KR20100133766A - Fe-based catalyst for the reaction of fischer-tropsch synthesis and preparation method thereof - Google Patents
Fe-based catalyst for the reaction of fischer-tropsch synthesis and preparation method thereof Download PDFInfo
- Publication number
- KR20100133766A KR20100133766A KR1020090052473A KR20090052473A KR20100133766A KR 20100133766 A KR20100133766 A KR 20100133766A KR 1020090052473 A KR1020090052473 A KR 1020090052473A KR 20090052473 A KR20090052473 A KR 20090052473A KR 20100133766 A KR20100133766 A KR 20100133766A
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- South Korea
- Prior art keywords
- catalyst
- cerium
- iron
- fischer
- metal
- Prior art date
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 82
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 32
- 238000001308 synthesis method Methods 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 207
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 84
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- 238000000034 method Methods 0.000 claims description 60
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- 239000000243 solution Substances 0.000 claims description 24
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- 239000007788 liquid Substances 0.000 claims description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 20
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- 239000011591 potassium Substances 0.000 claims description 19
- 229910052684 Cerium Inorganic materials 0.000 claims description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 17
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- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
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- 238000001354 calcination Methods 0.000 claims description 4
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- NEOOEFDJRSCWOU-UHFFFAOYSA-N iron(2+);dinitrate;hydrate Chemical compound O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NEOOEFDJRSCWOU-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
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- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
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- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical group [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
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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
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- 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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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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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
- B01J23/83—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 rare earths or actinides
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Abstract
Description
본 발명은 피셔-트롭쉬 합성(FTS; Fischer-Tropsch synthesis) 반응용 철계열의 촉매와 이의 제조방법에 관한 것이다.The present invention relates to an iron-based catalyst for Fischer-Tropsch synthesis (FTS) reaction and a method for producing the same.
합성가스를 이용한 액체탄화수소의 전환기술은 천연가스의 개질 및 석탄 및 바이오매스 등의 가스화를 통하여 합성가스를 제조하는 반응으로부터 시작된다. 일반적으로, 피셔-트롭쉬 합성(FTS; Fischer-Tropsch synthesis) 반응은 합성가스로부터 탄화수소 화합물들을 생성하는 반응으로서, 철계열 및 코발트 계열의 촉매상에서 다음의 주요 대표적인 반응에 의하여 진행되게 된다.The technology of converting liquid hydrocarbons using syngas starts with the reaction of producing syngas through reforming of natural gas and gasification such as coal and biomass. In general, Fischer-Tropsch synthesis (FTS) reaction is a reaction for generating hydrocarbon compounds from syngas and is performed by the following main representative reactions on iron-based and cobalt-based catalysts.
상기 반응식 (1)과 (3)의 FTS 반응과 경쟁반응인 상기 반응식 (2)의 수성가스 전환 (WGS; water-gas shift) 반응은 일산화탄소와 상기 반응식 (1)로부터 생성되는 물이 반응하여 이산화탄소와 수소를 발생하게 된다. 따라서, 상기 반응식 (1)에서 생성된 물은 전체 피셔-트롭쉬 합성 반응에서 수소와 일산화탄소의 비를 변화시키게 되며 이는 특히 WGS 반응 활성이 우수한 철계열의 촉매 상에서 잘 발생하는 것으로 알려져 있다. 피셔-트롭쉬 공정에 사용되고 있는 촉매는 반응조건이나 원하는 생성물에 따라서 상이한 성분의 촉매가 사용되고 있다. 그 대표적 예로서, 촉매의 주된 활성 성분으로서 표준주기율표상의 7A족 (코발트, 루테늄, 철 또는 니켈) 중에서 선택된 1종 이상의 성분과, 부가적으로 첨가되는 증진제 또는 구조안정제 등으로 사용되는 성분으로서 표준주기율표상의 3A족, 4A족, 5A족, 6A족 등의 원소들과 1B족 원소들 중 적어도 하나 이상의 성분을 사용하여 피셔-트롭쉬 촉매가 제조되어 사용되는 것으로 보고되어 있다 [미합중국 등록특허 제7067562호 B2].The water-gas shift (WGS) reaction of the reaction formula (2), which is in competition with the FTS reactions of the reaction schemes (1) and (3), results in carbon dioxide being reacted with carbon monoxide and water generated from the reaction scheme (1). And hydrogen is generated. Therefore, the water produced in Scheme (1) changes the ratio of hydrogen and carbon monoxide in the entire Fischer-Tropsch synthesis reaction, which is known to occur particularly well on the iron-based catalyst having excellent WGS reaction activity. As the catalyst used in the Fischer-Tropsch process, catalysts of different components are used depending on reaction conditions and desired products. As a representative example thereof, as a main active component of the catalyst, one or more components selected from Group 7A (cobalt, ruthenium, iron, or nickel) on the standard periodic table, and components used as additionally added enhancers or structural stabilizers, etc. Fischer-Tropsch catalysts have been reported to be manufactured and used using at least one or more of elements of Group 3A, Group 4A, Group 5A, Group 6A, etc., and Group 1B elements in the phases. [US Patent No. 7067562] B2].
