KR20220161847A - Catalyst Composition for Preparing Carbon Nanotubes - Google Patents
Catalyst Composition for Preparing Carbon Nanotubes Download PDFInfo
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- KR20220161847A KR20220161847A KR1020210070099A KR20210070099A KR20220161847A KR 20220161847 A KR20220161847 A KR 20220161847A KR 1020210070099 A KR1020210070099 A KR 1020210070099A KR 20210070099 A KR20210070099 A KR 20210070099A KR 20220161847 A KR20220161847 A KR 20220161847A
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B01J35/0006—
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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
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- 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
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
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Abstract
Description
본 발명은 탄소나노튜브 제조를 위한 촉매 조성물 및 상기 촉매 조성물을 이용하여 탄소나노튜브를 제조하는 방법에 관한 것이다.The present invention relates to a catalyst composition for preparing carbon nanotubes and a method for preparing carbon nanotubes using the catalyst composition.
탄소나노소재는 소재의 모양에 따라 퓰러렌(Fullerene), 탄소나노튜브(Carbon Nanotube; CNT), 그래핀(Graphene), 흑연 나노 플레이트(Graphite Nano Plate) 등이 있으며, 이 중 탄소나노튜브는 1개의 탄소 원자가 3개의 다른 탄소 원자와 결합한 육각형 벌집 모양의 흑연 면이 나노 크기의 직경으로 둥글게 말린 거대 분자이다.Carbon nanomaterials include fullerene, carbon nanotube (CNT), graphene, and graphite nanoplate depending on the shape of the material. It is a macromolecule in which six carbon atoms bonded to three other carbon atoms are hexagonal honeycomb-shaped graphite planes rolled into nanoscale diameters.
탄소나노튜브는 속이 비어 있어 가볍고 전기 전도도는 구리만큼 좋으며, 열전도도는 다이아몬드만큼 우수하고 인장력은 철강에 못지 않다. 말려진 형태에 따라서 단층벽 탄소나노튜브(Single-Walled Carbon Nanotube; SWCNT), 다중벽 탄소나노튜브(Multi-Walled Carbon Nanotube; MWCNT), 다발형 탄소나노튜브(Rope Carbon Nanotube)로 구분되기도 한다.Since carbon nanotubes are hollow, they are light, have electrical conductivity as good as copper, have thermal conductivity as good as diamond, and have tensile strength comparable to that of steel. Depending on the rolled form, it is also classified into single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), and bundled carbon nanotubes (Rope Carbon Nanotubes).
최근에는 한 번에 많은 양의 탄소나노튜브를 합성할 수 있는 탄소나노튜브 합성 기술에 대한 연구가 활발히 진행 중인 상황이며, 다양한 방법 중 유동층 반응기를 이용한 열화학 기상 증착법의 경우, 쉽게 연속적으로 많은 양의 탄소나노튜브를 합성할 수 있다는 점에서 특히 선호되고 있다.Recently, research on carbon nanotube synthesis technology capable of synthesizing a large amount of carbon nanotubes at once is actively underway. Among various methods, in the case of thermochemical vapor deposition using a fluidized bed reactor, a large amount of It is particularly preferred in that it can synthesize carbon nanotubes.
다만, 이러한 탄소나노튜브 제조방법에서는 촉매 표면에서 탄소나노튜브가 성장함에 따라 성장된 일부 탄소나노튜브 다량으로 엉겨 붙어 크기가 큰 응집체가 형성된다. 따라서, 기준 크기를 넘는 응집체의 생성량을 최소로 할 수 있는 방법에 관한 연구가 필요한 상황이다.However, in this method of manufacturing carbon nanotubes, as the carbon nanotubes grow on the surface of the catalyst, a large amount of the grown carbon nanotubes are entangled and a large aggregate is formed. Therefore, there is a need for research on a method capable of minimizing the amount of aggregates exceeding the standard size.
본 발명은 상기의 문제점을 해결하기 위한 것으로, 일정 크기 이상의 응집체 생성을 억제할 수 있는 촉매 조성물 및 이를 이용한 탄소나노튜브의 제조방법을 제공하기 위한 것이다.The present invention is to solve the above problems, and to provide a catalyst composition capable of suppressing the formation of aggregates of a certain size or more and a method for producing carbon nanotubes using the same.
본 발명은 촉매 조성이 상이한 N종의 담지 촉매를 포함하며, 상기 N종의 담지 촉매의 중량 평균 촉매 조성(활성 성분/지지체)은 0.25 내지 0.35이고, 상기 N종의 담지 촉매 중 촉매 조성의 최대값과 최소값의 차이는 0.05 내지 0.25이고, 상기 N은 2 이상의 정수인 것을 특징으로 하는 촉매 조성물을 제공한다.The present invention includes N types of supported catalysts having different catalyst compositions, the weight average catalyst composition (active component/support) of the N types of supported catalysts is 0.25 to 0.35, and the maximum catalyst composition among the N types of supported catalysts The difference between the value and the minimum value is 0.05 to 0.25, and N is an integer of 2 or more.
