KR20130034328A - Support of catalyst for cnt synthesis and catalyst prepared therefrom - Google Patents

Support of catalyst for cnt synthesis and catalyst prepared therefrom Download PDF

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KR20130034328A
KR20130034328A KR1020110098282A KR20110098282A KR20130034328A KR 20130034328 A KR20130034328 A KR 20130034328A KR 1020110098282 A KR1020110098282 A KR 1020110098282A KR 20110098282 A KR20110098282 A KR 20110098282A KR 20130034328 A KR20130034328 A KR 20130034328A
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catalyst
aluminum hydroxide
cnt synthesis
support
cnt
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KR101498755B1 (en
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김성진
김진도
강경연
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주식회사 엘지화학
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/021—After-treatment of oxides or hydroxides

Abstract

PURPOSE: A catalyst support, a CNT synthesizing catalyst using the same and a method of making the same are provided to reduce the cost of production, prevent particles from being made in CNT synthesizing process by keeping hardness and grain size, especially suitable for a fluid bed reactor. CONSTITUTION: A catalyst support is aluminum hydroxide powder containing boehmite over 40 by weight % or boehmite powder and used as a catalyst support for CNT synthesizing process. The particle size of the powder is 25-50Mm. The boehmite is manufactured by plastic-processing aluminum hydroxide at a temperature of 250-600>=. The average size(MN) of aluminum hydroxide is 20-65 Mm. The aluminum hydroxide is dried aluminum hydroxide. The CNT synthesizing catalyst is made through a way that a reactive metal is dipped in the catalyst support. In the CNT synthesizing catalyst, the amount of the reactive metal is over 10 by weight %. The CNT synthesizing catalyst is applied to a fluid bed reactor. [Reference numerals] (AA) Comparative example 1; (BB) Comparative example 2; (CC) Example 1; (DD) Example 2; (EE) Example 3; (FF) Example 4; (GG) Example 5; (HH) Example 6; (II) Example 7; (JJ) Example 8;

Description

ＣＮＴ 합성 촉매용 지지체 및 이를 포함하는 ＣＮＴ 합성 촉매{Support Of Catalyst For CNT Synthesis And Catalyst Prepared Therefrom}Support for Catalyst for CNT Synthesis And Catalyst Prepared Therefrom

본 발명은 CNT 합성 촉매용 지지체 및 이를 포함하는 CNT 합성 촉매에 관한 것으로, 보다 상세하게는 20 중량% 이상으로 금속 담지가 가능하고, 경도가 뛰어나며 입도가 안정적으로 유지되어 CNT 합성 시 미분이 발생하지 않는, 특히 유동층 반응기에 적합한 CNT 합성 촉매용 지지체 및 이를 포함하는 CNT 합성 촉매에 관한 것이다.
The present invention relates to a support for a CNT synthesis catalyst and a CNT synthesis catalyst including the same. More specifically, the metal can be supported by more than 20% by weight, has excellent hardness and stable particle size, so that fine powder does not occur during CNT synthesis. And a support for a CNT synthesis catalyst suitable for a fluidized bed reactor, and a CNT synthesis catalyst comprising the same.

대한민국 공개특허 제2007-86611호는 탄소 나노튜브의 제조를 위한 지지 촉매의 합성방법에 관한 것으로 담지체로 80 ㎛ 이하의 입자 크기를 가지는 수산화알루미늄 분말을 사용하여 함침법에 의해 탄소나노튜브 제조용 촉매를 제조하는 방법에 대하여 기술하고 있다. 그러나 상기 공개특허는 분쇄 및 체질의 분급 과정이 필요하고, 담지된 금속 함량이 2~10 %로 낮은 한계가 있다. Korean Unexamined Patent Publication No. 2007-86611 relates to a method for synthesizing a supported catalyst for the production of carbon nanotubes. The manufacturing method is described. However, the published patent requires a classification process of pulverization and sieving, and there is a limit that the supported metal content is 2 to 10%.

대한민국 공개특허 제2010-0045247호는 탄소나노튜브 합성용 담지 촉매, 그 제조방밥 및 이를 이용한 탄소나노튜브에 관한 것으로 알루미나, 산화마그네슘, 실리카 등의 담지체에 Fe, Co, Ni 등의 금속을 담지시킨 평균 직경 30~100 ㎛의 담지촉매 합성법에 대하여 기술하고 있고, 대한민국 공개특허 제2010-0077422호는 탄소나노튜브 제조용 촉매조성물에 관한 것으로 공침법을 통해 다양한 조성의 담지 촉매 합성하는 방법에 대해 기술하고 있다. 그러나, 이러한 방법들을 통해 합성된 촉매는 높은 수율을 얻을 수는 있으나, 촉매입자의 크기와 모양을 조절하는 것이 용이하지 않고, 공침제 등의 여러 부가물을 사용하여야 하며, 생산비용이 높아 경제성이 떨어지는 문제가 있다.
Korean Unexamined Patent Publication No. 2010-0045247 relates to a supported catalyst for synthesizing carbon nanotubes, a manufacturing method thereof, and a carbon nanotube using the same. The supported catalyst synthesis method having an average diameter of 30 to 100 μm is described, and Korean Unexamined Patent Publication No. 2010-0077422 relates to a catalyst composition for preparing carbon nanotubes, and a method for synthesizing a supported catalyst having various compositions through a coprecipitation method. Doing. However, the catalyst synthesized through these methods can obtain a high yield, but it is not easy to control the size and shape of the catalyst particles, and various additives such as co-precipitation should be used. There is a problem falling.