피셔-트롭쉬 합성 반응에 사용되는 촉매는 주요 활성 성분에 따라서 생성물의 분포가 변화하게 되지만, 일반적으로 피셔-트롭쉬 합성 반응은 H2/CO 비가 2.0의 경우에 반응 활성이 우수한 것으로 ASF (Anderson-Shulz-Flory) 메커니즘에 의하여 설명이 되고 있다. 그러나, 잘 알려진 바와 같이 철계열의 촉매를 사용하는 피셔-트롭쉬 합성 반응은 높은 수성가스 전환반응에 대한 활성으로 인하여 반응식 (3)이 우세하여 반응 중에 수소가 추가로 생성되어 넓은 H2/CO 몰비 (0.7 ∼ 2.0)의 영역에서도 활성이 우수한 반면에, 코발트계를 이용하는 피셔-트롭쉬 합성 반응은 반응식 (1)의 반응이 우세하고 수성가스 전환반응에 대한 활성이 적어서 적정한 H2/CO 몰비 (∼ 2.0)에서 우수한 활성을 보이는 특징이 있다. 이와 함께, 피셔-트롭쉬 합성 반응에서 철계열의 촉매는 코발트계열의 촉매보다 저가로 제조가 가능하며, WGS 반응에 의한 고유의 높은 촉매 활성을 지니고 있으며, 높은 수성가스 전환반응 활성으로 인하여 석탄 및 바이오매스로부터 생성되는 낮은 H2/CO 몰비의 합성가스 (H2/CO < 1.0)를 사용하는 경우에도 피셔-트롭쉬 반응이 원활하게 진행되는 장점이 있어서 추가로 H2/CO비를 조절하기 위한 공정의 도입이 필요 없는 장점이 있다. 따라서, 수성가스 전환 반응에 대한 우수한 활성을 지니고 있는 철계열의 촉매를 사용하여 피셔-트롭쉬 반응을 수행하는 경우에는 낮은 H2/CO 몰비를 지니는 합성가스의 처리를 위한 공정 개발에 대하여 우수한 장점을 지니고 있다.In the Fischer-Tropsch synthesis reaction, the distribution of the product varies depending on the main active ingredient. However, in general, the Fischer-Tropsch synthesis reaction exhibits excellent reaction activity when the H 2 / CO ratio is 2.0. This is explained by the Schulz-Flory mechanism. However, as is well known, the Fischer-Tropsch synthesis reaction using iron-based catalysts is predominantly due to its activity against high water gas shift reactions, resulting in the addition of hydrogen to the broad H 2 / CO The Fischer-Tropsch synthesis reaction using the cobalt system has a superior H 2 / CO molar ratio because the reaction of Scheme (1) is superior and the activity of the water gas conversion reaction is small while the activity of the molar ratio (0.7 to 2.0) is excellent. It is characterized by excellent activity at (˜2.0). In addition, the iron-based catalyst in the Fischer-Tropsch synthesis reaction can be manufactured at a lower cost than the cobalt-based catalyst, has a unique high catalytic activity by the WGS reaction, and due to the high water gas shift reaction activity, coal and Fisher, even when using synthesis gas (H 2 / CO <1.0) of the lower H 2 / CO molar ratio that is generated from biomass-to add in the advantage of being conducted to Tropsch reaction smoothly to adjust the H 2 / CO ratio There is an advantage that does not require the introduction of a process for. Thus, when the Fischer-Tropsch reaction is performed using an iron-based catalyst having excellent activity for water gas conversion, it is an excellent advantage for the process development for the treatment of syngas having a low H 2 / CO molar ratio. It has
반면에, 코발트계 계열의 촉매는 천연가스로부터 생성되는 H2/CO 몰비가 ∼2.0 정도인 경우에만 우수한 촉매 활성을 보이는 단점은 있지만, 피셔-트롭쉬 합성 반응에서 코발트계열의 촉매를 사용하는 경우에는 철계열의 촉매와 비교하여 저온에서 반응이 진행되므로 액체나 왁스와 같은 파라핀계열의 탄화수소의 생성에 보다 유리한 장점이 있으며 추가적인 수소처리공정에 의하여 필요한 탄화수소 (납사, 디젤 및 왁스 등)를 선택적으로 제조하는 공정이 필요하게 된다. 반면에 고온에서 사용되는 철계열의 촉매는 주로 C2-C4 올레핀의 직접적인 생성 반응이 유리하여 이를 활용하여 다양한 화학제품이나 석유화학제품을 생산하기 위한 원료로 사용될 수 있는 장점을 지니고 있다.On the other hand, the cobalt-based catalyst has a disadvantage in that it exhibits excellent catalytic activity only when the H 2 / CO molar ratio generated from natural gas is about -2.0, but the cobalt-based catalyst is used in the Fischer-Tropsch synthesis reaction. Compared to iron-based catalysts, the reaction proceeds at low temperatures, which is advantageous in producing paraffinic hydrocarbons such as liquids and waxes, and selectively requires hydrocarbons (naphtha, diesel, and waxes) by additional hydrotreating. The manufacturing process is required. On the other hand, iron-based catalysts used at high temperatures have the advantage of being able to be used as a raw material for producing various chemical products or petrochemical products by utilizing the direct formation reaction of mainly C 2 -C 4 olefins.
