CN103691446A - 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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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 title abstract description 10
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- 239000002041 carbon nanotube Substances 0.000 claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
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- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 13
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- 238000005245 sintering Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 67
- 239000007789 gas Substances 0.000 claims description 44
- 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 16
- 239000012018 catalyst precursor Substances 0.000 claims description 14
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- 230000008569 process Effects 0.000 claims description 13
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- 239000003595 mist Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 102000040350 B family Human genes 0.000 claims description 6
- 108091072128 B family Proteins 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- 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
- 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
- 239000012530 fluid Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
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- 229910052759 nickel Inorganic materials 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
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 3
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- 239000000243 solution Substances 0.000 description 12
- 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
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- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 8
- 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
- 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
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 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 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 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
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- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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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, relate in particular to and take the catalyst that Graphene is carrier and the carbon nanomaterial making thus.
Background technology
CNT is as monodimension nanometer material, lightweight, and hexagonal structure connects perfect, has many abnormal mechanics, electricity and chemical property.CNT application potential is huge, and it may application comprise: conduction and high strength composite, stored energy and reforming unit (fuel cell), sensor, Field Emission Display and emission source, Nanosemiconductor Device, microprobe and micro wiring etc.
The preparation method of CNT mainly contains chemical vapour deposition technique (CVD method), arc process, laser ablation method etc.Laser ablation method can obtain highly purified product.But high-power laser equipment price is high, and be not easy to amplify.Although arc process equipment is simple, product quality is high, cost is higher than CVD method.CVD method can be divided into two large types: a class is floating catalytic method; Another kind of is the fixed catalytic method of previously prepared catalyst.
No matter be which kind of CVD method, the preparation of catalyst is all most important to the control of caliber, and the particle diameter of controlling catalyst can obtain pipe with small pipe diameter, or even SWCN.The patent CN101189371A of U.S. Hyperion Catalysis International a kind of activating catalyst technology of preparing that can optionally make SWCN growth when reacting with carbonaceous gas of openly knowing clearly.The catalyst that this activating catalyst comprises complex oxide by reduction forms.The molecular formula of this complex oxide can be AxByOz, wherein x/y≤2, and z/y≤4, and A WeiⅤ III family element, and B makes element B oxide under the existence of hydrogen, is being less than or equal to unreducible element at the temperature of approximately 900 ℃.The poor Luo Enjite of the Pi Sangchong of the U.S. has disclosed rhenium catalyst and for the method for manufacture order wall carbon nano tube optionally in patent CN1922347A, catalyst comprises Lai He family V III transition metal, Co for example, it is preferably configured on carrier material, forms catalytic substrate.The people such as the Japan ball luxuriant husband in mountain, in the method disclosed in patent CN1633393A, are under heating-up temperature, to make the carbon source atmosphere consisting of oxygenatedchemicals contact to generate single-layer carbon nano-tube with catalyst.Its carbon source consisting of oxygenatedchemicals is preferably used alcohols and/or ethers, and catalyst is preferably used metal, preferably 500～1500 ℃ of heating-up temperatures.The method that patent CN1673073A is disclosed is with SiO
2deng being carrier, load magnesium-yttrium-transition metal salt obtains the catalyst of proper growth SWCN, and in growth course water flowing gas, prevented the generation of multi-walled carbon nano-tubes and agraphitic carbon.
The catalyst of nano level high dispersive is the key that obtains high-quality CNT, and its particle diameter also has a significant impact the diameter of carbon pipe.The particle diameter controllability of the catalyst of prior art is poor, and the Diameter distribution scope of the CNT of preparation is larger.
Summary 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 the particle diameter controllability of prepared carbon nano-tube catalyst stronger.
A preparation method for carbon nano-tube catalyst, is characterized in that, comprises the following steps:
(1) according to mass fraction, 1～112 part of 6～12 parts of Graphene, YiⅧ family element meter are dissolved in and in solvent, form mixed solution containing VIII group element compound, the compound of counting 0～135Fen HanⅥ B family element containing M group element compound, YiⅥ B family element in 0～135 part of M family element, described M family element is selected from a kind of in II A, III A, IV A family element or at least two kinds;
(2) described mixed solution is carried out at 100～150 ℃ to banburying and process 1～12H, obtain catalyst precursor;
(3) described catalyst precursor is inserted in the atmosphere of protective gas to sintering 1～2H at 400～1000 ℃ of temperature and make carbon nano-tube catalyst.
Wherein, the lamella of described Graphene is below 10 layers, and the specific area of Graphene is 200～1200m
2/ g.
Wherein, described II A family element is magnesium or calcium, and described III A family element is aluminium, and described IV A family element is silicon, and described VIII family element is a kind of in iron, cobalt, nickel or at least two kinds, and described VI B family element is manganese.
