CN103691446B - Catalyst taking graphene as carrier and carbon nano-material prepared by catalyst - Google Patents
Catalyst taking graphene as carrier and carbon nano-material prepared by catalyst Download PDFInfo
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- CN103691446B CN103691446B CN201310637340.0A CN201310637340A CN103691446B CN 103691446 B CN103691446 B CN 103691446B CN 201310637340 A CN201310637340 A CN 201310637340A CN 103691446 B CN103691446 B CN 103691446B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 title abstract description 14
- 239000002086 nanomaterial Substances 0.000 title abstract description 5
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000001681 protective effect Effects 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- 239000007789 gas Substances 0.000 claims description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008246 gaseous mixture Substances 0.000 claims description 13
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 241000446313 Lamella Species 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 230000002829 reductive effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- -1 Activated Graphite alkene Chemical class 0.000 description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Abstract
The invention discloses a catalyst taking graphene as a carrier and a carbon nano-material prepared by the catalyst. A preparation method for a carbon nano-tube catalyst comprises the following steps: (1) performing liquid-phase mixing on the graphene, a VIII-group element-containing compound, an M-group element-containing compound and a VI B-group element-containing compound; (2) mixing the mixed liquid to obtain a precursor; (3) sintering the precursor to obtain the catalyst. Carbon nano-tubes are prepared by first introducing a mixed gas of a reductive gas and a protective gas into the prepared catalyst, and then introducing a mixed gas of a carbon source gas and the protective gas by a CVD (chemical vapor deposition) method. According to the catalyst and the carbon nano-material, the graphene material with a nanopore structure is taken as a carrier, and a metal element is loaded in nanopores, so that the particle size of the prepared carbon nano-tube catalyst has high controllability; the tube diameters of the carbon nano-tubes prepared by the CVD method are small, uniform and high in quality.
Description
Technical field
The present invention relates to the technical field of CNT, the catalyst more particularly, to Graphene as carrier and being thus obtained
Carbon nanomaterial.
Background technology
CNT is as monodimension nanometer material, lightweight, and hexagonal structure connects perfection, has the power of many exceptions
, electricity and chemical property.CNT application potential is huge, and its possible application field includes：Conduction and high-strength composite material
Material, energy stores and reforming unit（Fuel cell）, sensor, Field Emission Display and emission source, Nanosemiconductor Device, micro-
Probe and micro wiring etc..
The preparation method of CNT mainly has chemical vapour deposition technique（CVD）, arc process, laser ablation method etc..Swash
Photoetch method can obtain highly purified product.But high-power laser equipment price is high, and it is not easy to amplify.Arc process
Although equipment is simple, product quality is high, cost is higher than CVD.CVD can be divided into two big types：One class is floating catalytic
Method；Another kind of be previously prepared catalyst fixed catalytic method.
Either which kind of CVD, the preparation of catalyst is all most important to the control of caliber, and the particle diameter controlling catalyst can
To obtain pipe with small pipe diameter, even SWCN.The patent of U.S. Hyperion Catalysis International
A kind of open work that can optionally make SWCN growth with carbonaceous gas when reacting of knowing clearly of CN101189371A
Change catalyst preparation technology,.This activated catalyst is formed by the catalyst that reduction comprises complex oxide.This complex oxide
Molecular formula can be AxByOz, wherein x/y≤2, and z/y≤4, A is V III race's elements, and B is to make element B oxide in hydrogen
In the presence of, unreducible element at a temperature of less than or equal to about 900 DEG C.The skin Sang Chong difference Luo Enjite of the U.S. exists
Rhenium catalyst and the method for optionally producing SWCN is disclosed, catalyst comprises in patent CN1922347A
Rhenium and race V III transition metal, such as Co, it is preferably arranged on carrier material, forms catalytic substrate.Japanese ball mountain cyclopentadienyl husband
Et al. method disclosed in patent CN1633393A, be the carbon source atmosphere making at the heating temperature to be made up of oxygenatedchemicalss
Contact to generate single-layer carbon nano-tube with catalyst.The carbon source that it is made up of oxygenatedchemicalss preferably uses alcohols and/or ethers,
Catalyst preferably uses metal, preferably 500～1500 DEG C of heating-up temperature.Method disclosed by patent CN1673073A, then be with
SiO2Deng for carrier, load transitions race slaine obtains the catalyst of proper growth SWCN, and in growth course
Water flowing gas is it is therefore prevented that the generation of multi-walled carbon nano-tubes and agraphitic carbon.