일반적으로 알려진 바에 의하면, 피셔-트롭쉬 합성 반응을 위한 철계열의 촉매는 용융법이나 침전법에 의하여 제조되어 사용되고 있다. 침전법을 사용하는 경우에는 수용액 속에 침전된 철촉매는 철수산화물과 철산화물로 구성되어 있으며, 세척, 건조 및 소성 과정을 거쳐서 철계열의 촉매를 제조하여 사용되고 있다. 이와 같이 침전법에 의하여 제조된 철계열의 촉매는 슬러리 반응기에서 고비점의 액체 생성물을 생산할 수는 있지만, 촉매의 마모에 의한 촉매의 활성이 감소하는 단점이 있다. 그러나, 철광석을 용융하여 제조된 철계열의 촉매는 조촉매와 함께 사용되는 경우가 일반적이며 촉매의 마모저항은 우수하지만 침전법에 의하여 제조된 촉매와 비교하여 낮은 촉매 활성을 나타내므로 슬러리 반응기에서는 활성이 이의 절반밖에 되지 않는 것으로 보고되어 있다 [Fuel Processing Technology 30 (1992) 83]. 이외에도, 피셔-트롭쉬 합성 반응을 위한 철계열의 촉매는 분무-건조법 (spray-drying method)에 의해서도 제조될 수 있으며, 이 경우에는 촉매의 마모 저항이 향상되며, 촉매의 활성에는 크게 영향을 주지 않으면서도 촉매의 물리적 강도를 향상시킨다는 보고가 있다 [Industrial & Engineering Chemistry Research 40 (2001) 1065].In general, iron-based catalysts for Fischer-Tropsch synthesis reactions are manufactured and used by melting or precipitation. In the case of using the precipitation method, the iron catalyst precipitated in the aqueous solution is composed of iron hydroxide and iron oxide, and is used to prepare an iron-based catalyst after washing, drying and firing. The iron-based catalyst prepared by the precipitation method can produce a liquid product having a high boiling point in the slurry reactor, but has a disadvantage in that the activity of the catalyst due to abrasion of the catalyst decreases. However, iron-based catalysts prepared by melting iron ore are generally used with cocatalysts, and have good catalytic resistance but low catalytic activity compared to catalysts prepared by precipitation. Only half this is reported [Fuel Processing Technology 30 (1992) 83]. In addition, iron-based catalysts for Fischer-Tropsch synthesis reactions can also be prepared by the spray-drying method, in which case the wear resistance of the catalyst is improved and the catalyst activity is not significantly affected. It has been reported to improve the physical strength of the catalyst without the need [Industrial & Engineering Chemistry Research 40 (2001) 1065).
일반적으로 철계열의 촉매는 CO의 흡착 능력이나 철의 환원성에 도움을 주는 하나 이상의 조촉매를 포함하여 제조되게 된다. 특히, 철계열의 촉매에 칼륨(potassium)을 추가함으로써 분자량이 큰 고비점 탄화수소에 대한 수율을 증가시 키는 것으로 알려져 있다. 철계열 촉매의 거동에 관한 칼륨의 영향은 다음과 같이 정리할 수 있다.In general, iron-based catalysts are prepared by including one or more cocatalysts to assist in the adsorption capacity of CO or reducing iron. In particular, the addition of potassium (potassium) to the iron-based catalyst is known to increase the yield for high molecular weight high boiling hydrocarbons. The effects of potassium on the behavior of iron-based catalysts can be summarized as follows.
1) 탄화수소 생성물의 평균 분자량을 증가시킴으로써 α 값을 높게 해 주며, 탄화수소 생성물에서 올레핀/파라핀에 대한 비를 증가시켜서 올레핀의 선택성을 증가시킨다.1) The α value is increased by increasing the average molecular weight of the hydrocarbon product and the selectivity of the olefin is increased by increasing the ratio to olefin / paraffin in the hydrocarbon product.
2) 촉매의 비활성화 억제에 도움이 되며, 최적의 칼륨 농도는 피셔-트롭쉬 합성반응의 활성을 증가시키며 메탄의 선택도를 감소시키는 장점이 있다.2) It helps to suppress the deactivation of the catalyst, the optimal potassium concentration increases the activity of the Fischer-Tropsch synthesis reaction and has the advantage of reducing the selectivity of methane.