Wherein, the flow velocity of described protective gas is 1～10L/H, and described protective gas is a kind of in nitrogen, hydrogen, helium, argon gas or at least two kinds.
Another aspect of the invention provides a kind of carbon nano-tube catalyst, and this carbon nano-tube catalyst can be prepared the CNT of pipe with small pipe diameter.
A carbon nano-tube catalyst, adopts above-mentioned preparation method to make.
Further aspect of the present invention provides a kind of method of preparing CNT, and the method can be prepared the CNT of pipe with small pipe diameter.
A kind of method detailed process that adopts carbon nano-tube catalyst described above to prepare CNT is: carbon nano-tube catalyst is inserted at 600～900 ℃; first lead to the gaseous mixture 1～3H of hydrogen and protective gas; then the mist 1～6H that passes into carbon-source gas and protective gas, makes CNT.
Wherein, in the gaseous mixture of described hydrogen and protective gas, hydrogen is 1:1～5 with the volume ratio of protection gas, and in the mist of carbon-source gas and protective gas, the volume ratio of carbon-source gas and protective gas is 1:1～4.
Wherein, described carbon-source gas is a kind of in methane, ethene, acetylene, natural gas, liquefied petroleum gas, benzene, ethanol or at least two kinds, and described protective gas is a kind of in nitrogen, hydrogen, helium, argon gas or at least two kinds.
Wherein, described reactor is horizontal reactor, vertical reactor, fixing or mobile fluid bed.
The present invention provides a kind of CNT of preparing on the other hand, and this CNT caliber is little and be evenly distributed.
A kind of CNT adopts said method to make.
It is carrier that the nano-pore of Graphene is take in the present invention, and metallic element is carried in this nano-pore, makes the particle diameter controllability of carbon nano-tube catalyst of preparation stronger, uses this catalyst less by the caliber of the standby CNT of CVD legal system.
Accompanying drawing explanation
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.
The specific embodiment
Below respectively in conjunction with the embodiments and accompanying drawing the present invention is described in further detail.
Embodiment 1: get the pure water of 100 parts of quality, the specific area of 6 parts of quality is 2000m
2the Activated Graphite alkene of/g, the cobalt nitrate that contains 1 part of quality cobalt element, the aluminum nitrate that contains 1 part of quality aluminium element, stirring and dissolving is transparent to solution, then in banbury at the temperature of 110 ℃ mixing 1H, obtain catalyst precursor.After presoma is pulverized, calcine 2H in tube furnace, temperature is 400 ℃, logical nitrogen, and gas flow rate 1L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 600 ℃, the hydrogen that first logical volume ratio is 1:5 and the gaseous mixture of nitrogen, time 1H, then passing into volume ratio is the methane of 1:1 and the mist of nitrogen, reaction time is 1H, obtains CNT, and its average grain diameter is 10nm.
Embodiment 2: get the pure water of 100 parts of quality, the specific area of 12 parts of quality is 1000m
2the Activated Graphite alkene of/g, the ferric nitrate that contains 112 parts of quality ferro elements, the magnesium nitrate that contains 135 parts of quality magnesium elements, the manganese nitrate that contains 135 parts of quality manganese elements, stirring and dissolving is transparent to solution, then then in banbury at the temperature of 110 ℃ mixing 1H, obtain catalyst precursor.After presoma is pulverized, calcine 2H in tube furnace, temperature is 500 ℃, logical nitrogen, and gas flow rate 5L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, and reaction temperature is 750 ℃, and first passing into volume ratio is the hydrogen of 1:5 and the gaseous mixture of nitrogen, time 1H, and then passing into volume ratio is that the liquefied petroleum gas of 1:1 and the mixing of nitrogen rise, the reaction time is 6H.Obtain CNT, its its average grain diameter is 20nm.
Embodiment 3: get 95% ethanolic solution of 100 parts of quality, the specific area of 10 parts of quality is 1500m
2/ g Activated Graphite alkene, the ferric nitrate that contains 56 parts of quality ferro elements, the aluminum nitrate that contains 81 parts of quality aluminium elements, the manganese nitrate that contains 56 parts of quality manganese elements, stirring and dissolving is transparent to solution, then then in banbury at the temperature of 150 ℃ mixing 1H, obtain catalyst precursor.After presoma is pulverized, calcine 2H in tube furnace, temperature is 500 ℃, logical nitrogen, and gas flow rate 5L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, and reaction temperature is 800 ℃, the hydrogen that first logical volume ratio is 1:1 and the gaseous mixture of nitrogen, and time 1H, then passing into volume ratio is that the liquefied petroleum gas of 1:2 and the mixing of nitrogen rise, the reaction time is 1H.Obtain CNT, its average grain diameter is 15nm.