상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 20 중량% 이상으로 금속 담지가 가능하고, 경도가 뛰어나며 입도가 안정적으로 유지되어 CNT 합성 시 미분이 발생하지 않는, 특히 유동층 반응기에 적합한 CNT 합성 촉매용 지지체 및 이를 포함하는 CNT 합성 촉매를 제공하는 것을 목적으로 한다. In order to solve the problems of the prior art as described above, the present invention is capable of supporting a metal in more than 20% by weight, excellent hardness and stable particle size, so that fine powder does not occur during CNT synthesis, particularly suitable for fluidized bed reactors. It is an object to provide a support for a catalyst and a CNT synthesis catalyst comprising the same.

본 발명의 상기 목적 및 기타 목적들은 하기 설명된 본 발명에 의하여 모두 달성될 수 있다.
The above and other objects of the present invention can be achieved by the present invention described below.

상기의 목적을 달성하기 위하여, 본 발명은 CNT 합성 촉매용 지지체 및 이를 포함하는 CNT 합성 촉매에 관한 것으로, 보다 상세하게는 보우마이트(boehmite) 분말 또는 보우마이트가 40 중량% 이상 함유된 수산화알루미늄 분말로, CNT 합성 촉매의 지지체로 사용됨을 특징으로 하는 촉매 지지체 및 이를 포함하는 CNT 합성 촉매를 제공한다.
In order to achieve the above object, the present invention relates to a support for a CNT synthesis catalyst and a CNT synthesis catalyst comprising the same, more specifically, boehmite powder or aluminum hydroxide powder containing at least 40% by weight of boehmite The present invention provides a catalyst support and a CNT synthesis catalyst comprising the same, wherein the catalyst support is used as a support for the CNT synthesis catalyst.

상기에서 살펴본 바와 같이, 본 발명에 따르면 생산비용을 크게 절감시킬 수 있으며, 20 중량% 이상으로 금속 담지가 가능하고, 경도가 뛰어나며 입도가 안정적으로 유지되어 CNT 합성 시 미분이 발생하지 않는, 특히 유동층 반응기에 적합한 CNT 합성 촉매용 지지체 및 이를 포함하는 CNT 합성 촉매를 제공하는 효과가 있다.
As described above, according to the present invention, it is possible to greatly reduce the production cost, to support the metal by more than 20% by weight, excellent hardness and stable particle size, so that no fine powder occurs during CNT synthesis, in particular fluidized bed There is an effect of providing a support for a CNT synthesis catalyst suitable for a reactor and a CNT synthesis catalyst comprising the same.

도 1은 입도 분석기에 의해 측정된 상용 수산화알루미늄(WH-50)의 입도 그래프 및 입도 분석 결과를 나타낸다.
도 2는 입도 분석기에 의해 측정된 상용 수산화알루미늄(WH-50)을 지지체로 사용한 Co, Mo 담지 촉매의 입도 그래프 및 입도 분석 결과를 나타낸다.
도 3, 4는 각각 실시예 1 내지 8 및 비교예 1 내지 2에서 제조된 CNT 합성 촉매용 지지체(ATH)에 대한 소니케이션 처리 시간에 따른 D50 및 평균입경(MN) 변화량을 나타내는 그래프이다.
도 5, 6은 각각 실시예 1 내지 8 및 비교예 1 내지 2에서 제조된 CNT 합성 촉매에 대한 소니케이션 처리 시간에 따른 D50 및 평균입경(MN) 변화량을 나타내는 그래프이다.
도 7 내지 10은 각각 입도 분석기에 의해 측정된 실시예 1, 2, 5와 비교예 2에서 제조된 각각의 CNT 합성 촉매에 대한 소니케이션 처리(15 분) 이전과 이후의 입도 그래프 및 입도 분석 결과를 나타낸다.1 shows particle size graphs and particle size analysis results of commercial aluminum hydroxide (WH-50) measured by a particle size analyzer.
2 shows particle size graphs and particle size analysis results of Co and Mo supported catalysts using a commercially available aluminum hydroxide (WH-50) as a support, measured by a particle size analyzer.
3 and 4 are graphs showing changes in D 50 and average particle diameter (MN) according to the sonication treatment time for the CNT synthesis catalyst supports (ATH) prepared in Examples 1 to 8 and Comparative Examples 1 and 2, respectively.
5 and 6 are graphs showing changes in D 50 and average particle diameter (MN) according to the sonication treatment time for the CNT synthesis catalysts prepared in Examples 1 to 8 and Comparative Examples 1 and 2, respectively.
7 to 10 are particle size graphs and particle size analysis results before and after the sonication treatment (15 minutes) for each of the CNT synthesis catalysts prepared in Examples 1, 2, and 5 and Comparative Example 2 measured by particle size analyzers, respectively. Indicates.