이외에도, 조촉매로 사용되는 구리의 경우에는 철의 환원성을 증진시키는 효과가 있는 것으로 알려져 있다. 그러나, 구리는 철의 환원성을 촉진시켜 피셔-트롭쉬 반응속도에 있어서는 칼륨보다는 더 효과적이지만, 수성가스 전환반응에 대한 활성을 감소시키기 때문에 낮은 H2/CO 몰비를 지니는 합성가스를 사용하는 경우(석탄 및 바이오매스 등을 활용하는 경우)에는 반응 중에 피셔-트롭쉬 합성에 적절한 H2/CO 비를 유지할 수 없는 단점이 있다. 이를 보완하기 위해 지지체를 사용하지 않은 철-망간에 구리와 1A나 2A족의 금속원소를 조촉매로 사용하여 높은 일산화탄소의 전환율에서 C5+의 탄화수소를 선택적으로 합성하기도 하는 방법이 보고되어 있다 [미합중국 등록 특허 제5118715호]. In addition, in the case of copper used as a promoter, it is known to have an effect of improving the reducibility of iron. However, copper is more effective than potassium in the Fischer-Tropsch reaction rate because it promotes the reducibility of iron, but decreases the activity for the water gas shift reaction, and therefore uses a synthesis gas with a low H 2 / CO molar ratio ( In the case of using coal and biomass), there is a disadvantage in that it is not possible to maintain a suitable H 2 / CO ratio for the Fischer-Tropsch synthesis during the reaction. To compensate for this, a method of selectively synthesizing C 5+ hydrocarbons at a high conversion rate of carbon monoxide using copper and metal elements of Groups 1A or 2A as a promoter for iron-manganese without support has been reported [ United States Registered Patent # 5118715].
촉매의 제조시 활성성분 입자의 분산성 증가와 활성성분인 철의 활성 증가를 위해서는 비표면적을 크게 유지하는 것이 중요하기 때문에, 철계열의 촉매에서는 구조 안정제로서 조촉매와 함께 바인더를 첨가하여 사용하기도 한다. 바인더로 주로 사용되는 실리카의 경우에는 철 성분의 침전 후에 촉매에 첨가하여 고정층 반응기에서 주로 사용되고 있으며, 촉매의 마모도가 커서 아직까지는 슬러리 반응기에서 활용되고 있지는 않은 것으로 보고되어 있다. 피셔-트롭쉬 합성을 위한 철계열의 촉매에 실리카가 포함되면, 일반적으로 지지체 양의 증가에 따라 활성 성분의 농도는 감소하지만, 금속의 분산도가 높게 유지되어 활성 금속성분인 철의 농도를 증가시키는 효과가 있는 것으로 알려져 있다. 또한, 슬러리 반응기에서의 피셔-트롭쉬 합성반응을 위하여 철계열의 촉매성분에 코발트를 동시에 공침시켜서 경질올레핀에 대한 선택도를 향상시키는 선행 연구결과들이 보고된 바도 있다 [미합중국 등록 특허 제4624967호 Applied Catalysis A: General 296 (2005) 222]. 이러한 철계열의 촉매는 촉매의 반응성 향상과 장기성능 확보를 위하여 최종적으로 증진제인 칼륨 및 구리와 망간 등을 첨가하는 것이 바람직하다고 보고되어 있다.It is important to maintain a large specific surface area in order to increase the dispersibility of active ingredient particles and increase the activity of iron as an active ingredient during the preparation of the catalyst. do. In the case of silica, which is mainly used as a binder, it is mainly used in a fixed bed reactor by adding iron to the catalyst after precipitation of the iron component. When silica is included in the iron-based catalyst for Fischer-Tropsch synthesis, the concentration of the active ingredient generally decreases with the increase in the amount of the support, but the dispersity of the metal is maintained to increase the concentration of the active metal ingredient iron. It is known to have an effect. In addition, previous studies have been reported to improve the selectivity for light olefins by co-precipitating cobalt in iron-based catalyst components for Fischer-Tropsch synthesis reactions in slurry reactors. Catalysis A: General 296 (2005) 222]. In order to improve the reactivity of the catalyst and to ensure long-term performance of the iron-based catalyst, it is reported that it is desirable to add potassium, copper, manganese, and the like, which are finally enhancers.
한편, 본 연구팀의 선행연구 결과에 의하면, 합성가스로부터 고비점의 탄화수소 및 경질 올레핀으로의 선택성을 증가시키기 위하여 피셔-트롭쉬 합성 반응에 사용되는 촉매계로서 제올라이트가 함유된 철계열의 촉매를 사용하되, 제올라이트의 비표면적이 200 ∼ 500 ㎡/g이며 Si/Al의 몰비가 50 이하인 제올라이트를 수소 형태로 전환하여 사용하거나 또는 IA, ⅡA, Zr, P 및 란탄계의 단일 금속전구체 또는 이원 금속전구체를 이용하여 이온교환 또는 담지의 방법으로 전 처리하여 사용하는 기술을 공개시킨 바도 있다 [한국특허공개 2009-0038267].On the other hand, according to the previous research results of the team, a zeolite-containing iron-based catalyst was used as a catalyst system used in the Fischer-Tropsch synthesis reaction to increase the selectivity from syngas to high boiling hydrocarbons and light olefins. Zeolites having a specific surface area of 200 to 500 m 2 / g and a molar ratio of Si / Al of 50 or less are converted to hydrogen form, or a single metal precursor or binary metal precursor of IA, IIA, Zr, P and lanthanum is used. It has been disclosed a technique that is used by pre-treatment by ion exchange or supported by using the method [Korean Patent Publication No. 2009-0038267].
