WO2013105780A1 - 카본나노튜브용 균질 담지 촉매의 제조방법 - Google Patents
카본나노튜브용 균질 담지 촉매의 제조방법 Download PDFInfo
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- WO2013105780A1 WO2013105780A1 PCT/KR2013/000158 KR2013000158W WO2013105780A1 WO 2013105780 A1 WO2013105780 A1 WO 2013105780A1 KR 2013000158 W KR2013000158 W KR 2013000158W WO 2013105780 A1 WO2013105780 A1 WO 2013105780A1
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- catalyst
- carbon nanotubes
- supported catalyst
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- aqueous solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 230000032683 aging Effects 0.000 claims abstract description 19
- 238000005470 impregnation Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 18
- 230000002401 inhibitory effect Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 239000011148 porous material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- -1 2 · 6H 2 O Chemical class 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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Definitions
- the present invention relates to a method for preparing a homogeneously supported catalyst for carbon nanotubes.
- Carbon nanotubes (hereinafter referred to as 'CNT') is understood to mean cylindrical carbon tubes having a diameter of 3 to 150 nm, preferably 3 to 100 nm and a length several times the diameter, that is, 100 times or more. These CNTs consist of aligned layers of carbon atoms and have different types of cores. Such CNTs are also called, for example, carbon fibrils or hollow carbon fibers.
- CNTs are industrially important in the manufacture of composites because of their size and specific properties, and are likely to be utilized in electronic, energy and additional applications.
- the CNT is generally manufactured by arc discharge, laser ablation, chemical vapor deposition, or the like.
- the arc discharge method and the laser evaporation method are difficult to mass-produce, and excessive arc production cost or laser equipment purchase cost is a problem.
- the chemical vapor deposition method has a problem that the synthesis rate is very slow in the case of using a gas phase dispersion catalyst and the particles of CNT synthesized are too small.
- the space utilization efficiency in the reactor is greatly decreased. There is a limit to mass production of CNTs.
- the catalyst may be a supported catalyst, co-precipitation catalyst, etc., mainly in which the catalytically active component has an oxide form, a partially or fully reduced form, or a hydroxide form, and which can be commonly used for preparing CNTs. It is preferable to use a double supported catalyst, which, when used, has a higher bulk density of the catalyst itself than the coprecipitation catalyst, and unlike the coprecipitation catalyst, there is less fineness of less than 10 microns, which prevents attrition that may occur during fluidization. This is because the possibility of fine powder generation can be reduced, and the mechanical strength of the catalyst itself is also excellent, which can stabilize the reactor operation.
- the present invention provides a method for preparing a homogeneously supported catalyst for carbon nanotubes that can increase the impregnation efficiency of the micropores of the metal loading, and improve the stability of the metal impregnated during the drying and firing process
- the purpose is to provide.
- the present invention comprises the steps of blending the precipitation inhibiting component (M) to the aqueous solution of the precursor of the active ingredient (A) and then mixing the precursor solution of the catalyst component to obtain a metal homogeneous aqueous solution;
- Vacuum drying the mixture to prepare a supported catalyst It provides a method for producing a homogeneously supported catalyst for carbon nanotubes comprising a.
- the metal catalyst for producing CNTs when the metal catalyst for producing CNTs is dried, a solid substance is formed and the removal of the solvent (water) is difficult, the yield of the final catalyst is lowered, and the activity in the firing step is decreased.
- the impregnation efficiency of the micropores of the catalyst loading amount in consideration of the impregnation efficiency of the micropores of the catalyst loading amount to provide a method for producing a homogeneously supported catalyst for carbon nanotubes by applying a high temperature aging process in the impregnation process.
- fine powder having a smaller particle size than the support is produced by precipitation reaction between the metal component and the active component at 100 ° C. or higher.
- the Fe of a metal component and if used as an active ingredient a Mo Fe 3+ + 3MoO - -> Fe (MoO) transparent homogeneous so dark yellow precipitate is formed by the reaction of 3 ⁇ (homogeneous) the supported catalyst It becomes impossible to manufacture.