본 발명자들은 연구를 거듭한 끝에 수산화알루미늄을 가열처리하여 제조된 보우마이트(boehmite) 분말 또는 보우마이트가 40 중량% 이상 함유된 수산화알루미늄 분말이 CNT 합성 촉매의 지지체로 사용되기에 적합한 강도 및 높은 표면적을 가지고, 활성금속의 원료물질이 포함되는 CNT 촉매 합성 단계에서 이를 그대로 지지체로 투입하여 제조된 CNT 촉매는 본래의 입도가 유지되고, 강도 등이 우수하며 반응수율이 향상되는 것을 확인하고, 이를 토대로 본 발명을 완성하게 되었다.
The inventors of the present invention have made strength and high surface area suitable for using boehmite powder or aluminum hydroxide powder containing 40 wt% or more of boehmite powder prepared by heat treatment of aluminum hydroxide as a support for CNT synthesis catalyst. In the step of synthesizing the CNT catalyst containing the active material of the raw material, the prepared CNT catalyst as it is confirmed that the original particle size is maintained, the strength is excellent and the reaction yield is improved, based on this The present invention has been completed.

이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.

본 발명의 촉매 지지체는 보우마이트(boehmite) 분말 또는 보우마이트가 40 중량% 이상 함유된 수산화알루미늄 분말로, CNT 합성 촉매의 지지체로 사용됨을 특징으로 한다.
The catalyst support of the present invention is a boehmite powder or aluminum hydroxide powder containing 40 wt% or more of boehmite powder, and is used as a support for a CNT synthesis catalyst.

상기 보우마이트(boehmite) 분말 또는 보우마이트가 40 중량% 이상 함유된 수산화알루미늄 분말은 평균입경이 25 내지 50 ㎛인 것이 바람직하다. The boehmite powder or aluminum hydroxide powder containing 40 wt% or more of boehmite powder preferably has an average particle diameter of 25 to 50 μm.

상기 보우마이트는 수산화알루미늄을 250 내지 600 ℃에서 소성처리하여 형성되는 것이 바람직하고, 보다 바람직하게는 수산화알루미늄을 300 내지 450 ℃에서 소성처리하여 형성되는 것이며, 더욱 바람직하게는 300 내지 425 ℃에서 소성처리하여 형성되는 것인데, 이 경우 소니케이션에도 D50 변화량 및 MN 변화량이 현저히 작고, 이를 이용하여 제조된 CNT 합성촉매의 경우 경도가 크며 CNT 합성 시에도 본래의 입도가 유지되고 미분의 발생이 억제되며 반응수율이 높은 효과가 있다.The bowmite is preferably formed by calcining aluminum hydroxide at 250 to 600 캜, more preferably calcined aluminum hydroxide at 300 to 450 캜, and more preferably calcining at 300 to 425 캜. In this case, the amount of change in D 50 and MN in Sony is remarkably small.In the case of CNT synthesis catalysts manufactured using this, the hardness is high and the original particle size is maintained even during CNT synthesis, and the generation of fine powder is suppressed. The reaction yield is high.

상용 수산화알루미늄(aluminum trihydroxide)은 일정한 입도를 가지나 충분한 경도를 가지지 못하여, 그 자체를 촉매 지지체로 사용하는 경우 촉매 합성 과정 중 본래의 입도가 유지되지 못하고, 다량의 미분이 발생한다.Commercial aluminum hydroxide (aluminum trihydroxide) has a constant particle size, but does not have a sufficient hardness, when using itself as a catalyst support does not maintain the original particle size during the catalyst synthesis process, a large amount of fine powder is generated.

하기 도 1, 2는 각각 상용 수산화알루미늄(WH-50)과 상용 수산화알루미늄(WH-50)을 지지체로 사용한 Co, Mo 담지 촉매의 입도 분석 결과인데, 상용 수산화알루미늄(WH-50)의 입도는 일정하나, 이를 지지체로 사용한 Co, Mo 담지 촉매의 입도는 불균일하고 다량의 미분이 포함되어 있음을 확인할 수 있다. 그리고, 이러한 담지 촉매는 경도가 낮아 특히 유동층 반응기에 적합하지 않다.1 and 2 are particle size analysis results of Co and Mo supported catalysts using commercial aluminum hydroxide (WH-50) and commercial aluminum hydroxide (WH-50), respectively, and the particle size of commercial aluminum hydroxide (WH-50) is However, it can be seen that the particle size of the Co and Mo supported catalyst using this as a support is nonuniform and contains a large amount of fine powder. In addition, these supported catalysts have low hardness and are not particularly suitable for a fluidized bed reactor.

그러나, 250 내지 600 ℃에서 열처리된 수산화알루미늄은 본래의 입도를 유지하여 분급과정이 필요치 않고, 적절한 경도를 갖게 되어 성공적으로 CNT 합성 촉매의 지지체로 사용될 수 있으며, 높은 함량으로 활성 금속 담지가 가능한 효과가 있다.However, the aluminum hydroxide heat-treated at 250 to 600 ℃ does not require a classification process by maintaining the original particle size, has an appropriate hardness, can be successfully used as a support for the CNT synthesis catalyst, it is possible to support the active metal with a high content There is.

상기 소성 처리는 1 내지 10 시간 동안 실시되는 것이 바람직하고, 보다 바람직하게는 2 내지 8 시간 동안 실시되는 것이며, 가장 바람직하게는 3 내지 6 시간 동안 실시되는 것인데, 이 범위 내에서 입경, 경도 등이 뛰어난 효과가 있다.The firing treatment is preferably carried out for 1 to 10 hours, more preferably for 2 to 8 hours, most preferably for 3 to 6 hours, the particle diameter, hardness and the like within this range Excellent effect.