본 발명은 종래의 피셔-트롭쉬 합성 반응용 촉매로서 일반적으로 보고되고 있는 철계열의 촉매와 비교하여 높은 촉매 활성 및 안정성을 확보함과 동시에 고비점의 탄화수소 및 경질탄화수소로의 선택성을 향상시킨 새로운 철계열의 촉매를 제공하는 것을, 해결하고자 하는 과제로 한다.The present invention ensures high catalytic activity and stability and improves the selectivity to high boiling point hydrocarbons and light hydrocarbons, as compared to iron-based catalysts, which are generally reported as catalysts for Fischer-Tropsch synthesis reactions. Providing an iron-based catalyst is a problem to be solved.
본 발명은 철촉매와 증진용 금속을 담지하는 지지체로서 세륨-지르코늄산화물(CexZr1-xO2) 지지체를 졸-겔(Sol-Gel) 방법에 의하여 제조하는 방법을 제공하는 것을, 해결하고자 하는 과제로 한다.The present invention provides a method for preparing a cerium-zirconium oxide (Ce x Zr 1-x O 2 ) support by a sol-gel method as a support supporting an iron catalyst and an enhancement metal. Let's do the task.
본 발명은 철촉매의 분산성 및 활성을 증대시키고 피셔-트롭쉬 합성반응조건에서 촉매의 비활성화가 억제되어 장기 안정성이 증대되는 효과를 확보할 수 있는 새로운 피셔-트롭쉬 합성 반응용 철계열의 촉매의 제조방법을 제공하는 것을, 해결하고자 하는 과제로 한다.The present invention is an iron-based catalyst for the new Fischer-Tropsch synthesis reaction that can increase the dispersibility and activity of the iron catalyst, and to inhibit the deactivation of the catalyst under the Fischer-Tropsch synthesis reaction conditions to increase the long-term stability It is an object of the present invention to provide a method for producing the same.
본 발명은 세륨-지르코늄산화물 지지체 100 중량부에, Fe 5 ∼ 50 중량부, K 0 ∼ 15 중량부(바람직하게는 0.001 ∼ 15 중량부), 및 Cu, Co 및 Mn 중에서 선택된 금속원소 0.25 ∼ 10 중량부가 담지된 철계열의 피셔-트롭쉬 합성 반응용 촉매를 제공함으로써, 상기 과제를 해결한다.The present invention, 100 parts by weight of the cerium-zirconium oxide support, 5 to 50 parts by weight Fe, 0 to 15 parts by weight (preferably 0.001 to 15 parts by weight), and 0.25 to 10 metal elements selected from Cu, Co and Mn The above problem is solved by providing a catalyst for Fischer-Tropsch synthesis reaction of iron-based parts by weight.
또한, 본 발명은 구연산과 에틸렌글리콜의 혼합 용액에, 세륨 전구체 수용액을 첨가하여 세륨 함유액을 제조하는 단계; 구연산과 에틸렌글리콜의 혼합 용액에, 지르코늄 전구체 수용액을 첨가하여 지르코늄 함유액을 제조하는 단계; 상기 세륨 함유액과 지르코늄 함유액을 혼합한 혼합액을 50 ∼ 100 ℃에서 교반시킨 후, 120 ∼ 150 ℃에서 가열시켜 혼합액에 포함된 물을 완전히 제거하여 졸(Sol)을 제조하는 단계; 상기 졸을 3 ∼ 7 ℃/min의 승온 속도로 100 ∼ 500 ℃ 범위에서 단계적으로 승온시켜 소성하는 단계; 를 포함하여 이루어지는 졸-겔 반응에 의한 철계열의 피셔-트롭쉬 합성 반응 촉매용 세륨-지르코늄산화물 지지체의 제조방법을 제공함으로써, 상기 과제를 해결한다.In addition, the present invention comprises the steps of preparing a cerium-containing liquid by adding a cerium precursor aqueous solution to a mixed solution of citric acid and ethylene glycol; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed solution of citric acid and ethylene glycol; Preparing a sol (Sol) by thoroughly stirring the mixed solution of the cerium-containing solution and the zirconium-containing solution at 50 to 100 ° C., and then heating at 120 to 150 ° C. to completely remove water contained in the mixed solution; Calcining the sol by heating up stepwise in a range of 100 to 500 ° C. at a temperature rising rate of 3 to 7 ° C./min; By providing a method for producing a cerium-zirconium oxide support for a Fischer-Tropsch synthesis reaction catalyst of iron series by a sol-gel reaction comprising a, to solve the above problems.