The catalyst of nano level high dispersive is the key obtaining high-quality CNT, the diameter to carbon pipe for its particle diameter
Have a significant impact.The size tunable of the catalyst of prior art is poor, and the Diameter distribution scope of the CNT of preparation is larger.
Content of the invention
In view of this, one aspect of the present invention provides a kind of preparation method of carbon nano-tube catalyst, and the method makes made
The size tunable of standby carbon nano-tube catalyst is stronger.
A kind of preparation method of carbon nano-tube catalyst is it is characterised in that comprise the following steps：
（1）According to mass fraction by 6～12 parts of Graphenes, 1～112 part in terms of VIII race's element contain VIII group element compound,
0～135 part in terms of M race element group element compound containing M, 0～135 part in terms of the VI B race element compound containing VI B race element are molten
Solution forms mixed solution in solvent, and described M race element is selected from one of II A, III A, IV A race element or at least two；
（2）Described mixed solution is carried out at 100～150 DEG C banburying and process 1～12H, obtain catalyst precursor；
（3）Described catalyst precursor is inserted in the atmosphere of protective gas at a temperature of 400～1000 DEG C sintering 1～
2H is obtained carbon nano-tube catalyst.
Wherein, the lamella of described Graphene is less than 10 layers, and the specific surface area of Graphene is 200～1200m2/g.
Wherein, described II A race element is magnesium or calcium, and described III A race element is aluminum, and described IV A race element is silicon, described VIII
Race's element is one of ferrum, cobalt, nickel or at least two, and described VI B race element is manganese.
Wherein, the flow velocity of described protective gas is 1～10L/H, and described protective gas is nitrogen, hydrogen, helium, argon
One of gas or at least two.
Another aspect of the invention provides a kind of carbon nano-tube catalyst, and this carbon nano-tube catalyst can prepare pipe with small pipe diameter
CNT.
A kind of carbon nano-tube catalyst, is obtained using above-mentioned preparation method.
Further aspect of the present invention provides a kind of method preparing CNT, and the method can prepare the carbon nanometer of pipe with small pipe diameter
Pipe.
A kind of prepare CNT using carbon nano-tube catalyst described above method detailed process be：By CNT
Catalyst is inserted at 600～900 DEG C, first leads to the gaseous mixture 1～3H of hydrogen and protective gas, then passes to carbon-source gas and guarantor
Mixed gas 1～the 6H of shield property gas, prepared CNT.
Wherein, in the gaseous mixture of described hydrogen and protective gas, hydrogen and the volume ratio of shielding gas are 1：1～5, carbon source
In the mixed gas of gas and protective gas, carbon-source gas and the volume ratio of protective gas are 1：1～4.
Wherein, described carbon-source gas be one of methane, ethylene, acetylene, natural gas, liquefied petroleum gas, benzene, ethanol or
At least two, described protective gas is one of nitrogen, hydrogen, helium, argon or at least two.
Wherein, described reactor be horizontal reactor, vertical reactor, fixation or mobile fluid bed.
Another aspect of the present invention provides one kind to prepare CNT, and this CNT caliber is little and is evenly distributed.
A kind of CNT adopts said method to be obtained.
The present invention with the nano-pore of Graphene as carrier, metallic element is carried on this nanometer of in the hole so that preparation carbon
The size tunable of nano tube catalyst is stronger, and the caliber of the CNT prepared by CVD using this catalyst is less.
Brief description
Fig. 1 is the SEM figure of the CNT of the embodiment of the present invention 2.
Fig. 2 is the SEM figure of the CNT of the embodiment of the present invention 3.
Specific embodiment
Separately below in conjunction with the embodiments and accompanying drawing the present invention is described in further detail.
Embodiment 1：Take the pure water of 100 parts of quality, the specific surface area of 6 parts of quality is 2000m2The Activated Graphite alkene of/g, contains
There are cobalt nitrate, the aluminum nitrate containing 1 part of quality aluminium element of 1 part of quality cobalt element, stirring and dissolving is transparent to solution, then close
Knead 1H at a temperature of 110 DEG C in mill, obtain catalyst precursor.Calcined in tube furnace after presoma is pulverized
2H, temperature is 400 DEG C, logical nitrogen, gas flow rate 1L/H, prepared carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 600 DEG C, first leading to volume ratio is 1：5
Hydrogen and the gaseous mixture of nitrogen, time 1H, then passing to volume ratio is 1：1 methane and the mixed gas of nitrogen, the response time
For 1H, obtain CNT, its mean diameter is 10nm.