상기 수산화알루미늄은 수평균입경(MN)이 20 내지 65 ㎛인 것이 바람직하고, 보다 바람직하게는 25 내지 45 ㎛인 것이다.It is preferable that the number average particle diameter (MN) of the said aluminum hydroxide is 20-65 micrometers, More preferably, it is 25-45 micrometers.

상기 수산화알루미늄은 분말상인 것이 바람직한데, 이 경우 촉매 합성 이후에도 경도가 뛰어나 본래의 입도가 유지되고 미분의 발생이 억제되며, 반응수율이 높은 효과가 있다.The aluminum hydroxide is preferably in the form of a powder, in which case the hardness is excellent even after the synthesis of the catalyst, the original particle size is maintained, the generation of fine powder is suppressed, and the reaction yield is high.

상기 수산화알루미늄은 WH-50인 것이 바람직하다 It is preferable that the said aluminum hydroxide is WH-50.

상기 수산화알루미늄은 자유수분 함량이 5 중량% 이하인 것이 바람직하고, 보다 바람직하게는 1 내지 5 중량%인 것이다.The aluminum hydroxide preferably has a free moisture content of 5% by weight or less, more preferably 1 to 5% by weight.

상기 수산화알루미늄은 건조 처리된 것이 바람직하다.The aluminum hydroxide is preferably dried.

상기 건조 처리는 그 처리 온도가 통상의 수산화알루미늄 건조 온도인 경우 특별히 제한되지 않으나, 80 내지 160 ℃인 것이 바람직하고, 보다 바람직하게는 100 내지 140 ℃인 것이며, 가장 바람직하게는 110 내지 130 ℃인 것이다.The drying treatment is not particularly limited when the treatment temperature is a normal aluminum hydroxide drying temperature, but is preferably 80 to 160 ° C, more preferably 100 to 140 ° C, and most preferably 110 to 130 ° C. will be.

상기 건조 처리는 그 처리 시간이 통상의 수산화알루미늄 건조 시간인 경우 특별히 제한되지 않으나, 1 내지 20 시간인 것이 바람직하고, 보다 바람직하게는 5 내지 12 시간이며, 가장 바람직하게는 6 내지 10 시간인 것이다
The drying treatment is not particularly limited when the treatment time is a normal aluminum hydroxide drying time, but is preferably 1 to 20 hours, more preferably 5 to 12 hours, and most preferably 6 to 10 hours.

본 발명의 CNT 합성 촉매는 상기 촉매 지지체에 활성금속이 담지되어 이루어진 것을 특징으로 한다.CNT synthesis catalyst of the present invention is characterized in that the active metal is supported on the catalyst support.

상기 활성금속은 CNT 합성에 사용될 수 있는 활성금속인 경우 특별히 제한되지 않으나, Co, Fe, Ni 등으로 이루어진 군으로부터 선택된 1종 이상이 바람직하고, 보다 바람직하게는 Co이다.The active metal is not particularly limited as long as it is an active metal that can be used for CNT synthesis, but at least one selected from the group consisting of Co, Fe, Ni, and the like is preferable, and more preferably Co.

상기 활성금속은 Co, Fe, Ni 등으로 이루어진 군으로부터 선택된 1종 이상에 Mo가 조촉매 성분으로 혼합된 것일 수 있다.The active metal may be a mixture of Mo as a cocatalyst component in at least one selected from the group consisting of Co, Fe, Ni and the like.

상기 Mo 조촉매 성분은 상기 활성금속 1 몰당 0.01 내지 1 몰인 것이 바람직하다.
The Mo cocatalyst component is preferably 0.01 to 1 mol per mol of the active metal.

상기 촉매 지지체와 혼합되는 상기 활성금속의 원료물질로는 물에 용해될 수 있는 금속 산화물, 금속 염 또는 금속 수산화물 형태일 수 있고, 바람직하게는 금속 염 형태이다.The raw material of the active metal mixed with the catalyst support may be in the form of a metal oxide, a metal salt or a metal hydroxide, which is soluble in water, and preferably in the form of a metal salt.

상기 활성금속은 CNT 합성 촉매 내에서 금속 산화물 형태로 존재할 수 있다.The active metal may be present in the form of a metal oxide in a CNT synthesis catalyst.

상기 CNT 합성 촉매는 활성 금속 함량이 10 중량%인 것이 바람직하고, 보다 바람직하게는 20 중량% 이상이며, 가장 바람직하게는 20 내지 40 중량%인 것이다.
The CNT synthesis catalyst preferably has an active metal content of 10% by weight, more preferably 20% by weight or more, and most preferably 20-40% by weight.

상기 CNT 합성 촉매는 수평균입경(MN)이 20 내지 60 ㎛인 것이 바람직하고, 보다 바람직하게는 25 내지 50 ㎛이며, 가장 바람직하게는 30 내지 50 ㎛인데, 이 범위 내에서 반응수율이 높은 효과가 있다.The CNT synthesis catalyst preferably has a number average particle diameter (MN) of 20 to 60 µm, more preferably 25 to 50 µm, and most preferably 30 to 50 µm, and the reaction yield is high within this range. There is.

상기 CNT 합성 촉매는 유동층 반응기에 적용되는 것이 바람직하다. The CNT synthesis catalyst is preferably applied to a fluidized bed reactor.