또한, 본 발명은 구연산과 에틸렌글리콜의 혼합 용액에, 세륨 전구체 수용액을 첨가하여 세륨 함유액을 제조하는 단계; 구연산과 에틸렌글리콜의 혼합 용액에, 지르코늄 전구체 수용액을 첨가하여 지르코늄 함유액을 제조하는 단계; 상기 세륨 함유액과 지르코늄 함유액을 혼합한 혼합액을 50 ∼ 100 ℃에서 교반시킨 후, 120 ∼ 150 ℃에서 가열시켜 혼합액에 포함된 물을 완전히 제거하여 졸(Sol)을 제조하는 단계; 상기 졸을 3 ∼ 7 ℃/min의 승온 속도로 100 ∼ 500 ℃ 범위에서 단계적으로 승온시켜 소성하여 세륨-지르코늄산화물 지지체를 제조하는 단계; 및 상기 세륨-지르코늄산화물 지지체에, Fe 금속 전구체, Cu, Co 및 Mn 중에서 선택된 증진용 금속(M)의 전구체, 그리고 필요에 따라 K 전구체를 함침법 또는 공침법으로 담지시켜 촉매를 얻는 단계; 를 포함하여 이루어지는 철계열의 피셔-트롭쉬(Fischer-Tropsch) 촉매의 제조방법을 제공함으로써, 상기 과제를 해결한다.In addition, the present invention comprises the steps of preparing a cerium-containing liquid by adding a cerium precursor aqueous solution to a mixed solution of citric acid and ethylene glycol; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed solution of citric acid and ethylene glycol; Preparing a sol (Sol) by thoroughly stirring the mixed solution of the cerium-containing solution and the zirconium-containing solution at 50 to 100 ° C., and then heating at 120 to 150 ° C. to completely remove water contained in the mixed solution; Step by heating the sol step by step in a range of 100 to 500 ℃ at a temperature increase rate of 3 to 7 ℃ / min to prepare a cerium-zirconium oxide support; And impregnating the cerium-zirconium oxide support with a Fe metal precursor, a precursor of an enhancement metal (M) selected from Cu, Co, and Mn, and, if necessary, a K precursor by impregnation or coprecipitation. By providing a method for producing an iron-based Fischer-Tropsch catalyst comprising a, to solve the above problems.
본 발명이 제안하고 있는 졸-겔 방법으로 제조된 세륨-지르코늄산화물을 지지체로 사용하는 철계열 촉매는, 피셔-트롭쉬 합성 반응에 사용되어 일산화탄소의 전환율 향상과 주요 부산물인 메탄으로의 선택성을 감소시켜서 고비점의 탄화수소 및 경질올레핀으로의 수율을 향상시키는 효과가 탁월하다.The iron-based catalyst using cerium-zirconium oxide prepared by the sol-gel method proposed by the present invention as a support is used in the Fischer-Tropsch synthesis reaction to improve the conversion rate of carbon monoxide and reduce the selectivity to methane, the main byproduct. The effect of improving the yield to high boiling hydrocarbons and light olefins is excellent.
본 발명은 천연가스로부터 제조된 합성가스를 이용하여 고비점의 탄화수소 및 경질올레핀을 선택적으로 생산하기에 적합한 촉매계로서, 졸-겔법으로 제조된 세륨-지르코늄산화물 지지체에 철과 증진용 금속 그리고 필요에 따라 칼륨 금속이 함침법 또는 공침법으로 담지되어 제조된 철계열의 피셔-트롭쉬 합성 반응용 촉매에 관한 것이다.The present invention is a catalyst system suitable for the selective production of high boiling point hydrocarbons and light olefins using a synthesis gas prepared from natural gas. Iron and an enhancement metal on a cerium-zirconium oxide support prepared by the sol-gel method and Accordingly, the present invention relates to an iron-based catalyst for Fischer-Tropsch synthesis reaction prepared by supporting potassium metal by impregnation or coprecipitation.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명이 특징으로 하는 철계열의 피셔-트롭쉬 합성 반응용 촉매는 세륨-지르코늄산화물 지지체 100 중량부에 대하여, Fe 5 ∼ 50 중량부, K 0 ∼ 15 중량부(바람직하게는 0.001 ∼ 15 중량부), 그리고 Cu, Co 및 Mn 중에서 선택된 1종의 금속원소 0.25 ∼ 10 중량부를 포함하여 이루어진다. 특히, 본 발명의 촉매는 주요 활성 성분인 철(Fe) 금속에 대하여 Cu, Co 및 Mn 중에서 선택된 증진용 금속(M)의 중량비인 M/Fe는 0.05 ∼ 0.20의 범위를 유지하며, 철(Fe) 금속에 대하여 K 금 속의 중량비인 K/Fe는 0.0 ∼ 0.3의 범위(바람직하게는 0.01 ∼ 0.3)를 유지한다. 그리고 상기한 활성성분의 지지체로 사용되는 세륨-지르코늄산화물(CexZr1-xO2)에서 지르코늄(Zr)에 대한 Ce의 중량비인 Ce/Zr가 0.05 ∼ 0.50의 범위를 유지하는 것에 그 특징이 있다.The catalyst for the Fischer-Tropsch synthesis reaction of the iron series of the present invention is based on 100 parts by weight of the cerium-zirconium oxide support, Fe 5-50 parts by weight, K 0-15 parts by weight (preferably 0.001-15 parts by weight). Parts) and 0.25 to 10 parts by weight of one metal element selected from Cu, Co and Mn. In particular, in the catalyst of the present invention, M / Fe, which is a weight ratio of the enhancement metal (M) selected from Cu, Co, and Mn with respect to iron (Fe) metal as the main active component, maintains a range of 0.05 to 0.20, and iron (Fe) K / Fe, the weight ratio of K metal to metal, is maintained in the range of 0.0 to 0.3 (preferably 0.01 to 0.3). And Ce / Zr, which is a weight ratio of Ce to zirconium (Zr) in cerium-zirconium oxide (Ce x Zr 1-x O 2 ) used as a support of the active ingredient, maintains a range of 0.05 to 0.50. There is this.