또한, 본 발명은 유동층 반응기에 상기의 촉매 조성물과 베드용 탄소나노튜브를 충전하는 단계 및 상기 유동층 반응기에 탄소원 가스를 주입하고 가열하여 탄소나노튜브를 합성하는 단계를 포함하는 탄소나노튜브의 제조방법을 제공한다.In addition, the present invention is a method for producing carbon nanotubes comprising the steps of filling a fluidized bed reactor with the catalyst composition and carbon nanotubes for a bed, and injecting a carbon source gas into the fluidized bed reactor and synthesizing carbon nanotubes by heating provides
본 발명의 촉매 조성물을 이용하여 탄소나노튜브를 제조할 경우, 기준 크기 이상의 응집체 생성이 억제되어 동일한 양의 원료로부터 더 많은 탄소나노튜브를 제조할 수 있다.In the case of producing carbon nanotubes using the catalyst composition of the present invention, the generation of agglomerates of a standard size or larger is suppressed, so that more carbon nanotubes can be produced from the same amount of raw material.
이하, 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to explain their invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.
본 발명에서 사용하는 용어 '탄소나노튜브'는 탄소나노튜브의 단위체가 전체 또는 부분적으로 번들형을 이루도록 집합되어 형성된 2차 구조물로서, 상기 탄소나노튜브의 단위체는 흑연면(graphite sheet)이 나노 크기 직경의 실린더 형태를 가지며, sp2 결합 구조를 갖는다. 이때 상기 흑연면이 말리는 각도 및 구조에 따라서 도체 또는 반도체의 특성을 나타낼 수 있다. 탄소나노튜브의 단위체는 벽을 이루고 있는 결합수에 따라서 단일벽 탄소나노튜브(SWCNT, single-walled carbon nanotube), 이중벽 탄소나노튜브(DWCNT, double-walled carbon nanotube) 및 다중벽 탄소나노튜브(MWCNT, multi-walled carbon nanotube)로 분류될 수 있으며, 벽 두께가 얇을수록 저항이 낮다. The term 'carbon nanotube' used in the present invention is a secondary structure formed by assembling units of carbon nanotubes in whole or in part to form a bundle, and the units of carbon nanotubes are nano-sized graphite sheets. It has the shape of a cylinder in diameter and has an sp2 bonding structure. At this time, the characteristics of a conductor or a semiconductor may be exhibited according to the angle and structure of the graphite surface being rolled. The units of carbon nanotubes are single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), and multi-walled carbon nanotubes (MWCNTs), depending on the number of bonds constituting the wall. , multi-walled carbon nanotubes), and the thinner the wall thickness, the lower the resistance.
본 발명의 탄소나노튜브는 단일벽, 이중벽 및 다중벽의 탄소나노튜브 단위체 중 어느 하나 또는 둘 이상을 포함할 수 있다. The carbon nanotubes of the present invention may include any one or two or more of single-walled, double-walled, and multi-walled carbon nanotube units.
촉매 조성물catalyst composition
본 발명의 일 실시예에 따르면, 본 발명은 촉매 조성이 상이한 N종의 담지 촉매를 포함하며, 상기 N종의 담지 촉매의 중량 평균 촉매 조성(활성 성분/지지체)은 0.25 내지 0.35이고, 상기 N종의 담지 촉매 중 촉매 조성의 최대값과 최소값의 차이는 0.05 내지 0.25이고, 상기 N은 2 이상의 정수인 것을 특징으로 하는 촉매 조성물을 제공한다.According to one embodiment of the present invention, the present invention includes N types of supported catalysts having different catalyst compositions, the weight average catalyst composition (active component/support) of the N types of supported catalysts is 0.25 to 0.35, and the N The difference between the maximum value and the minimum value of the catalyst composition among supported catalysts of the species is 0.05 to 0.25, and N is an integer of 2 or more.
유동층 반응기를 이용한 탄소나노튜브의 제조 공정에 있어서, 종래에는 단일한 조성의 촉매를 사용하여 탄소나노튜브를 합성하는 것이 일반적이었다. 다만, 이와 같이 단일한 조성의 촉매를 이용할 경우, 반응 초반 동일한 활성도를 갖는 촉매로부터 탄소나노튜브가 성장하다 보니, 동일한 탄소나노튜브 간 응집력이 상호작용하여 최종 합성이 완료된 이후에는 상대적으로 크기가 큰 응집체 생성량이 적지 않다는 문제점이 있었다.In the manufacturing process of carbon nanotubes using a fluidized bed reactor, conventionally, it is common to synthesize carbon nanotubes using a catalyst having a single composition. However, in the case of using a catalyst of a single composition as described above, since carbon nanotubes grow from a catalyst having the same activity at the beginning of the reaction, the cohesive force between the same carbon nanotubes interacts and after the final synthesis is completed, a relatively large size There was a problem that the amount of aggregate production was not small.