상기 CNT 합성 촉매는 소니케이션(sonication)을 통해 물리적 힘이 가해지는 경우에도 입도가 유지되고 미분 발생이 억제되어, 특히 유동층 반응기에 적합하고, 사전에 입도와 경도가 조절된 고가의 상용 알루미나의 사용을 대체하는 효과가 있다.
The CNT synthesis catalyst maintains the particle size and suppresses the generation of fine particles even when physical force is applied through sonication, and is particularly suitable for a fluidized bed reactor, and the use of expensive commercially available alumina whose particle size and hardness are controlled in advance. Has the effect of replacing

본 발명의 CNT 합성 촉매의 제조방법은 상기 활성금속의 원료물질의 수용액에 상기 촉매 지지체를 투입하여 페이스트 또는 슬러리를 형성하는 단계를 포함하여 이루어지는 것을 특징으로 한다.
Method for producing a CNT synthesis catalyst of the present invention is characterized in that it comprises the step of forming the paste or slurry by adding the catalyst support to the aqueous solution of the raw material of the active metal.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[실시예][Example]

실시예Example 1 내지 8 1 to 8

<상용 수산화알루미늄의 열처리><Heat treatment of commercial aluminum hydroxide>

수산화알루미늄(WH-50)을 120 ℃에서 8 시간 동안 건조한 후, 이를 다시 각각 120~600 ℃에서 4 시간 동안 소성시켜, 파우더 형태의 CNT 합성 촉매용 지지체를 제조하였다. 제조된 CNT 합성 촉매용 지지체를 입도 분석기(Microtrac, bluewave)를 이용하여 소니케이션(40 watt)하면서 입도 변화를 관찰하였고, 그 결과를 하기 도 3, 4에 기재하였다.Aluminum hydroxide (WH-50) was dried at 120 ° C. for 8 hours, and then calcined at 120 ° C. to 600 ° C. for 4 hours, thereby preparing a support for a CNT synthesis catalyst in powder form. The prepared CNT synthesis catalyst support was observed by using a particle size analyzer (Microtrac, bluewave) while sonication (40 watts), and the results are described in FIGS. 3 and 4.

또한, XRD 분석 결과 실시예 1에서 제조된 CNT 합성 촉매용 지지체는 보우마이트가 40 중량%(Rietveld refinement에 의해 계산됨)이었고, 실시예 2 내지 6에서 제조된 CNT 합성 촉매용 지지체는 수산화알루미늄(Al(OH)3에 의한 패턴이 더 이상 관찰되지 않고 보우마이트에 의한 패턴만이 관찰되었으며, 실시예 7 및 8에서 제조된 CNT 합성 촉매용 지지체는 XRD 피크가 전체적으로 크게 감소하고 브로드한(broad) 피크들만이 관찰되었다.In addition, as a result of XRD analysis, the support for the CNT synthesis catalyst prepared in Example 1 was 40% by weight of boehmite (calculated by Rietveld refinement), and the support for the CNT synthesis catalyst prepared in Examples 2 to 6 was aluminum hydroxide ( The pattern by Al (OH) 3 was no longer observed, only by pattern of boehmite, and the support for CNT synthesis catalysts prepared in Examples 7 and 8 had a large overall decrease in XRD peaks and broad Only peaks were observed.

참고로, 실시예 7 및 8에서 제조된 CNT 합성 촉매용 지지체는 AlO(OH)에서 Al2O3로 변화되는 중에 있는 구조인 것으로 추측된다.
For reference, the support for the CNT synthesis catalyst prepared in Examples 7 and 8 is assumed to have a structure in the process of changing from AlO (OH) to Al 2 O 3 .

<수산화알루미늄으로부터 담지 촉매의 합성><Synthesis of Supported Catalysts from Aluminum Hydroxide>

Co(NO3)2·6H2O 870 ㎎과 (NH4)6Mo7O24 120 mg을 증류수 5.0 ml에 완전히 용해시킨 후, 제조된 CNT 합성 촉매용 지지체 1.0 g을 더한 후, 계속하여 교반하면서 70 ℃, 10 밀리바(mb) 하에서 45 분간 두어 고형분의 촉매 전구체를 수득하였다. 상기 촉매 전구체를 120 ℃에서 1 시간 동안 건조시킨 다음 분쇄하고, 이후 600 ℃에서 4 시간 동안 소성시켜 1.12 g의 CNT 합성 촉매를 제조하였다.
870 mg of Co (NO 3 ) 2 .6H 2 O and 120 mg of (NH 4 ) 6 Mo 7 O 24 were completely dissolved in 5.0 ml of distilled water, and then 1.0 g of the prepared support for CNT synthesis catalyst was added, followed by continued stirring. The mixture was allowed to stand for 45 minutes at 70 ° C. and 10 millibars (mb) to obtain a solid catalyst precursor. The catalyst precursor was dried at 120 ° C. for 1 hour and then ground, and then calcined at 600 ° C. for 4 hours to prepare 1.12 g of CNT synthesis catalyst.

<< CNTCNT 의 합성>Synthesis of

제조된 CNT 합성용 촉매를 이용하여 실험실 규모의 고정층 반응장치에서 탄소나노튜브 합성을 시험하였다. Carbon nanotube synthesis was tested in a laboratory scale fixed bed reactor using the prepared CNT synthesis catalyst.

