modified
One of the biomass that can be carbonized after property Carbon fibe, heating, pitch, coal tar, petroleum coke or more than one.
Further, the reacting furnace is the electric heating rotary kiln that Chinese patent CN103335513A is disclosed.
Further, being provided with preheating section before the bringing-up section of the reacting furnace and/or in the bringing-up section
It is provided with temperature descending section later, material is preheated and/or is cooled down.
Further, the solvent of the solution is water, liquefied ammonia, ionic liquid, methanol, ethyl alcohol and/or other organic
One of solvent or more than one mixture.
Further, it is primary or multiple to repeat step s1 and s2, then carry out step s3；Or repeat step s1, s2
It is primary or multiple with s3.
Compared with the prior art, the invention has the following beneficial effects:
1) apply direct current or alternating voltage directly into material with electrode and be passed through electric current, material accumulation, which is got up, itself has one
Fixed resistance, the resistance generate heat under the function of current, eliminate diabatic process of the heat from heater element to material, avoid pair
Fire resisting material of furnace body and the nondistinctive heating of material, heat utilization ratio is high, and power consumption is low.And it avoids and is caused because of thermal transmission requirement
Make the limitation of material accumulation thinner thickness, furnace cavity utilization rate improves, and productivity improves, but also electric heating reacting furnace can be with
That does is smaller.
2) it due to carrying out heating reaction by the way of to the heating of raw material direct-electrifying, avoids using Elema, silicon molybdenum
The resistance heating elements such as stick or molybdenum filament and crucible.Easy to operate, cost is relatively low.
3) heating process can carry out in directly-heated type rotary kiln, material obtain it is lasting stir, further improve anti-
Heat and mass transfer process during answering, so that the reaction time is short, the thermal efficiency is high, and uniform in quality is stablized, and material is in directly-heated type
Traveling can be continuously moved inside rotary kiln and directly-heated type shaft kiln, be convenient for large-scale industrial production, good product consistency.
4) due in directly-heated type rotary kiln and having preheating section in directly-heated type shaft kiln, a heating section and a cooling section can pass through control
Revolving speed or discharging speed the control material of directly-heated type rotary kiln processed avoid excessive heating in the residence time of each temperature section
The carbonitride granularity for causing carbon carrier inner surface to generate increases.
5) using the method to load carbon carrier direct-electrifying heating removal solvent, solvent in carbon carrier particle inner surface and
Synchronous evaporation, avoids in the external heating process that the prior art uses, heat passes through dielectric gas on particle exterior surface
The mode of convection current or heat transfer passes to carbon carrier, the evaporation of solvent occur mainly on the part carbon carrier of heat source and
On the outer surface of carbon carrier particle, metallic compound will follow solvent to move to outer surface from the inner surface of carbon carrier particle, from
And metallic element is accumulated in the close outer surface of carbon carrier particle, dispersion is uneven, brings catalytic activity to reduce, catalysis
The problems such as agent service life is short.
6) maximum heating temperature that material process can be improved, improves the graphite rate of carbon carrier, to improve its conduction
Property.The raising of electric conductivity, the material for being beneficial to prepared are used for fuel cell and secondary cell.
Specific embodiment
Illustrate specific technical solution of the invention now in conjunction with embodiment.Following embodiment only illustrates skill of the invention
Art scheme reliable and effective can be realized, but technical solution of the invention is not limited in following embodiment.
Embodiment 1
Carbon carrier: active carbon, heap density 0.38g/ml, BET specific surface area 1091m2/g, partial size 2.5mm, particle length 2~
6mm.Measure active carbon 200ml.
Metallic compound: ammonium paratungstate, wherein WO3Content >=88.5%, 20.0g be dissolved in about 150ml distilled water obtain it is molten
Liquid A.
Load type carbon nitride: foregoing active charcoal is poured into solution A, room temperature immersion 1h.Extra moisture is filtered out, is filled
Enter formation active carbon stock column in the glass tube of internal diameter 3cm.Heating power supply is connected at the both ends of the stock column, controls the electricity of heating power supply
Stream≤1A heats stock column, controls not more than 150 DEG C of stock column temperature, is heated in stock column that there is no apparent vapor
When releasing, stop heating.Load carbon carrier is fitted into the silicon carbide tube furnace of internal diameter 3cm and forms stock column, nitrogen is passed through, at this
The both ends of stock column connect heating power supply, control electric current≤5A of heating power supply, are slowly warming up to 850 DEG C, keep the temperature 1h, cool to room
Temperature discharging.Activated carbon supported tungsten carbide is prepared.