이러한 점에 착안하여 연구한 결과, 본 발명의 발명자는 서로 다른 조성을 갖는 촉매를 혼합하여 사용하되, 그 중량 평균 촉매 조성과, 촉매 조성 중 최대값과 최소값의 차이를 특정 범위 내로 함으로써 거대 응집체 형성을 최소화하면서도 합성되는 탄소나노튜브의 물성을 우수하게 유지될 수 있는 촉매 조성물을 개발하였다.As a result of research focusing on this point, the inventors of the present invention mixed and used catalysts having different compositions, but the formation of large aggregates was prevented by keeping the difference between the weight average catalyst composition and the maximum and minimum values of the catalyst composition within a specific range. A catalyst composition capable of minimizing and maintaining excellent physical properties of synthesized carbon nanotubes was developed.
구체적으로, 본 발명의 촉매 조성물은 촉매 조성이 상이한 N종의 담지 촉매를 포함한다. 본 발명에 있어서, “촉매 조성”이라 함은, 담지 촉매에 있어서 지지체에 대한 활성 성분의 몰 비율을 뜻한다. 예컨대, Co 3몰을 Al 지지체 10몰에 담지시켜 제조한 촉매의 경우, 촉매 조성은 0.3이 된다. 따라서, 본 발명의 촉매 조성물이 촉매 조성이 상이한 N종의 담지 촉매를 포함한다는 것은, 지지체에 대한 활성 성분의 몰 비율을 달리하는 N종의 담지 촉매가 촉매 조성물에 동시에 포함됨을 의미한다.Specifically, the catalyst composition of the present invention includes N types of supported catalysts having different catalyst compositions. In the present invention, "catalyst composition" means the molar ratio of the active ingredient to the support in the supported catalyst. For example, in the case of a catalyst prepared by supporting 3 moles of Co on 10 moles of an Al support, the catalyst composition is 0.3. Therefore, the fact that the catalyst composition of the present invention includes N types of supported catalysts having different catalyst compositions means that N types of supported catalysts having different molar ratios of the active component to the support are simultaneously included in the catalyst composition.
한편, 상기 촉매 조성은 ICP OES 분석 장비를 사용하여 측정될 수 있으며, 합성 과정에서 혼합되는 전구체 및 지지체의 비율부터로도 계산될 수 있다. ICP OES 분석 장비를 이용하는 경우, 통상적으로 적용하는 분석 조건을 적용하여 측정될 수 있다. 또한, 활성 성분으로 복수 종의 금속이 사용되는 경우에는, 해당하는 복수 종의 금속 성분의 합산 몰 비율을 기준으로 상기 촉매 조성을 계산할 수 있다.On the other hand, the catalyst composition can be measured using ICP OES analysis equipment, and can also be calculated from the ratio of the precursor and the support mixed in the synthesis process. In the case of using ICP OES analysis equipment, it can be measured by applying commonly applied analysis conditions. In addition, when a plurality of metals are used as the active component, the catalyst composition may be calculated based on the combined molar ratio of the corresponding metal components of the plurality of metals.
본 발명의 촉매 조성물에 있어서, 상기 N은 2 이상의 정수이되, 바람직하게는 2 내지 4의 정수일 수 있다. N이 5 이상의 정수인 촉매 조성물은 제조가 어려우며, 거대 응집체 생성을 억제한다는 측면에서도 N이 2 내지 4인 경우 대비 개선된 효과를 보이지 않는다.In the catalyst composition of the present invention, N is an integer of 2 or more, preferably an integer of 2 to 4. A catalyst composition in which N is an integer of 5 or more is difficult to prepare, and does not show an improved effect compared to the case where N is 2 to 4 in terms of suppressing the formation of large aggregates.