Embodiment 2：Take the pure water of 100 parts of quality, the specific surface area of 12 parts of quality is 1000m2The Activated Graphite alkene of/g, contains
There are the ferric nitrate of 112 parts of quality ferrum element, the magnesium nitrate containing 135 parts of quality magnesium elements, the nitre containing 135 parts of quality manganese elements
Sour manganese, stirring and dissolving is transparent to solution, is then then kneading 1H at a temperature of 110 DEG C in banbury, is obtaining catalyst
Presoma.Carry out after presoma is pulverized calcining 2H in tube furnace, temperature is 500 DEG C, logical nitrogen, gas flow rate 5L/H, system
Obtain carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 750 DEG C, being first passed through volume ratio is 1：5
Hydrogen and nitrogen gaseous mixture, time 1H, then pass to volume ratio be 1：1 liquefied petroleum gas and the mixing of nitrogen rise, instead
It is 6H between seasonable.Obtain CNT, its its mean diameter is 20nm.
Embodiment 3：Take the 95% of 100 parts of quality ethanol solution, the specific surface area of 10 parts of quality is 1500m2/ g activity stone
Black alkene, the ferric nitrate containing 56 parts of quality ferrum element, the aluminum nitrate containing 81 parts of quality aluminium elements, contain 56 parts of quality manganese elements
Manganese nitrate, stirring and dissolving is transparent to solution, then then knead 1H at a temperature of 150 DEG C in banbury, urged
Agent presoma.Carry out after presoma is pulverized calcining 2H in tube furnace, temperature is 500 DEG C, logical nitrogen, gas flow rate 5L/
H, prepared carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 800 DEG C, first leading to volume ratio is 1：1
Hydrogen and the gaseous mixture of nitrogen, time 1H, then passing to volume ratio is 1：2 liquefied petroleum gas and the mixing of nitrogen rise, reaction
Time is 1H.Obtain CNT, its mean diameter is 15nm.
Embodiment 4：Take the pure water of 100 parts of quality, the specific surface area of 6 parts of quality is 600m2The Activated Graphite alkene of/g, contains
The cobalt nitrate of 1 part of quality cobalt element, the manganese nitrate containing 1 part of quality aluminium element, stirring and dissolving is transparent to solution, then in banburying
Knead 12H at a temperature of 100 DEG C in machine, obtain catalyst precursor.Calcined in tube furnace after presoma is pulverized
2H, temperature is 400 DEG C, logical nitrogen, gas flow rate 1L/H, prepared carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 600 DEG C, first leading to volume ratio is 1：5
Hydrogen and the gaseous mixture of nitrogen, time 1H, then passing to volume ratio is 1：1 methane and the mixed gas of nitrogen, the response time
For 1H, obtain CNT, its mean diameter is 12nm.
Embodiment 5：Take the 95% of 100 parts of quality ethanol solution, the specific surface area of 10 parts of quality is 600m2/ g activity stone
Black alkene, the ferric nitrate containing 56 parts of quality ferrum element, the aluminum nitrate containing 68 parts of quality aluminium elements, contain 68 parts of quality manganese elements
Manganese nitrate, stirring and dissolving is transparent to solution, then then knead 6H at a temperature of 120 DEG C in banbury, urged
Agent presoma.Carry out after presoma is pulverized calcining 1.5H in tube furnace, temperature is 700 DEG C, logical nitrogen, gas flow rate
5L/H, prepared carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 900 DEG C, first leading to volume ratio is 1：1
Hydrogen and the mixed gas of nitrogen, time 1H, then pain volume ratio is 1：2 liquefied petroleum gas and the mixing of nitrogen rise, reaction
Time is 1H.Obtain CNT, its mean diameter is 22nm.
Embodiment 6：Take the pure water of 100 parts of quality, the specific surface area of 6 parts of quality is 2000m2The Activated Graphite alkene of/g, contains
There is the cobalt nitrate of 1 part of quality cobalt element, stirring and dissolving is transparent to solution, then knead at a temperature of 150 DEG C in banbury
1H, obtains catalyst precursor.Carry out after presoma is pulverized calcining 1H in tube furnace, temperature is 1000 DEG C, logical nitrogen, gas
Rate of flow of fluid 10L/H, prepared carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 900 DEG C, first leading to volume ratio is 1：5
Hydrogen and the gaseous mixture of nitrogen, time 1H, then passing to volume ratio is 1：4 methane and the mixed gas of nitrogen, the response time
For 1H, obtain CNT, its mean diameter is 14nm.