Embodiment 4: get the pure water of 100 parts of quality, the specific area of 6 parts of quality is 600m
2the Activated Graphite alkene of/g, the cobalt nitrate that contains 1 part of quality cobalt element, the manganese nitrate that contains 1 part of quality aluminium element, stirring and dissolving is transparent to solution, then in banbury at the temperature of 100 ℃ mixing 12H, obtain catalyst precursor.After presoma is pulverized, calcine 2H in tube furnace, temperature is 400 ℃, logical nitrogen, and gas flow rate 1L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 600 ℃, the hydrogen that first logical volume ratio is 1:5 and the gaseous mixture of nitrogen, time 1H, then passing into volume ratio is the methane of 1:1 and the mist of nitrogen, reaction time is 1H, obtains CNT, and its average grain diameter is 12nm.
Embodiment 5: get 95% ethanolic solution of 100 parts of quality, the specific area of 10 parts of quality is 600m
2/ g Activated Graphite alkene, the ferric nitrate that contains 56 parts of quality ferro elements, the aluminum nitrate that contains 68 parts of quality aluminium elements, the manganese nitrate that contains 68 parts of quality manganese elements, stirring and dissolving is transparent to solution, then then in banbury at the temperature of 120 ℃ mixing 6H, obtain catalyst precursor.After presoma is pulverized, calcine 1.5H in tube furnace, temperature is 700 ℃, logical nitrogen, and gas flow rate 5L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, and reaction temperature is 900 ℃, the hydrogen that first logical volume ratio is 1:1 and the mist of nitrogen, and time 1H, the liquefied petroleum gas that then pain volume ratio is 1:2 and the mixing of nitrogen rise, and the reaction time is 1H.Obtain CNT, its average grain diameter is 22nm.
Embodiment 6: get the pure water of 100 parts of quality, the specific area of 6 parts of quality is 2000m
2the Activated Graphite alkene of/g, the cobalt nitrate that contains 1 part of quality cobalt element, stirring and dissolving is transparent to solution, then in banbury at the temperature of 150 ℃ mixing 1H, obtain catalyst precursor.After presoma is pulverized, calcine 1H in tube furnace, temperature is 1000 ℃, logical nitrogen, and gas flow rate 10L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 900 ℃, the hydrogen that first logical volume ratio is 1:5 and the gaseous mixture of nitrogen, time 1H, then passing into volume ratio is the methane of 1:4 and the mist of nitrogen, reaction time is 1H, obtains CNT, and its average grain diameter is 14nm.
Embodiment 7: get the pure water of 100 parts of quality, the specific area of 12 parts of quality is 1000m
2the Activated Graphite alkene of/g, the ferric nitrate that contains 112 parts of quality ferro elements, the magnesium nitrate that contains 135 parts of quality magnesium elements, stirring and dissolving is transparent to solution, then then in banbury at the temperature of 110 ℃ mixing 1H, obtain catalyst precursor.After presoma is pulverized, calcine 2H in tube furnace, temperature is 500 ℃, logical nitrogen, and gas flow rate 5L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, and reaction temperature is 750 ℃, and first passing into volume ratio is the hydrogen of 1:5 and the gaseous mixture of nitrogen, time 3H, and then passing into volume ratio is that the liquefied petroleum gas of 1:4 and the mixing of nitrogen rise, the reaction time is 6H.Obtain CNT, its average grain diameter is 22nm.
Embodiment 8: get the pure water of 100 parts of quality, the specific area of 12 parts of quality is 1000m
2the Activated Graphite alkene of/g, the ferric nitrate that contains 112 parts of quality ferro elements, the manganese nitrate that contains 135 parts of quality manganese elements, stirring and dissolving is transparent to solution, then then in banbury at the temperature of 110 ℃ mixing 1H, obtain catalyst precursor.After presoma is pulverized, calcine 2H in tube furnace, temperature is 500 ℃, logical nitrogen, and gas flow rate 5L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, and reaction temperature is 750 ℃, and first passing into volume ratio is the hydrogen of 1:5 and the gaseous mixture of nitrogen, time 3H, and then passing into volume ratio is the liquefied petroleum gas of 1:4 and the gaseous mixture of nitrogen, the reaction time is 6H.Obtain CNT, its average grain diameter is 22nm.