일반적으로 합성가스를 이용하여 액체 탄화수소를 제조하는 피셔-트롭쉬 반응에 있어서 철계열의 촉매를 사용하는 경우에는 피셔-트롭쉬 합성 메커니즘에 의하여 넓은 생성물 분포와 낮은 올레핀 선택성을 나타내는 것으로 보고되어 있는데, C2-C4 탄화수소의 선택성은 약 30 % 정도이며, 그 중의 올레핀 선택성은 약 80 % 정도로 낮은 것으로 보고되고 있다. 또한, 피셔-트롭쉬 합성반응은 CH2 체인성장 메카니즘의 특성 때문에 앤더슨-슐츠-플로리 중합(Anderson-Schulz-Flory polymerization) 모델에 의하면 C2-C4 탄화수소의 최대 수율이 56 %를 넘을 수 없는 것으로 알려져 있다.In general, in the Fischer-Tropsch reaction for producing liquid hydrocarbons using syngas, iron-based catalysts have been reported to exhibit wide product distribution and low olefin selectivity by the Fischer-Tropsch synthesis mechanism. The selectivity of C 2 -C 4 hydrocarbons is about 30%, of which the olefin selectivity is reported to be as low as about 80%. In addition, the Fischer-Tropsch synthesis reaction showed that the maximum yield of C 2 -C 4 hydrocarbons could not exceed 56% according to the Anderson-Schulz-Flory polymerization model due to the nature of the CH 2 chain growth mechanism. It is known.
본 연구팀의 선행연구 결과인 대한민국 특허출원공개 제2009-0038267호와 특허출원 제2008-0058457호에 의하면 합성가스로부터 경질올레핀을 생산하기 위한 방법으로서 고비점의 탄화수소를 2차로 열분해하거나 제올라이트 계열의 산촉매를 이용하는 혼성촉매를 이용하여 촉매 열분해하는 방법을 통하여 올레핀으로의 선택성을 향상시키는 방법을 보고하였다. 상기의 선행 연구결과에서는 철촉매를 제올라이트나 산화칼슘 지지체에 함침법 또는 공침법을 이용하여 제조한 촉매상에서 C2- C4의 수율을 향상하고 카본 효율을 증대하기 위하여 반응 중에 생성되는 부산물인 메탄 및 이산화탄소를 재순환하여 리포밍 (Reforming) 반응에 이용함으로써 경질올레핀의 생산성을 향상함과 동시에 부산물의 활용을 극대화 할 수 있는 방법을 제시하였다. 일례로, 대한민국 특허출원 제10-2008-0058457호에서는 철계열의 촉매는 일산화탄소의 수소화 반응에 활성을 나타내는 성분으로서 Fe를 제올라이트 지지체의 중량 대비 10 ∼ 70 중량%, Cu는 1 ∼ 10 중량% 및 K는 1 ∼ 10 중량%를 함유하는 Fe-Cu-K계열의 촉매를 활성 성분으로 사용하는 방법을 제시한 바도 있다.According to the results of the previous research of the team, Korean Patent Application Publication No. 2009-0038267 and Patent Application No. 2008-0058457 are methods for producing light olefins from syngas and secondary thermal decomposition of high boiling hydrocarbons or acid catalysts of zeolite series. A method of improving the selectivity to olefins has been reported through a method of catalytic pyrolysis using a hybrid catalyst using. In the preceding studies, methane, a by-product produced during the reaction, was used to improve the yield of C 2 -C 4 and to increase the carbon efficiency on the catalyst prepared by impregnating or co-precipitating an iron catalyst with a zeolite or calcium oxide support. And by recycling the carbon dioxide used in the reforming (Reforming) reaction to improve the productivity of the light olefins while presenting a method to maximize the use of by-products. For example, in Korean Patent Application No. 10-2008-0058457, the iron-based catalyst is an active ingredient in the hydrogenation reaction of carbon monoxide, and Fe is 10 to 70% by weight relative to the weight of the zeolite support, Cu is 1 to 10% by weight and K has also suggested a method of using a Fe-Cu-K-based catalyst containing 1 to 10% by weight as an active ingredient.
본 발명에서는 피셔-트롭쉬 합성 반응에 사용되는 철계열의 촉매를 세륨-지르코늄산화물 지지체에 함침법 또는 공침법으로 함유시켜서 부산물인 메탄으로의 선택성을 최소화함으로써 고비점 탄화수소 및 경질탄화수소로의 선택성을 향상하기 위한 신규한 촉매계를 제시한 것이다.In the present invention, the iron-based catalyst used in the Fischer-Tropsch synthesis reaction is contained in the cerium-zirconium oxide support by impregnation or coprecipitation to minimize the selectivity to high by-products of hydrocarbons and light hydrocarbons by minimizing the selectivity to methane as a by-product. A novel catalyst system for improvement is presented.