제조된 CNT 합성용 촉매를 55 mm의 내경을 가진 석영관의 중간부에 장착한 후, 질소와 수소의 부피 혼합비 50:3에서 700 ℃까지 승온한 다음 유지시키고, 질소와 수소, 그리고 에틸렌 가스의 부피 혼합비를 50:3:10으로 흘리면서 1 시간 동안 합성을 행하여 소정량의 탄소나노튜브를 합성하였다. 합성된 탄소나노튜브를 상온에서 수득하여 그 양을 측정하였다. 이때 반응수율은 사용한 CNT 합성용 촉매의 중량과 반응 후 중량 증가량을 기준으로 계산되었다(반응수율(%)=(반응 후 총 중량-사용한 촉매의 중량)/사용한 촉매의 중량*100).
The prepared catalyst for synthesizing CNT was mounted in the middle of a quartz tube having an internal diameter of 55 mm, and then heated up to 700 ° C. at a volume mixing ratio of nitrogen and hydrogen at 50: 3, and then maintained. Synthesis was carried out for 1 hour while flowing a volume mixing ratio of 50: 3: 10 to synthesize a predetermined amount of carbon nanotubes. Synthesized carbon nanotubes were obtained at room temperature and their amounts were measured. The reaction yield was calculated based on the weight of the CNT synthesis catalyst used and the weight increase after the reaction (reaction yield (%) = (total weight after the reaction-weight of the catalyst used) / weight of the catalyst used * 100).

비교예Comparative example 1 One

상기 실시예 1에서 수산화알루미늄(WH-50)을 소성하지 않은 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except that the aluminum hydroxide (WH-50) was not calcined in Example 1 was carried out in the same manner as in Example 1.

비교예Comparative example 2 2

상기 실시예 1에서 수산화알루미늄(WH-50)을 소성 처리하는 대신 120 ℃에서 추가 건조 처리한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.
The same procedure as in Example 1 was performed except that the aluminum hydroxide (WH-50) was further dried at 120 ° C. instead of calcining.

[시험예][Test Example]

상기 실시예 1 내지 8 및 비교예 1 내지 2에서 제조된 CNT 합성 촉매용 지지체 및 CNT 합성용 촉매의 특성을 하기의 방법으로 측정하고, 그 결과를 하기의 표 1(지지체), 2(촉매)에 나타내었다.The properties of the support for the CNT synthesis catalyst and the catalyst for the synthesis of CNT prepared in Examples 1 to 8 and Comparative Examples 1 to 2 were measured by the following method, and the results are shown in Tables 1 (support) and 2 (catalyst) below. Shown in

* 평균입경(㎛): 제조된 CNT 합성 촉매용 지지체 또는 CNT 합성용 촉매를 소정 시간(지지체 9분, 촉매 15분) 소니케이션(40 watt)한 후, 입도 분석기(Microtrac, bluewave)를 이용하여 평균입경을 측정하였다.* Average particle size (μm): After a predetermined time (support 9 minutes, catalyst 15 minutes) sonication (40 watts) of the prepared support for CNT synthesis catalyst or CNT synthesis catalyst (40 watt), using a particle size analyzer (Microtrac, bluewave) The average particle diameter was measured.

* D50(㎛): 제조된 CNT 합성 촉매용 지지체 또는 CNT 합성용 촉매를 소정 시간(지지체 9분, 촉매 15분) 소니케이션(40 watt)한 후, 입도 분석기(Microtrac, bluewave)를 이용하여 D50을 측정하였다.* D 50 (μm): After a predetermined time (support 9 minutes, catalyst 15 minutes) sonication (40 watts) of the prepared support for CNT synthesis catalyst or CNT synthesis catalyst, using a particle size analyzer (Microtrac, bluewave) D 50 was measured.

* XRD 분석: Bruker AXS D4 Endeavor XRD (2)(전압: 40 Kv, 전류: 40 mA, Cu Kα radiation(파장: 1.5418 Å), LynxEye position sensitive detector)를 이용하여, 일반 분말용 홀더(holder)의 가운데 패인 홈에 분말을 넣고 슬라이드 글라스(slide glass)를 이용하여 표면을 고르게, 높이를 홀더의 가장자리와 같게 하여 준비한 후, FDS 0.5를 이용하여 2-theta 15 도에서 90 도 영역을 매 0.02 도 마다 175초씩 측정하였다.
* XRD analysis: Bruker AXS D4 Endeavor XRD (2) (voltage: 40 Kv, current: 40 mA, Cu Kα radiation (wavelength: 1.5418 Å), LynxEye position sensitive detector) Put the powder in the middle groove and prepare the surface evenly using slide glass and make the height the same as the edge of the holder, and then use the FDS 0.5 to make the 2-theta 15 to 90 degrees area every 0.02 degrees. 175 seconds were measured.

구분division 실시예Example 비교예Comparative example 1One 22 33 44 55 66 77 88 1One 22 ATH소성온도ATH firing temperature 250250 300300 350350 375375 400400 425425 450450 600600 -- 120120 D50(㎛)
(sonication
0 min)D 50 (占 퐉)
(sonication
0 min) 37.3337.33 28.6728.67 33.3133.31 37.9937.99 25.6525.65 31.3131.31 33.4933.49 30.6230.62 33.0433.04 36.7736.77 D50(㎛)
(sonication
9 min)D 50 (占 퐉)
(sonication
9 min) 31.7131.71 24.1124.11 31.1131.11 32.4332.43 24.3624.36 26.6626.66 31.1931.19 25.7425.74 18.7118.71 24.1524.15 D50 변화량D 50 variation 5.625.62 4.564.56 2.22.2 5.565.56 1.291.29 4.654.65 2.32.3 4.884.88 14.3314.33 12.6212.62 MN(㎛)
(sonication
0 min)MN (㎛)
(sonication
0 min) 38.8538.85 31.9631.96 35.2535.25 39.3839.38 29.8729.87 33.9933.99 35.4535.45 33.4533.45 35.735.7 38.4238.42 MN(㎛)
(sonication
9 min)MN (㎛)
(sonication
9 min) 33.8433.84 28.1728.17 33.3533.35 34.4234.42 28.6728.67 30.2130.21 33.4133.41 29.4729.47 28.3128.31 29.1629.16 MN 변화량MN variation 5.015.01 3.793.79 1.91.9 4.964.96 1.21.2 3.783.78 2.042.04 3.983.98 7.397.39 9.269.26