Embodiment 9: get the pure water of 100 parts of quality, the specific area of 6 parts of quality is 2000m
2the Activated Graphite alkene of/g, the cobalt nitrate that contains 1 part of quality cobalt element, the manganese nitrate that contains 1 part of quality manganese element, stirring and dissolving is transparent to solution, then in banbury at the temperature of 110 ℃ mixing 1H, obtain catalyst precursor.After presoma is pulverized, calcine 2H in tube furnace, temperature is 400 ℃, logical nitrogen, and gas flow rate 1L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 600 ℃, the hydrogen that first logical volume ratio is 1:5 and the gaseous mixture of nitrogen, time 1H, then passing into volume ratio is the methane of 1:1 and the mist of nitrogen, reaction time is 1H, obtains CNT, and its average grain diameter is 13nm.
Embodiment 10: get the pure water of 100 parts of quality, the specific area of 6 parts of quality is 2000m
2the Activated Graphite alkene of/g, the cobalt nitrate that contains 1 part of quality cobalt element, the manganese nitrate that contains 1 part of quality manganese element, the manganese nitrate that contains 1 part of quality manganese element, stirring and dissolving is transparent to solution, then in banbury at the temperature of 110 ℃ mixing 1H, obtain catalyst precursor.After presoma is pulverized, calcine 2H in tube furnace, temperature is 400 ℃, logical nitrogen, and gas flow rate 1L/H, makes carbon nano-tube catalyst.
The above-mentioned catalyst preparing is positioned in tube furnace, reaction temperature is 600 ℃, the hydrogen that first logical volume ratio is 1:5 and the gaseous mixture of nitrogen, time 1H, then passing into volume ratio is the methane of 1:1 and the mist of nitrogen, reaction time is 1H, obtains CNT, and its average grain diameter is 11nm.
It is controlled that above embodiment prepares the particle diameter of carbon nano-tube catalyst, can be used for preparing uniform pipe with small pipe diameter CNT, is applicable to industrialization large-scale production.Simultaneously pipe with small pipe diameter carbon nano-tube conductive of the present invention is good, the fields such as available and ultracapacitor, lithium battery.
Should be noted that and understand, in the situation that do not depart from the spirit and scope of accompanying claim the present invention for required protection, can make various modifications and improvement to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not subject to the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for carbon nano-tube catalyst, is characterized in that, comprises the following steps:
(1) according to mass fraction, 1～112 part of 6～12 parts of Graphene, YiⅧ family element meter are dissolved in and in solvent, form mixed solution containing VIII group element compound, the compound of counting 0～135Fen HanⅥ B family element containing M group element compound, YiⅥ B family element in 0～135 part of M family element, described M family element is selected from a kind of in II A, III A, IV A family element or at least two kinds;
(2) described mixed solution is carried out at 100～150 ℃ to mixing processing 1～12H, obtain catalyst precursor;
(3) described catalyst precursor is inserted in the atmosphere of protective gas to sintering 1～2H at 400～1000 ℃ of temperature and make carbon nano-tube catalyst.
2. preparation method according to claim 1, is characterized in that, the lamella of described Graphene is below 10 layers, and the specific area of Graphene is 200～1200m
2/ g.
3. preparation method according to claim 1, is characterized in that, described II A family element is magnesium or calcium, described III A family element is aluminium, described IV A family element is silicon, and described VIII family element is a kind of in iron, cobalt, nickel or at least two kinds, and described VI B family element is manganese.
4. preparation method according to claim 1, is characterized in that, the flow velocity of described protective gas is 1～10L/H, and described protective gas is a kind of in nitrogen, hydrogen, helium, argon gas or at least two kinds.
5. a carbon nano-tube catalyst, is characterized in that, adopts preparation method as described in claim 1～5 any one to make.
6. a method that adopts carbon nano-tube catalyst as claimed in claim 1 to prepare CNT; it is characterized in that; detailed process is: carbon nano-tube catalyst is inserted to reactor at 600～900 ℃; first lead to the gaseous mixture 1～3H of hydrogen and protective gas; then the mist 1～6H that passes into carbon-source gas and protective gas, makes CNT.
7. method according to claim 6; it is characterized in that; in the gaseous mixture of described hydrogen and protective gas, the volume ratio of hydrogen and protective gas is 1:1～5, and in the mist of carbon-source gas and protective gas, the volume ratio of carbon-source gas and protective gas is 1:1～4.
8. method according to claim 6; it is characterized in that; described carbon-source gas is a kind of in methane, ethene, acetylene, natural gas, liquefied petroleum gas, benzene, ethanol or at least two kinds, and described protective gas is a kind of in nitrogen hydrogen, helium, argon gas or at least two kinds.
9. method according to claim 6, is characterized in that, described reactor is horizontal reactor, vertical reactor, fixing or mobile fluid bed.
10. a CNT, is characterized in that, adopts method method as described in claim 7～9 any one to make.
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