The outer layer and internal layer of careful separation active carbon particle measure W content therein respectively, find tungsten in ectonexine
Percentage composition is equal (difference is within the scope of analytical error).
Embodiment 2
Carbon carrier: active carbon, heap density 0.38g/ml, BET specific surface area 1091m2/g, partial size 2.5mm, particle length 2~
5mm.The active carbon 200ml, 200ml aniline hydrochloric acid solution dipping and ammonium persulfate hydrochloric acid solution dipping containing 0.1mol are measured,
At room temperature in nitrogen atmosphere 50 DEG C be dried under reduced pressure 5h.
Metallic compound: ammonium tetramolybdate solution 200ml, wherein molybdenum content 7.5g.
Load type carbon nitride: foregoing active charcoal is poured into solution ammonium tetramolybdate solution, room temperature immersion 1h.It filters out more
Remaining moisture is fitted into formation active carbon stock column in the glass tube of internal diameter 3cm.Heating power supply is connected at the both ends of the stock column, is controlled
Electric current≤1A of heating power supply, to stock column heat, control not more than 150 DEG C of stock column temperature, be heated in stock column there is no
When apparent vapor is released, stop heating.Load carbon carrier is fitted into the silicon carbide tube furnace of internal diameter 3cm and forms stock column,
It is passed through ammonia, heating power supply is connected at the both ends of the stock column, controls electric current≤5A of heating power supply, be slowly warming up to 1000 DEG C,
1h is kept the temperature, room temperature discharging is cooled to.Activated carbon supported molybdenum nitride is prepared.
The outer layer and internal layer of careful separation active carbon particle measure molybdenum content therein respectively, find molybdenum in ectonexine
Percentage composition is equal (difference is within the scope of analytical error).
Embodiment 3
Carbon carrier: Soybean Meal 200g+5g white glue with vinyl.
Metallic compound: chrome green, content >=99%, 10g.
Load type carbon nitride: aforementioned carbon carrier and chrome green are added in high-speed mixer and stir 1 minute, extrusion at
Type is then charged into the stainless steel reaction pipe of internal diameter 20mm, Resistant heating is used outside reaction tube, by material under ammonia atmosphere
400 DEG C are heated to, 2h is kept the temperature, cools to room temperature discharging.The material is fitted into the silicon carbide tube furnace of internal diameter 3cm and forms material
Column is passed through high pure nitrogen, connects heating power supply at the both ends of the stock column, controls electric current≤5A of heating power supply, be slowly warming up to
1200 DEG C, 1h is kept the temperature, cools to room temperature discharging.Activated carbon supported chromium nitride and chromium carbide is prepared.Carrier carbon therein
Middle nitrogen content reaches 3% or more (x-ray fluorescence spectrometry and x-ray photoelectron spectroscopy analysis).
Claims (8)
1. a kind of method for preparing load type carbon compound, nitride and/or carbonitride, it is characterised in that: pass through following steps
It is prepared:
S1 one or more kinds of metallic element compound or its solution are mixed with carbon carrier), form load carbon carrier；
S2) all or part of solvent therein to load carbon carrier heat drying or removal in reacting furnace；
S3) in the reacting furnace same or different from the step s2, to the load carbon carrier after drying under protective atmosphere
Be further heated to 300 DEG C or more progress carbon (and/or nitrogen) and change reaction, obtain the metal carbides of support type, nitride and/or
Carbonitride；
In one of two step of the step s2 and s3 or in two step of s2 and s3, using to load carbon carrier direct-electrifying
Mode heated.