구분division 실시예Example 비교예Comparative example 1One 22 33 44 55 66 77 88 1One 22 ATH소성온도ATH firing temperature 250250 300300 350350 375375 400400 425425 450450 600600 -- 120120 MN(㎛)
(sonication
0 min)MN (㎛)
(sonication
0 min) 27.4527.45 39.4939.49 43.1943.19 35.5335.53 41.1541.15 47.847.8 41.4541.45 44.5944.59 3.73.7 19.3619.36 MN(㎛)
(sonication
15 min)MN (㎛)
(sonication
15 min) 20.6920.69 34.1134.11 39.9439.94 33.9433.94 39.739.7 43.9743.97 36.8936.89 40.5540.55 0.9760.976 1.3031.303 MN 변화량MN variation 6.766.76 5.385.38 3.253.25 1.591.59 1.451.45 3.833.83 4.564.56 4.044.04 2.7242.724 18.05718.057 D50(㎛)
(sonication
0 min)D 50 (占 퐉)
(sonication
0 min) 21.7521.75 38.338.3 42.1842.18 33.6333.63 40.5540.55 46.1946.19 40.7540.75 43.5943.59 2.6152.615 13.413.4 D50(㎛)
(sonication
15 min)D 50 (占 퐉)
(sonication
15 min) 14.5114.51 32.3132.31 39.3439.34 31.8831.88 39.1339.13 42.9542.95 36.3236.32 40.0440.04 0.7920.792 1.2041.204 D50 변화량D 50 variation 7.247.24 5.995.99 2.842.84 1.751.75 1.421.42 3.243.24 4.434.43 3.553.55 1.8231.823 12.19612.196 반응수율(%)Reaction yield (%) 161161 217217 306306 437437 588588 318318 374374 417417 128128 204204

상기 표 1에 나타낸 바와 같이, 본 발명의 CNT 합성 촉매(실시예 1 내지 8)는 보우마이트가 40 중량% 이상 형성되지 않은 수산화알루미늄(ATH)을 지지체로 포함하는 CNT 합성 촉매(비교예 1 및 2)에 비하여 평균입경이 크고, 미분이 현저히 적으며, 소니케이션에 따른 MN 및 D50 변화량이 매우 작고(경도가 높고 입도가 안정적임), 반응수율이 크게 높은 것을 확인할 수 있었다.As shown in Table 1, the CNT synthesis catalyst (Examples 1 to 8) of the present invention is a CNT synthesis catalyst (Comparative Example 1 and 1) containing aluminum hydroxide (ATH) in which at least 40 wt% of boehmite is not formed. Compared to 2), the average particle diameter was large, the derivative was significantly smaller, the variation of MN and D 50 according to the sonication was very small (hardness and stable particle size), and the reaction yield was very high.

또한, 하기 도 3, 4에 나타난 바와 같이, 본 발명의 CNT 합성 촉매용 지지체(실시예 1 내지 8)는 보우마이트가 40 중량% 이상 형성되지 않은 CNT 합성 촉매용 지지체 (비교예 1 및 2)에 비하여 소니케이션 처리 시간에 따른 D50 및 평균입경 변화량이 적고, 미분 발생이 억제됨을 확인할 수 있었다.In addition, as shown in Figures 3 and 4, the support for the CNT synthesis catalyst of the present invention (Examples 1 to 8) is a support for a CNT synthesis catalyst (Comparative Examples 1 and 2) in which no baumite is formed at least 40% by weight. Compared with the Sony treatment time, D 50 and the average particle size change were small, and it was confirmed that the generation of derivatives was suppressed.

또한, 하기 도 5, 6에 나타난 바와 같이, 본 발명의 CNT 합성 촉매 (실시예 1 내지 8)는 보우마이트가 40 중량% 이상 형성되지 않은 수산화알루미늄(ATH)을 지지체로 포함하는 CNT 합성 촉매(비교예 1 및 2)에 비하여 소니케이션 처리 시간에 따른 D50 및 평균입경 변화량이 현저히 적음을 확인할 수 있었다.In addition, as shown in Figures 5 and 6, the CNT synthesis catalysts (Examples 1 to 8) of the present invention is a CNT synthesis catalyst containing aluminum hydroxide (ATH) in which at least 40% by weight of boehmite is not formed. Compared with Comparative Examples 1 and 2) it was confirmed that the amount of D 50 and the average particle size change according to the sonication processing time is significantly less.