본 발명의 촉매 조성물에 있어서, 상기 N종의 담지 촉매의 중량 평균 촉매 조성(활성 성분/지지체)은 0.25 내지 0.35일 수 있고, 바람직하게는 0.28 내지 0.32일 수 있다. 상기 중량 평균 촉매 조성이 상기 범위에 미치지 못할 경우, 상대적으로 활성 성분의 함량이 적어 투입한 촉매 대비 적은 양의 탄소나노튜브가 제조된다는 단점이 있고, 상기 중량 평균 촉매 조성이 상기 범위를 넘어 지나치게 큰 경우에는 지지체 대비 활성 성분이 과도하여 탄소나노튜브의 물리적인 특성, 예컨대 벌크 밀도와 같은 물성들이 종래의 탄소나노튜브 대비 크게 달라지는 문제점이 발생할 수 있다. 한편, 상기 중량 평균 촉매 조성은 각 촉매의 촉매 조성과 전체 촉매 조성물의 중량을 기준으로 한 해당 촉매의 함량 백분율을 곱한 후, N종의 촉매에 대해 모두 합산하여 계산할 수 있다. 예컨대, 촉매 조성이 0.2인 제1 촉매 20 중량%와 촉매 조성이 0.4인 제2 촉매 80중량%를 포함하는 촉매 조성물의 중량 평균 촉매 조성은 0.2*0.2+0.4*0.8=0.36이다.In the catalyst composition of the present invention, the weight average catalyst composition (active component/support) of the N types of supported catalysts may be 0.25 to 0.35, preferably 0.28 to 0.32. When the weight average catalyst composition does not fall within the above range, there is a disadvantage in that a small amount of carbon nanotubes is produced compared to the input catalyst because the content of the active component is relatively small, and the weight average catalyst composition exceeds the above range and is excessively large. In this case, physical properties of carbon nanotubes, such as bulk density, may be significantly different from those of conventional carbon nanotubes due to an excessive amount of the active ingredient compared to the support. Meanwhile, the weight average catalyst composition may be calculated by multiplying the catalyst composition of each catalyst by the content percentage of the corresponding catalyst based on the weight of the entire catalyst composition, and then summing all of the N types of catalysts. For example, the weight average catalyst composition of a catalyst composition including 20 wt% of a first catalyst having a catalyst composition of 0.2 and 80 wt% of a second catalyst having a catalyst composition of 0.4 is 0.2*0.2+0.4*0.8=0.36.
본 발명의 촉매 조성물에 있어서, 상기 N종의 담지 촉매 중 촉매 조성의 최대값과 최소값의 차이는 0.05 내지 0.25일 수 있고, 바람직하게는 0.10 내지 0.15일 수 있다. 촉매 조성의 최대값과 최소값의 차이가 지나치게 클 경우, 전체적인 촉매 조성물의 균일성이 떨어져 제조되는 탄소나노튜브의 균일성 역시 떨어질 수 있고, 촉매 조성의 최대값과 최소값의 차이가 너무 작은 경우에는 서로 다른 N종의 촉매를 함께 사용하는 실익이 없다.In the catalyst composition of the present invention, the difference between the maximum value and the minimum value of the catalyst composition among the N types of supported catalysts may be 0.05 to 0.25, preferably 0.10 to 0.15. If the difference between the maximum and minimum values of the catalyst composition is too large, the uniformity of the overall catalyst composition may be reduced, and the uniformity of the produced carbon nanotubes may also decrease. If the difference between the maximum and minimum values of the catalyst composition is too small, There is no practical benefit of using different N catalysts together.
본 발명의 촉매 조성물은 탄소나노튜브 제조를 위한 것일 수 있으며, 더욱 구체적으로는 다중벽 탄소나노튜브 제조를 위한 것일 수 있다. 본 발명의 촉매 조성물을 탄소나노튜브 제조에 사용할 경우, 앞서 설명한 바와 같이 거대 응집체의 형성이 억제되어 제조 공정의 경제성을 개선할 수 있다. The catalyst composition of the present invention may be for producing carbon nanotubes, and more specifically, may be for producing multi-walled carbon nanotubes. When the catalyst composition of the present invention is used for manufacturing carbon nanotubes, as described above, the formation of macroaggregates is suppressed, thereby improving the economics of the manufacturing process.
본 발명의 촉매 조성물에 있어서, 조성물에 포함되는 담지 촉매의 지지체는 알루미늄, 마그네슘, 칼슘 및 실리콘으로 이루어진 군에서 선택되는 1 이상을 포함하는 것일 수 있으며, 상기 활성 성분은 니켈, 코발트 및 철로부터 선택되는 1 이상을 포함하는 것일 수 있다. 상기 나열한 지지체와 활성 성분을 포함하는 담지 촉매를 사용할 경우, 탄소나노튜브 제조 속도가 빠르면서도 우수한 물성의 탄소나노튜브를 제조할 수 있고, 촉매 자체의 내구성 역시 우수하다는 장점이 있다. 본 발명의 촉매 조성물에 포함되는 N종의 촉매에서, 지지체와 활성 성분은 N종의 촉매 간 서로 같을 수도 있고, 다를 수도 있다. 다만, 균일한 품질의 탄소나노튜브 제조를 위해서는 상기 N종 촉매의 지지체 및 활성 성분은 서로 같은 것이 바람직하다. In the catalyst composition of the present invention, the support of the supported catalyst included in the composition may include one or more selected from the group consisting of aluminum, magnesium, calcium, and silicon, and the active component is selected from nickel, cobalt, and iron. It may include one or more that are. In the case of using the supported catalyst including the above-listed supports and active components, carbon nanotubes can be produced at a high speed and have excellent physical properties, and the durability of the catalyst itself is excellent. In the N types of catalysts included in the catalyst composition of the present invention, the support and the active component may be the same or different between the N types of catalysts. However, in order to manufacture carbon nanotubes of uniform quality, it is preferable that the support and active components of the N-type catalyst are the same.