- the catalyst provided in the present invention is not only a supported supported catalyst for use in a fluidized bed (FBR) reactor for producing carbon nanotubes, but also corresponds to a homogeneous catalyst because it prevents such precipitation through rapid drying.
- FBR fluidized bed
- the precipitation inhibiting component and the catalyst component precursor aqueous solution are sequentially mixed with the precursor aqueous solution of the active ingredient to obtain a transparent metal homogeneous aqueous solution (first step).
- the obtained metal homogeneous aqueous solution is mixed with the support and impregnated with hot aging to obtain a mixture (second step).
- the obtained mixture is dried in vacuo to prepare a supported catalyst coated with a catalyst component on the support surface (third step).
- the catalyst component used in the present invention may be one or more selected from Fe, Co and Ni, for example Fe salt, Fe oxide, Fe compound, Co salt, Co oxide, Co compound, Ni salt, Ni oxide, Ni compound It may be one or more selected from the group consisting of, and in another example Fe (NO 3 ) 2 ⁇ 6H 2 O, Fe (NO 3 ) 2 ⁇ 9H 2 O, Ni (NO 3 ) 2 ⁇ 6H 2 O, Co (NO 3 ) a nitride such as 2 ⁇ 6H 2 O, or the like.
- the active ingredient used in the present invention may be, for example Mo, another example may be Mo salt, Mo oxide, or Mo compound, another example (NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O Nitride and the like can be dissolved in distilled water and used.
- a multicarboxylic acid can be used as an example, As another example, 1 or more types chosen from dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid can be used.
- the first step using these components is a step of preparing a Mo precursor aqueous solution (a step), a step of mixing a precipitation inhibiting component with the Mo precursor aqueous solution (b step) and the (C process) of mixing the catalyst component precursor with the aqueous solution.
- the Mo precursor used in step a of the first step is not limited thereto, but nitrides of Mo and the like may be dissolved and used in distilled water.
- the aqueous precursor solution of Mo is preferably included in the range of 0.5 to 12 mol% based on the active ingredient when considering the efficiency of the reaction.
- the precipitation inhibiting component used in step b in the first step is a molar ratio (M / A) of at least one (M) selected from dicarboxylic acid, tricarboxylic acid and tetracarboxylic acid to the Mo precursor (A). ) To 0.2 to 0.5 is preferable when considering the improvement of CNT yield due to the prevention of precipitation of aqueous solution and the production of uniform catalyst.
- the catalyst component precursor used in step c of the first step may be at least one selected from Fe, Co, and Ni, and specifically, at least one of these nitrides may be dissolved and used in distilled water.
- a specific usage amount it is preferable to include in the range of 10 to 40 mol% based on the catalyst component when considering the efficiency of the reaction.
- the concentration of the homogeneous aqueous solution thus obtained is 0.1 to 0.4 g / ml, or 0.1 to 0.3 g / ml, which is efficient when considering the reactivity.
- the support is mixed with the metal homogeneous aqueous solution obtained through the first step (second step).
- the support used in the second step is alumina, magnesium oxide and silica It may be selected from among them, it is preferable to use alumina as identified in the examples below.
- the support is commercially available Al 2 O 3 , MgO, SiO 2 Support such as this can be used.
- the aging impregnation is not limited to this, but is carried out for more than 30 minutes to less than 15 hours, or 1 to 15 hours under 20 °C ⁇ 100 °C or less, 60 ⁇ 100 °C, as it is clear in the following Examples, Aging at high temperature can increase the mobility of the metal salt in the homogeneous metal solution to reach deep pores of alumina to provide high supporting efficiency.
- the mixture obtained after the aging is subjected to a rapid drying process.
- rapid drying is rapid drying under vacuum, and for example, performing within 1 hour or 1 minute to 1 hour at 45 ° C. to 80 ° C. is not impregnated into the deep pores of alumina, as shown in the following Examples.