Embodiment 7：Take the pure water of 100 parts of quality, the specific surface area of 12 parts of quality is 1000m2The Activated Graphite alkene of/g, contains
There are ferric nitrate, the magnesium nitrate containing 135 parts of quality magnesium elements of 112 parts of quality ferrum element, stirring and dissolving is transparent to solution, then
Then knead 1H at a temperature of 110 DEG C in banbury, obtain catalyst precursor.In tube furnace after presoma is pulverized
In carry out calcine 2H, temperature be 500 DEG C, logical nitrogen, gas flow rate 5L/H, prepared carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 750 DEG C, being first passed through volume ratio is 1：5
Hydrogen and nitrogen gaseous mixture, time 3H, then pass to volume ratio be 1：4 liquefied petroleum gas and the mixing of nitrogen rise, instead
It is 6H between seasonable.Obtain CNT, its mean diameter is 22nm.
Embodiment 8：Take the pure water of 100 parts of quality, the specific surface area of 12 parts of quality is 1000m2The Activated Graphite alkene of/g, contains
There are ferric nitrate, the manganese nitrate containing 135 parts of quality manganese elements of 112 parts of quality ferrum element, stirring and dissolving is transparent to solution, then
Then knead 1H at a temperature of 110 DEG C in banbury, obtain catalyst precursor.In tube furnace after presoma is pulverized
In carry out calcine 2H, temperature be 500 DEG C, logical nitrogen, gas flow rate 5L/H, prepared carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 750 DEG C, being first passed through volume ratio is 1：5
Hydrogen and nitrogen gaseous mixture, time 3H, then pass to volume ratio be 1：4 liquefied petroleum gas and the gaseous mixture of nitrogen, instead
It is 6H between seasonable.Obtain CNT, its mean diameter is 22nm.
Embodiment 9：Take the pure water of 100 parts of quality, the specific surface area of 6 parts of quality is 2000m2The Activated Graphite alkene of/g, contains
There are cobalt nitrate, the manganese nitrate containing 1 part of quality manganese element of 1 part of quality cobalt element, stirring and dissolving is transparent to solution, then close
Knead 1H at a temperature of 110 DEG C in mill, obtain catalyst precursor.Calcined in tube furnace after presoma is pulverized
2H, temperature is 400 DEG C, logical nitrogen, gas flow rate 1L/H, prepared carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 600 DEG C, first leading to volume ratio is 1：5
Hydrogen and the gaseous mixture of nitrogen, time 1H, then passing to volume ratio is 1：1 methane and the mixed gas of nitrogen, the response time
For 1H, obtain CNT, its mean diameter is 13nm.
Embodiment 10：Take the pure water of 100 parts of quality, the specific surface area of 6 parts of quality is 2000m2The Activated Graphite alkene of/g, contains
There are the cobalt nitrate of 1 part of quality cobalt element, the manganese nitrate containing 1 part of quality manganese element, the manganese nitrate containing 1 part of quality manganese element,
Stirring and dissolving is transparent to solution, then kneads 1H at a temperature of 110 DEG C in banbury, obtains catalyst precursor.Will be front
Drive and carry out calcining 2H in tube furnace after body is pulverized, temperature is 400 DEG C, logical nitrogen, gas flow rate 1L/H, and prepared CNT is urged
Agent.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 600 DEG C, first leading to volume ratio is 1：5
Hydrogen and the gaseous mixture of nitrogen, time 1H, then passing to volume ratio is 1：1 methane and the mixed gas of nitrogen, the response time
For 1H, obtain CNT, its mean diameter is 11nm.
Above example prepares the size tunable of carbon nano-tube catalyst, can be used for preparing uniform pipe with small pipe diameter carbon nanometer
Pipe, suitable industrialization large-scale production.Pipe with small pipe diameter carbon nano-tube conductive of the present invention is good simultaneously, can use and ultracapacitor, lithium
The fields such as battery.