특히 구체적으로, 본 발명의 촉매 조성물은 N은 2이고, 촉매 조성이 0.2인 제1 촉매와 촉매 조성이 0.4인 제2 촉매를 1:1의 중량비로 포함하는 것일 수 있다. Specifically, the catalyst composition of the present invention may include a first catalyst having a catalyst composition of 0.2 and a second catalyst having a catalyst composition of 0.4 in a weight ratio of 1:1, in which N is 2.
탄소나노튜브의 제조방법Manufacturing method of carbon nanotube
본 발명은 앞서 설명한 촉매 조성물을 이용하여 탄소나노튜브를 제조하는 방법을 제공하며, 구체적으로 유동층 반응기에 상기의 촉매 조성물과 베드용 탄소나노튜브를 충전하는 단계 및 상기 유동층 반응기에 탄소원 가스를 주입하고 가열하여 탄소나노튜브를 합성하는 단계를 포함하는 탄소나노튜브의 제조방법을 제공한다.The present invention provides a method for producing carbon nanotubes using the catalyst composition described above, specifically, the steps of filling the catalyst composition and carbon nanotubes for a bed in a fluidized bed reactor, and injecting a carbon source gas into the fluidized bed reactor Provided is a method for producing carbon nanotubes comprising synthesizing carbon nanotubes by heating.
본 발명의 제조방법에서 이용되는 촉매 조성물은 앞서 설명한 바와 같다.The catalyst composition used in the production method of the present invention is as described above.
한편, 본 발명의 제조방법에 있어서, 상기 탄소원 가스는 고온 상태에서 분해되어 탄소나노튜브를 형성할 수 있는 탄소 함유 가스이고, 구체적인 예로 지방족 알칸, 지방족 알켄, 지방족 알킨, 방향족 화합물 등 다양한 탄소 함유 화합물이 사용 가능하며, 보다 구체적으로는 메탄, 에탄, 에틸렌, 아세틸렌, 에탄올, 메탄올, 아세톤, 일산화탄소, 프로판, 부탄, 벤젠, 시클로헥산, 프로필렌, 부텐, 이소부텐, 톨루엔, 자일렌, 큐멘, 에틸벤젠, 나프탈렌, 페난트렌, 안트라센, 아세틸렌, 포름알데히드, 아세트알데히드 등의 화합물을 사용할 수 있다. Meanwhile, in the production method of the present invention, the carbon source gas is a carbon-containing gas capable of forming carbon nanotubes by decomposition at a high temperature, and specific examples include various carbon-containing compounds such as aliphatic alkanes, aliphatic alkenes, aliphatic alkynes, and aromatic compounds. Can be used, more specifically, methane, ethane, ethylene, acetylene, ethanol, methanol, acetone, carbon monoxide, propane, butane, benzene, cyclohexane, propylene, butene, isobutene, toluene, xylene, cumene, ethylbenzene , naphthalene, phenanthrene, anthracene, acetylene, formaldehyde, acetaldehyde and the like can be used.
본 발명의 제조방법에서는 탄소원 가스와 함께 유동 가스를 유동층 반응기로 주입할 수 있다. 상기 유동 가스는 유동층 반응기 내에서 합성되는 탄소나노튜브와 촉매 입자의 유동성을 부여하기 위한 것으로, 탄소원 가스나 탄소나노튜브와 반응하지 않으면서도, 높은 열적 안정성을 갖는 가스를 사용할 수 있다. 예컨대, 질소 가스나 불활성 가스를 상기 유동 가스로 사용할 수 있다.In the manufacturing method of the present invention, a fluidizing gas together with a carbon source gas may be injected into the fluidized bed reactor. The fluidizing gas is for imparting fluidity to the carbon nanotubes and catalyst particles synthesized in the fluidized bed reactor, and a gas having high thermal stability without reacting with the carbon source gas or the carbon nanotubes can be used. For example, nitrogen gas or an inert gas may be used as the fluidizing gas.
본 발명의 제조방법에 사용되는 유동층 반응기는 탄소나노튜브 제조에 사용될 수 있는 것으로 알려진 것이라면 특별한 제한 없이 사용할 수 있다.Any fluidized bed reactor used in the production method of the present invention may be used without particular limitation as long as it is known to be used for producing carbon nanotubes.