- the remaining excess metal salt may be subjected to a drying process to provide a coating impregnation of the uniform alumina surface.
- vacuum in the vacuum drying of the present disclosure is not particularly limited as long as it corresponds to the vacuum range that is typically applied to vacuum drying.
- the granular supported catalyst may be a spherical type having a diameter or an average diameter in the range of 30 to 200 ⁇ m and a surface particle size of 10 to 100 nm during SEM observation, but depends on the support particle size used, but is not limited to the particle size. .
- a device for producing a metal homogeneous aqueous solution a device for mixing a metal homogeneous aqueous solution and a support conveyed from the device for producing a homogeneous metal homogeneous aqueous solution, an apparatus for impregnating the obtained product by high temperature aging, and an aging impregnated conveyed from the impregnation device. It consists of a device for drying water.
- the apparatus for producing a metal homogeneous aqueous solution may be a solution stirring mixing device, comprising a catalyst component input means, an active component input means, a precipitation inhibiting component input means, and a control means for the three kinds of input means.
- control means of the three kinds of means is turned on the active ingredient injecting means (on) while turning off the catalyst component injecting means and the precipitation inhibiting component injecting means (on) complete the addition of the precursor of the active ingredient,
- the catalyst component input means and the active ingredient input means are turned off, the precipitation inhibiting component input means is turned on to complete the input of the precipitation inhibiting component, and the active ingredient input means and the precipitation inhibiting component input means are It can be controlled sequentially by turning off the catalyst component input means while turning off the catalyst component input means.
- the drying device may be a vacuum drying device, preferably a rotary heating device.
- the vacuum drying apparatus may have a form in which a wall surface inside the apparatus is straight or a baffle is present, or may be inclined at a predetermined angle with respect to the vertical and rotated at a predetermined speed.
- the aging impregnation device may be aged for 1 to 15 hours at 60 ⁇ 100 °C using a reflux (reflux) to enable the reflux of the solvent by overheating before the transfer to the drying device. .
- Example 1 is a photograph showing an SEM image of a particulate catalyst prepared according to Example 1 of the present invention (X35).
- Example 2 is a photograph showing an SEM image of CNTs synthesized using the catalyst of Example 1 of the present invention (X100).
- Example 3 is a photograph showing an SEM high magnification image of CNTs synthesized using the catalyst of Example 1 of the present invention (X50,000).
- the concentration of the aqueous metal solution was 0.3g / ml and a clear solution without precipitation is observed.
- the obtained sample was vacuum dried by rotary evaporation and then calcined at 700 ° C. for 3 hours to prepare a homogeneous supported catalyst.
- the prepared catalyst forms a granule upon drying, and the yield of the final catalyst obtained was 95% based on the amount of the obtained catalyst based on the amount of the metal solution and alumina used in the preparation. .
- Example 1 The same process as in Example 1 was repeated except that the aging step in Example 1 was carried out at 70 ° C. for 6 hours and further dried by rotary evaporation twice at 30 ° C. for 30 minutes.
- the prepared catalyst also formed a granule upon drying, and the yield of the finally obtained catalyst was 93% when the amount of the obtained catalyst was calculated based on the amount of the metal solution and alumina used in the preparation.
- Example 1 The same process as in Example 1 was repeated except that the aging step was carried out at 20 ° C. for 15 minutes and further dried by rotary evaporation twice at 30 ° C. for 30 minutes.
- the prepared catalyst also formed a granule upon drying, and the yield of the finally obtained catalyst was 92% as a result of calculating the amount of the obtained catalyst based on the amount of the metal solution and alumina used in the preparation.
- Example 1 The same process as in Example 1 was repeated except that the aging step in Example 1 was carried out for 30 minutes and further dried by rotary evaporation twice at 60 ° C. for 30 minutes.
- Carbon nanotube synthesis was tested in a laboratory scale fixed bed reactor using the catalyst for synthesizing CNTs prepared in Examples 1 and 2.