또한, 하기 도 7 내지 10에 나타난 바와 같이, 본 발명의 CNT 합성 촉매(실시예 1, 2, 4)는 소니케이션 처리(15 분) 전과 후의 입도가 일정 (변화가 적음)하나, 보우마이트가 40 중량% 이상 형성되지 않은 수산화알루미늄(ATH)을 지지체로 포함하는 CNT 합성 촉매(비교예 2)는 소니케이션 처리(15 분) 전과 후의 입도가 불균일(변화가 매우 큼)하고, 소니케이션 처리 이후 다량의 미분이 발생됨을 확인할 수 있었다.In addition, as shown in Figures 7 to 10 below, the CNT synthesis catalysts (Examples 1, 2, 4) of the present invention have a constant particle size (little change) before and after the sonication treatment (15 minutes), The CNT synthesis catalyst (Comparative Example 2) comprising aluminum hydroxide (ATH) not formed at least 40% by weight as a support has a nonuniformity (very large change) before and after the sonication treatment (15 minutes), and after the sonication treatment. It was confirmed that a large amount of fine powder was generated.

참고로, 비교예 1에서 제조된 CNT 합성 촉매의 경우 D50 변화량이 작으나, 이는 소니케이션 처리 전 D50 값이 작고 이미 미분화되어 있어 소니케이션의 영향을 적게 받기 때문인 것으로 여겨진다.For reference, in the case of the CNT synthesis catalyst prepared in Comparative Example 1, the amount of D 50 change is small, but this is because the D 50 value before the sonication treatment is small and is already micronized, so it is considered to be less affected by sonication.

Claims (10)

보우마이트(boehmite) 분말 또는 보우마이트가 40 중량% 이상 함유된 수산화알루미늄 분말로, CNT 합성 촉매의 지지체로 사용됨을 특징으로 하는
촉매 지지체.Boehmite powder or aluminum hydroxide powder containing 40% by weight or more of boehmite powder, characterized in that used as a support for the CNT synthesis catalyst
Catalyst support. 제 1항에 있어서,
상기 분말은, 평균입경이 25 내지 50 ㎛인 것을 특징으로 하는
촉매 지지체. The method of claim 1,
The powder is characterized in that the average particle diameter of 25 to 50 ㎛
Catalyst support. 제 1항에 있어서
상기 보우마이트는, 수산화알루미늄을 250 내지 600 ℃에서 소성처리하여 형성됨을 특징으로 하는
촉매용 지지체. The method of claim 1, wherein
The bowmite is formed by calcining aluminum hydroxide at 250 to 600 ° C.
Catalyst support. 제 1항에 있어서,
상기 보우마이트는, 수산화알루미늄을 300 내지 450 ℃에서 소성처리하여 제조됨을 특징으로 하는
촉매 지지체. The method of claim 1,
The bowmite is manufactured by calcining aluminum hydroxide at 300 to 450 ° C.
Catalyst support. 제 3항 또는 제 4항에 있어서,
상기 수산화알루미늄은, 수평균입경(MN)이 20 내지 65 ㎛인 것을 특징으로 하는
촉매 지지체. The method according to claim 3 or 4,
The aluminum hydroxide is characterized in that the number average particle diameter (MN) is 20 to 65 ㎛
Catalyst support. 제 4항 또는 제 5항에 있어서,
상기 수산화알루미늄은, 건조 처리된 수산화알루미늄인 것을 특징으로 하는
촉매 지지체. The method according to claim 4 or 5,
The aluminum hydroxide is dried aluminum hydroxide, characterized in that
Catalyst support. 제 1항 내지 제 4항 중에 어느 한 항의 촉매 지지체에 활성금속이 담지되어 이루어진 것을 특징으로 하는
CNT 합성 촉매. An active metal is supported on the catalyst support according to any one of claims 1 to 4, characterized in that
CNT synthesis catalyst. 제 7항에 있어서,
상기 CNT 합성 촉매는, 활성 금속 함량이 10 중량% 이상인 것을 특징으로 하는
CNT 합성 촉매.8. The method of claim 7,
The CNT synthesis catalyst, characterized in that the active metal content of 10% by weight or more
CNT synthesis catalyst. 제 7항에 있어서,
상기 CNT 합성 촉매는, 유동층 반응기에 적용되는 것임을 특징으로 하는
CNT 합성 촉매.8. The method of claim 7,
The CNT synthesis catalyst is characterized in that it is applied to a fluidized bed reactor
CNT synthesis catalyst. 활성금속 원료물질의 수용액에 보우마이트(boehmite) 분말 또는 보우마이트가 40 중량% 이상 함유된 수산화알루미늄 분말을 투입하여 페이스트 또는 슬러리를 형성시키는 단계를 포함하여 이루어지는 것을 특징으로 하는
CNT 합성 촉매의 제조방법.Boehmite powder or aluminum hydroxide powder containing at least 40% by weight of the boehmite powder in an aqueous solution of the active metal raw material to form a paste or slurry characterized in that it comprises a
Process for preparing CNT synthesis catalyst.
KR1020110098282A 2011-09-28 2011-09-28 Support Of Catalyst For CNT Synthesis And Catalyst Prepared Therefrom KR101498755B1 (en)

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KR100559262B1 (en) * 2004-04-16 2006-03-15 한국화학연구원 Process for preparation of ?-alumina from Al dross
EP1674154A1 (en) * 2004-12-23 2006-06-28 Nanocyl S.A. Preparation process of a supported catalyst for producing carbon nanotubes
KR100579207B1 (en) * 2005-03-23 2006-05-12 한국화학연구원 PREPARATION METHOD OF BOEHMITE AND Gamma;-ALUMINA WITH HIGH SURFACE AREA
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