본 발명의 제조방법에 있어서, 합성 단계에서의 가열은 유동층 반응기 내부 온도를 600 내지 800℃가 되게끔 하는 것일 수 있다. 반응기 내 온도가 상술한 범위 내일 경우 탄소원 가스가 쉽게 분해되어 용이하게 탄소나노튜브를 합성할 수 있다. 온도가 상술한 범위에 미치지 못한 경우에는 탄소나노튜브가 잘 제조되지 않는 문제가 있을 수 있고, 온도가 상술한 범위를 넘어서는 경우에는 가열에 많은 비용에 소모될 뿐 아니라, 촉매 입자 자체가 분해되는 문제점이 발생할 수 있다.In the production method of the present invention, the heating in the synthesis step may be such that the temperature inside the fluidized bed reactor becomes 600 to 800 ° C. When the temperature in the reactor is within the above-described range, the carbon source gas is easily decomposed and carbon nanotubes can be easily synthesized. If the temperature does not fall within the above-mentioned range, there may be a problem that carbon nanotubes are not well produced, and if the temperature exceeds the above-mentioned range, not only a lot of cost is consumed for heating, but also the catalyst particles themselves are decomposed. this can happen
이하, 본 발명을 구체적으로 설명하기 위해 실시예 및 실험예를 들어 더욱 상세하게 설명하나, 본 발명이 이들 실시예 및 실험예에 의해 제한되는 것은 아니다. 본 발명에 따른 실시예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, examples and experimental examples will be described in more detail to specifically describe the present invention, but the present invention is not limited by these examples and experimental examples. Embodiments according to the present invention may be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
실시예 및 비교예 - 촉매 조성물의 제조Examples and Comparative Examples - Preparation of Catalyst Compositions
지지체로 알루미나를 사용하고, 활성 성분으로는 코발트를 사용하여 다양한 촉매 조성 값을 갖는 촉매를 제조하였다. 구체적으로, 코발트 전구체가 용해된 수용액을 제조한 후, 상기 수용액을 알루미나에 담지하고, 건조 및 소성하여 상기 촉매를 제조하였으며, 코발트의 사용량만을 달리하되, 나머지 조건은 모두 동일하게 하여 촉매를 제조하였다. 제조된 촉매를 다양한 중량비로 혼합하여 실시예 및 비교예의 촉매 조성물을 제조하였다. 각 경우에 혼합되는 촉매의 촉매 조성 값과 혼합 중량비를 정리하여 아래 표 1로 나타내었다.Catalysts having various catalyst composition values were prepared using alumina as a support and cobalt as an active component. Specifically, after preparing an aqueous solution in which the cobalt precursor was dissolved, the aqueous solution was supported on alumina, dried and calcined to prepare the catalyst, and only the amount of cobalt was changed, but the rest of the conditions were the same. . Catalyst compositions of Examples and Comparative Examples were prepared by mixing the prepared catalysts at various weight ratios. In each case, the catalyst composition values and mixing weight ratios of the catalysts mixed are summarized in Table 1 below.
상기 실시예 1-1 내지 1-3과 비교예 1-1 내지 1-2는 동일한 촉매 조성을 갖는 두 종의 촉매를 서로 다른 중량비로 혼합한 경우에 대한 것으로, 실시예 1-1 내지 1-3은 중량 평균 촉매 조성이 0.25 내지 0.35 범위에 포함되는 반면, 비교예 1-1 및 1-2는 중량 평균 촉매 조성이 0.25보다 작거나 0.35보다 크다. Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2 are for mixing two types of catalysts having the same catalyst composition at different weight ratios, and Examples 1-1 to 1-3 While the silver weight average catalyst composition is included in the range of 0.25 to 0.35, Comparative Examples 1-1 and 1-2 have a weight average catalyst composition of less than 0.25 or greater than 0.35.
또한, 상기 실시예 2-1 내지 2-3과 비교예 2-1 내지 2-2는 두 종의 촉매를 1:1의 중량비로 혼합하되, 혼합되는 촉매 두 종의 촉매 조성을 달리한 것으로, 실시예 2-1 내지 2-3은 촉매 조성 최대값과 최소값의 차가 0.05 내지 0.25 범위에 포함되는 한편, 비교예 2-1 및 2-2는 촉매 조성 최대값과 최소값의 차가 0.05보다 작거나(단일 촉매), 0.25보다 크다.In addition, in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-2, the two catalysts were mixed at a weight ratio of 1:1, but the catalyst composition of the two catalysts to be mixed was different. In Examples 2-1 to 2-3, the difference between the maximum value and the minimum value of the catalyst composition is included in the range of 0.05 to 0.25, while in Comparative Examples 2-1 and 2-2, the difference between the maximum value and the minimum value of the catalyst composition is less than 0.05 (single catalyst), greater than 0.25.