- the catalyst for synthesizing CNT prepared in Example 1 was mounted in the middle of a quartz tube having an internal diameter of 55 mm, and then heated to 700 ° C. in a nitrogen atmosphere, and then maintained.
- the volumetric mixing ratio was flowed in the same manner, and the total flow rate was set to 180 ml per minute, and then synthesized for 1 hour to synthesize a predetermined amount of carbon nanotubes.
- the synthesized carbon nanotubes were obtained at room temperature, and their contents were measured.
- the reaction yield was calculated based on the weight of the catalyst for synthesizing CNTs used and the weight increase after the reaction based on the following formula:
- CNT yield (gross weight after reaction (g)-weight of catalyst used (g)) / weight of catalyst used (g).
- Example 2 CNT collected in the CNT recovery unit after the 1 hour reaction showed a CNT yield of 28.6gCNT / gCat compared to the catalyst input in Example 1, wherein the diameter or average diameter of the obtained CNT was 20 ⁇ 30nm.
- the results of Example 2 are summarized together in Table 1 below.
- the CNT collected in the CNT recovery unit after the 1 hour reaction showed a CNT yield of 15.3 gCNT / gCat compared to the catalyst input in the case of Comparative Example 1, and the diameter or the average diameter of the obtained CNT was 20 to 30 nm.
- the results of Comparative Example 2 were also summarized in Table 1 below.
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Abstract
Description
구분 | 실시예 1 | 실시예 2 | 비교예 1 | 비교예 2 | |
촉매 | 숙성 | 95℃, 12hr | 70℃, 6hr | 20℃, 15min | 95℃, 30min |
건조 | O(회전증발) | ||||
촉매의 입자상태 | 입상 | 입상 | 입상 | 입상 | |
최종 촉매수율(wt%) | 95 | 95 | 92 | 90 | |
CNT 수율(gCNT/gCat) | 28.6 | 24.5 | 15.3 | 17.4 |
Claims (10)
- 활성 성분(A)의 전구체 수용액에 침전 억제 성분(M)을 배합한 다음 촉매성분 전구체 수용액을 배합하여 금속 균질 수용액을 수득하는 단계;상기 금속 균질 수용액을 지지체와 혼합하고 20℃ 초과~100℃ 이하 및 30분 초과 ~15시간 이하 조건 하에 숙성 함침시켜 혼합물을 수득하는 단계; 및상기 혼합물을 진공 건조시켜 담지 촉매를 제조하는 단계; 를 포함하는 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제1항에 있어서,상기 숙성 함침은 60~100℃ 하에 1~15시간 동안 수행하는 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제1항에 있어서,상기 침전 억제 성분(M)과 상기 활성 성분(A)은 상기 침전 억제 성분과 상기 활성 성분(A)간 몰비(M/A)가 0.2~0.5가 되도록 투입하는 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제1항에 있어서,상기 침전 억제 성분은 멀티 카르복실산인 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제4항에 있어서,상기 멀티 카르복실산은 디카르복실산, 트리카르복실산 및 테트라카르복실산 중에서 선택된 1종 이상인 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제1항에 있어서,상기 촉매 성분의 전구체 수용액은 Fe, Co 및 Ni로부터 선택된 1종 이상의 전구체 수용액을 사용하는 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제1항에 있어서,상기 활성 성분의 전구체 수용액은 Mo 전구체 수용액을 사용하는 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제1항에 있어서,상기 금속 균질 수용액의 농도는 0.1~0.4g/ml 인 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제1항에 있어서,상기 지지체는 알루미나, 산화마그네슘 및 실리카 중에서 선택된 1종 이상인 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
- 제1항에 있어서,상기 진공 건조 단계는 회전식 진공 건조 장치를 사용하여 45~80℃ 하에 1시간 이내로 수행되는 급속 진공 건조 단계인 것을 특징으로 하는 카본나노튜브용 균질 담지 촉매의 제조방법.
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