2. the method according to claim 1 for preparing load type carbon compound, nitride and/or carbonitride, feature exist
In:
The reacting furnace described in the step s2 or s3 are as follows: burner hearth has the electric heating reacting furnace of bringing-up section, described
Bringing-up section is provided with heating power supply electrode, applies voltage on the material being heated by the electrode thus to the material being heated
Feed-in electric current heats the material being heated using the resistance heating for the material being heated accumulated in bringing-up section；
Described uses the method heated to the mode for loading carbon carrier direct-electrifying to put the load carbon carrier
Enter in the reacting furnace, the load carbon carrier passes through heating process；In the heating process, pass through power electrode pair
The load carbon carrier in the bringing-up section and/or its change resulting material in the heating process
(hereafter referred to collectively as material) direct-electrifying, by bringing-up section material itself resistance or material particles or block between
Contact resistance fever and heated material, and the maximum temperature that the material passes through in the reacting furnace is not less than
300℃。
3. load type carbon compound, nitride and/or the carbonitride as claimed in any of claims 1 to 2 of preparing
Method, it is characterised in that: the protective atmosphere are as follows: helium, nitrogen, argon gas, ammonia, hydrogen, air, oxygen, natural gas, one
One of carbonoxide, gaseous state or volatile organic matter or more than one mixture vacuumize.
4. load type carbon compound, nitride and/or the carbonitride as claimed in any of claims 1 to 3 of preparing
Method, it is characterised in that: the carbon carrier be graphite, graphene, carbon nanotube, active carbon, activated carbon fibre, by modification
Graphite, graphene modified, carbon nanotube modified, active carbon modified, active carbon modified
One of the biomass that can be carbonized after fiber, heating, pitch, coal tar, petroleum coke or more than one.
5. load type carbon compound, nitride and/or the carbonitride as claimed in any of claims 1 to 4 of preparing
Method, it is characterised in that: the reacting furnace is the electric heating rotary kiln that Chinese patent CN103335513A is disclosed.
6. load type carbon compound, nitride and/or the carbonitride as claimed in any of claims 1 to 5 of preparing
Method, it is characterised in that: preheating section is provided with before the bringing-up section of the reacting furnace and/or after the bringing-up section
It is provided with temperature descending section, material is preheated and/or is cooled down.
7. load type carbon compound, nitride and/or the carbonitride as claimed in any of claims 1 to 6 of preparing
Method, it is characterised in that: the solvent of the solution is water, liquefied ammonia, ionic liquid, methanol, ethyl alcohol and/or other organic solvents
One of or more than one mixture.
8. load type carbon compound, nitride and/or the carbonitride as claimed in any of claims 1 to 7 of preparing
Method, it is characterised in that: it is primary or multiple to repeat step s1 and s2, then carries out step s3；
It is primary or multiple either to repeat step s1, s2 and s3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441110A (en) * | 2021-08-13 | 2021-09-28 | 成都中科普瑞净化设备有限公司 | Method for preparing adsorbent for adsorbing and separating carbon monoxide |
| CN113649082A (en) * | 2021-08-13 | 2021-11-16 | 成都中科普瑞净化设备有限公司 | Method for preparing vinyl acetate catalyst by acetylene method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762297A (en) * | 2010-02-05 | 2012-10-31 | 巴斯夫欧洲公司 | Process for producing a catalyst and catalyst |
| CN103118779A (en) * | 2010-09-14 | 2013-05-22 | 巴斯夫欧洲公司 | Process for producing carbon-comprising support |
| CN103335513A (en) * | 2012-12-10 | 2013-10-02 | 冯良荣 | Electric heating rotary kiln |
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2019
- 2019-02-14 CN CN201910115204.2A patent/CN109686982A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762297A (en) * | 2010-02-05 | 2012-10-31 | 巴斯夫欧洲公司 | Process for producing a catalyst and catalyst |
| CN103118779A (en) * | 2010-09-14 | 2013-05-22 | 巴斯夫欧洲公司 | Process for producing carbon-comprising support |
| CN103335513A (en) * | 2012-12-10 | 2013-10-02 | 冯良荣 | Electric heating rotary kiln |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441110A (en) * | 2021-08-13 | 2021-09-28 | 成都中科普瑞净化设备有限公司 | Method for preparing adsorbent for adsorbing and separating carbon monoxide |
| CN113649082A (en) * | 2021-08-13 | 2021-11-16 | 成都中科普瑞净化设备有限公司 | Method for preparing vinyl acetate catalyst by acetylene method |
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