실험예 - 탄소나노튜브의 물성 및 응집체 생성량 확인Experimental Example - Confirmation of physical properties of carbon nanotubes and the amount of aggregates produced
앞선 실시예 및 비교예로부터 제조된 촉매 조성물을 사용하여 탄소나노튜브를 합성한 후, 그, 물성을 확인하였다. 직경 0.1m의 유동층 반응기를 사용하였으며, 유동 가스로는 질소 가스를 12slpm의 유속으로 투입하였으며, 탄소원 가스로는 에틸렌을 3slpm의 유속으로 투입하였다. 각 실시예 및 비교예에서의 온도, 반응 시간 및 촉매 사용량은 동일하게 적용하였으며, 총 15회(batch) 반복한 후, 각 경우에 대한 탄소나노튜브의 평균 벌크 밀도 및 순도를 확인하였다. 상기 벌크 밀도 및 순도는 하기 방법을 통해 측정 및 계산하였다.After synthesizing carbon nanotubes using the catalyst compositions prepared in the previous Examples and Comparative Examples, their physical properties were confirmed. A fluidized bed reactor having a diameter of 0.1 m was used, nitrogen gas was introduced at a flow rate of 12 slpm as a fluid gas, and ethylene was introduced at a flow rate of 3 slpm as a carbon source gas. Temperature, reaction time, and catalyst usage in each Example and Comparative Example were applied the same, and after a total of 15 batches were repeated, the average bulk density and purity of the carbon nanotubes for each case were confirmed. The bulk density and purity were measured and calculated through the following methods.
1) 벌크 밀도1) Bulk density
제조된 탄소나노튜브를 내부 부피 50mL 컵에 자유낙하 시켜 채운 후, 무게를 측정하고, 상기 무게를 내부 부피 50mL로 나누어 계산하였다.After filling the prepared carbon nanotubes in a cup with an internal volume of 50mL by free fall, the weight was measured, and the weight was calculated by dividing the weight by the internal volume of 50mL.
2) 순도2) Purity
Ash Test 방식을 사용하여 ((샘플 무게 - ash 무게) / 샘플 무게)) * 100%로 계산하였다. It was calculated as ((sample weight - ash weight) / sample weight)) * 100% using the Ash Test method.
또한, 각 경우에 대해 15회 반응을 진행한 후, 탄소나노튜브를 전량 회수한 뒤 반응기 내부에 잔류하는 응집체를 회수하여 그 무게를 측정하였다. 반응기 하부뿐 아니라, 내부 벽면에 부착된 응집체도 함께 회수하였으며, 회수된 응집체 중 2mm 메쉬망을 통과하는 크기가 작은 응집체는 제외하고, 메쉬망에 남는 크기가 큰 응집체에 대해서만 그 무게를 측정하였다. 그 결과를 하기 표 2로 나타내었다.In addition, after 15 reactions were performed for each case, the total amount of carbon nanotubes was recovered, and then aggregates remaining in the reactor were recovered and their weight was measured. In addition to the bottom of the reactor, aggregates attached to the inner wall were also collected, and among the collected aggregates, small aggregates passing through the 2 mm mesh were excluded, and only large aggregates remaining on the mesh were weighed. The results are shown in Table 2 below.
중량 평균 촉매 조성을 달리하는 실시예 1-1 내지 1-3과 비교예 1-1 내지 1-2의 경우, 본 발명이 요구하는 중량 평균 촉매 조성을 만족하는 실시예의 촉매 조성물로부터 제조된 탄소나노튜브 대비 비교예의 촉매 조성물로부터 제조된 탄소나노튜브의 벌크 밀도가 너무 낮거나 너무 높게 확인되었다. 탄소나노튜브의 벌크 밀도가 너무 낮거나 너무 높다는 것은 타겟하는 탄소나노튜브의 물성이 구현되지 않았음을 의미하는 것으로, 비교예의 촉매 조성물을 사용하였을 때에는 목적하는 품질의 탄소나노튜브가 수득되지 않았음을 의미한다. 또한, 회수된 응집체의 양에서도 실시예 대비 2배 많은 것으로 확인되어, 비교예 1-1 및 1-2의 촉매 조성물을 사용한 경우 실시예 대비 탄소나노튜브 제조 공정의 수율이 떨어짐을 확인하였다. In the case of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2 having different weight average catalyst compositions, compared to carbon nanotubes prepared from the catalyst compositions of Examples satisfying the weight average catalyst composition required by the present invention It was confirmed that the bulk density of the carbon nanotubes prepared from the catalyst composition of Comparative Example was too low or too high. If the bulk density of the carbon nanotubes is too low or too high, it means that the physical properties of the target carbon nanotubes are not implemented, and when the catalyst composition of the comparative example is used, the carbon nanotubes of the desired quality are not obtained. means In addition, it was confirmed that the amount of recovered agglomerates was twice as high as in Example, and when the catalyst compositions of Comparative Examples 1-1 and 1-2 were used, it was confirmed that the yield of the carbon nanotube manufacturing process was lower than that of Example.