It should be noted that and understanding, in the spirit and scope without departing from appended claims the present invention for required protection
In the case of, various modifications and improvements can be made to the present invention of foregoing detailed description.It is therefore desirable to the technical scheme of protection
Scope do not limited by given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (8)
1. a kind of preparation method of carbon nano-tube catalyst is it is characterised in that comprise the following steps：
(1) according to mass fraction by 6～12 parts of Graphenes, 1～112 part in terms of VIII race's element contain VIII group element compound, with M race
0～135 part of group element compound containing M of element meter, in terms of VIIB race element 0～135 part of element of race containing VIIB compound dissolution
Form mixed solution in solvent, described M race element is selected from one of II A, III A, IV A race element or at least two；Described
II A race element is magnesium or calcium, and described III A race element is aluminum, and described IV A race element is silicon, and described VIII race's element is ferrum, cobalt, nickel
One of or at least two, described VIIB race element be manganese；
(2) described mixed solution is carried out mixing process 1～12h at 100～150 DEG C, obtain catalyst precursor；
(3) described catalyst precursor is inserted 1～2h system that sinters at a temperature of 400～1000 DEG C in the atmosphere of protective gas
Obtain carbon nano-tube catalyst；The specific surface area of Graphene is 200～1200m2/g；
Described carbon nano-tube catalyst is with the nano-pore of Graphene as carrier, and metallic element is carried on this nanometer of in the hole.
2. preparation method according to claim 1 is it is characterised in that the lamella of described Graphene is less than 10 layers.
3. preparation method according to claim 1 it is characterised in that described protective gas flow velocity be 1～10L/h,
Described protective gas is one of nitrogen, hydrogen, helium, argon or at least two.
4. a kind of carbon nano-tube catalyst is it is characterised in that adopt preparation method system as described in claims 1 to 3 any one
?.
5. a kind of using carbon nano-tube catalyst as claimed in claim 4 prepare CNT method it is characterised in that tool
Body process is：Carbon nano-tube catalyst is inserted reactor at 600～900 DEG C, first leads to the mixing of hydrogen and protective gas
Gas 1～3h, then passes to the mixed gas 1～6h of carbon-source gas and protective gas, prepared CNT.
6. method according to claim 5 it is characterised in that in the gaseous mixture of described hydrogen and protective gas hydrogen with
The volume ratio of protective gas is 1：1～5, carbon-source gas and protectiveness gas in the mixed gas of carbon-source gas and protective gas
The volume ratio of body is 1：1～4.
7. method according to claim 5 it is characterised in that described carbon-source gas be methane, ethylene, acetylene, natural gas,
One of liquefied petroleum gas, benzene, ethanol or at least two, described protective gas is nitrogen, hydrogen, helium, in argon
One kind or at least two.
8. method according to claim 5 it is characterised in that described reactor be horizontal reactor, vertical reactor, solid
Fixed or mobile fluid bed.
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| CN104241062B (en) * | 2014-09-12 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Carbon nanotube emission cathode preparation method and carbon nanotube emission negative electrode |
| CN105504341B (en) * | 2015-11-20 | 2017-06-16 | 营口圣泉高科材料有限公司 | A kind of compound and preparation method thereof and a kind of macromolecular material and preparation method thereof |
| WO2017063434A1 (en) | 2015-10-15 | 2017-04-20 | 济南圣泉集团股份有限公司 | Carbon-containing nanostructure composite, polymer material using same and preparation method |
| CN105525377B (en) | 2015-11-26 | 2018-08-17 | 济南圣泉集团股份有限公司 | A kind of functional regenerated cellulose fibre and its preparation method and application |
| WO2017084507A1 (en) | 2015-11-20 | 2017-05-26 | 济南圣泉集团股份有限公司 | Graphene-containing modified latex as well as preparation method therefor and application thereof |
| CN106517159A (en) * | 2016-11-11 | 2017-03-22 | 苏州赛福德备贸易有限公司 | A preparing method of a composite nanometer carbon material |
| CN107507985A (en) * | 2017-09-04 | 2017-12-22 | 浙江大学 | A kind of three-dimensional Fe N C oxygen reduction catalysts of new high effectively iron load and preparation method thereof |
| CN109280425A (en) * | 2018-11-02 | 2019-01-29 | 杭州超探新材料科技有限公司 | A kind of preparation method of floor heating electric hot plate |
| CN110349848B (en) * | 2019-06-28 | 2021-05-18 | 华中科技大学 | Carbon-carbon bond-based high-performance interface preparation method |
| CN114068927B (en) * | 2020-08-04 | 2023-10-13 | 北京大学 | Graphene carbon nanotube composite material and preparation method thereof |
| CN115805076B (en) * | 2021-09-15 | 2023-09-08 | 江苏天奈科技股份有限公司 | Catalyst and preparation method thereof, array carbon nanotube and preparation method thereof |
| CN114405513A (en) * | 2022-01-29 | 2022-04-29 | 江门道氏新能源材料有限公司 | Metal composite material and preparation method and application thereof |
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