한편, 촉매 조성의 최대값과 최소값 사이의 차이를 달리하는 실시예 2-1 내지 2-3과 비교예 2-1 내지 2-2의 경우, 본 발명이 요구하는 촉매 조성의 최대값과 최소값 차이 범위를 만족하지 못한 비교예 2-1 및 2-2에서도, 제조된 탄소나노튜브의 물성이 실시예의 촉매 조성물을 사용하여 제조된 탄소나노튜브의 물성과 유사함이 확인되었다. 다만, 응집체 생성량의 경우, 비교예 2-1 및 2-2의 촉매 조성물을 사용한 경우, 실시예 대비 몹시 많은 양의 응집체가 생성되었으며, 비교예 1-1 및 1-2과 비교하더라도 더 많은 양의 응집체가 생성되었다. 이는 즉 비교예 2-1 및 비교예 2-2의 촉매 조성물을 사용하는 경우에는 많은 양의 탄소나노튜브가 응집체를 생성하여, 제조 공정의 경제성이 크게 떨어짐을 의미한다.On the other hand, in the case of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-2, in which the difference between the maximum and minimum values of the catalyst composition is different, the difference between the maximum and minimum values of the catalyst composition required by the present invention Even in Comparative Examples 2-1 and 2-2, which did not satisfy the range, it was confirmed that the physical properties of the produced carbon nanotubes were similar to those of the carbon nanotubes prepared using the catalyst composition of Example. However, in the case of the amount of aggregates produced, when the catalyst compositions of Comparative Examples 2-1 and 2-2 were used, a very large amount of aggregates were produced compared to the examples, and even compared to Comparative Examples 1-1 and 1-2, a larger amount aggregates were formed. That is, in the case of using the catalyst compositions of Comparative Examples 2-1 and 2-2, a large amount of carbon nanotubes generate aggregates, which means that the economical efficiency of the manufacturing process is greatly reduced.
상기 결과로부터 본 발명의 촉매 조성물을 사용할 경우, 우수한 물성의 탄소나노튜브를 제조할 수 있으면서도, 제조 공정 중 발생하는 응집체의 형태로 손실되는 탄소나노튜브의 양을 최소화하여, 효율적으로 탄소나노튜브를 제조할 수 있음을 확인하였다.From the above results, when using the catalyst composition of the present invention, it is possible to produce carbon nanotubes with excellent physical properties, while minimizing the amount of carbon nanotubes lost in the form of aggregates generated during the manufacturing process, thereby efficiently producing carbon nanotubes. It was confirmed that it could be produced.
Claims (7)
상기 N종의 담지 촉매의 중량 평균 촉매 조성(활성 성분/지지체)은 0.25 내지 0.35이고,
상기 N종의 담지 촉매 중 촉매 조성의 최대값과 최소값의 차이는 0.05 내지 0.25이고,
상기 N은 2 이상의 정수인 것을 특징으로 하는 촉매 조성물.
It includes N types of supported catalysts having different catalyst compositions,
The weight average catalyst composition (active component / support) of the N types of supported catalysts is 0.25 to 0.35,
The difference between the maximum value and the minimum value of the catalyst composition among the N types of supported catalysts is 0.05 to 0.25,
Catalyst composition, characterized in that the N is an integer of 2 or more.
상기 N은 2 내지 4의 정수인 촉매 조성물.
According to claim 1,
The catalyst composition wherein N is an integer of 2 to 4.
상기 촉매 조성물은 탄소나노튜브 제조를 위한 것인 촉매 조성물.
According to claim 1,
The catalyst composition is a catalyst composition for producing carbon nanotubes.
상기 담지 촉매의 지지체는 알루미늄, 마그네슘, 칼슘 및 실리콘으로 이루어진 군에서 선택되는 1 이상을 포함하는 것인 촉매 조성물.
According to claim 1,
The catalyst composition of claim 1, wherein the support of the supported catalyst includes at least one selected from the group consisting of aluminum, magnesium, calcium, and silicon.
상기 활성 성분은 니켈, 코발트 및 철로부터 선택되는 1 이상을 포함하는 것인 촉매 조성물.
According to claim 1,
The catalyst composition according to claim 1, wherein the active component comprises at least one selected from nickel, cobalt and iron.
상기 N은 2이고,
촉매 조성이 0.2인 제1 촉매와 촉매 조성이 0.4인 제2 촉매를 1:1의 중량비로 포함하는 것인 촉매 조성물.
According to claim 1,
wherein N is 2,
A catalyst composition comprising a first catalyst having a catalyst composition of 0.2 and a second catalyst having a catalyst composition of 0.4 in a weight ratio of 1:1.
상기 유동층 반응기에 탄소원 가스를 주입하고 가열하여 탄소나노튜브를 합성하는 단계;를 포함하는 탄소나노튜브의 제조방법.Filling a fluidized bed reactor with the catalyst composition according to any one of claims 1 to 6 and carbon nanotubes for a bed; and
A method for producing carbon nanotubes comprising: injecting a carbon source gas into the fluidized bed reactor and synthesizing carbon nanotubes by heating.
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