본 발명에 따른 촉매를 제조하기 위해 사용되는 철(Fe) 전구체로는 아이언 나이트레이트 수화물 (Fe(NO3)3 H2O), 아이언 아세테이트 (Fe(CO2CH3)2), 아이언 옥살레이트 수화물 (Fe(C2O4)3 H2O), 아이언 아세틸아세트네이트 (Fe(C5H7O2)3) 및 아이언 클로라이드 (FeCl3) 등의 Fe(Ⅱ) 및 Fe(Ⅲ) 전구체가 사용될 수 있다. 또한, 철(Fe)의 환원성 및 분산성을 향상하기 위하여 추가로 사용되는 증진제로서 구리(Cu), 코발트(Co) 또는 망간(Mn) 금속원소는 아세테이트, 나이트레이트 또는 클로라이드 계열의 금속 전구체 화합물 중에서 선택된 1종 또는 2종 이상의 혼합물을 사용할 수 있다. 또한, 본 발명에서는 올레핀의 선택성을 향상하기 위한 성분 으로서 칼륨(K)를 추가로 사용할 수 있으며, 칼륨(K) 전구체로는 K2CO3, KOH 및 KHCO3 등 중에서 선택하여 사용될 수 있다. Iron (Fe) precursors used to prepare the catalyst according to the invention include iron nitrate hydrate (Fe (NO 3 ) 3 H 2 O), iron acetate (Fe (CO 2 CH 3 ) 2 ), iron oxalate Fe (II) and Fe (III) precursors such as hydrate (Fe (C 2 O 4 ) 3 H 2 O), iron acetylacetonate (Fe (C 5 H 7 O 2 ) 3 ), and iron chloride (FeCl 3 ) Can be used. In addition, copper (Cu), cobalt (Co) or manganese (Mn) metal element as an additionally used to improve the reducibility and dispersibility of iron (Fe) in the acetate, nitrate or chloride-based metal precursor compound One or a mixture of two or more selected may be used. In addition, in the present invention, potassium (K) may be additionally used as a component for improving the selectivity of the olefin, and the potassium (K) precursor may be selected from K 2 CO 3 , KOH, and KHCO 3 .
상기한 철 전구체, 증진제 금속 전구체, 및 칼륨 전구체를 이용하여 제조된 Fe-Cu(또는 Co, Mn)-K계열의 촉매는 세륨-지르코늄산화물 지지체에 함침법 또는 공침법으로 담지되어 본 발명의 촉매를 제조하게 된다. 제조된 촉매는 300 ∼ 700 ℃의 영역에서 소성 처리하여 촉매 활성성분의 구조를 미리 안정화시켜 줄 필요성이 있다.The Fe-Cu (or Co, Mn) -K-based catalyst prepared by using the iron precursor, the enhancer metal precursor, and the potassium precursor is supported on the cerium-zirconium oxide support by impregnation or coprecipitation. It will be prepared. The prepared catalyst needs to be calcined in the region of 300 to 700 ° C. to stabilize the structure of the catalytically active component in advance.
이상에서 설명한 본 발명에 따른 철계열의 촉매의 제조방법을 보다 구체적으로 설명하면 다음과 같다.Hereinafter, the method for preparing the iron-based catalyst according to the present invention described above will be described in more detail.
먼저, 세륨-지르코늄산화물 지지체를 제조한다. 지지체의 제조과정은 구연산과 에틸렌글리콜의 혼합 용액에, 세륨 전구체 수용액을 첨가하여 세륨 함유액을 제조하는 단계와; 구연산과 에틸렌글리콜의 혼합 용액에, 지르코늄 전구체 수용액을 첨가하여 지르코늄 함유액을 제조하는 단계와; 상기 세륨 함유액과 지르코늄 함유액을 혼합한 혼합액을 50 ∼ 100 ℃에서 교반시킨 후, 120 ∼ 150 ℃에서 5 ∼ 10 시간 동안 가열시켜 혼합액에 포함된 물을 완전히 제거하여 졸(Sol)을 제조하는 단계와; 상기 졸을 3 ∼ 7 ℃/min의 승온 속도로 100, 150, 200, 300 ℃에서 각각 0.5 ∼ 2시간 동안 유지하고 350 ∼ 450 ℃에서는 2 ∼ 10시간 동안 유지하고, 최종적으로 470 ∼ 550 ℃에서 3 ∼ 5 시간 동안 유지하는 단계적으로 소성하는 단계; 를 포함하여 이루어진다.First, a cerium-zirconium oxide support is prepared. The preparation process of the support includes the steps of preparing a cerium-containing solution by adding a cerium precursor aqueous solution to a mixed solution of citric acid and ethylene glycol; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed solution of citric acid and ethylene glycol; The mixture containing the cerium-containing liquid and zirconium-containing liquid was stirred at 50 to 100 ° C., and then heated at 120 to 150 ° C. for 5 to 10 hours to completely remove water contained in the mixed liquid to prepare a sol. Steps; The sol is maintained at 100, 150, 200, and 300 ° C. for 0.5 to 2 hours at a heating rate of 3 to 7 ° C./min, and for 2 to 10 hours at 350 to 450 ° C., and finally at 470 to 550 ° C. Calcining stepwise to maintain for 3 to 5 hours; It is made, including.
지지체 제조에 사용되는 세륨 및 지르코늄 전구체로는 아세테이트, 나이트레이트 또는 클로라이드 계열의 금속 전구체 화합물을 사용할 수 있다. 본 발명에서는 일 구현예로서, 세륨나이트레이트 (Ce(NO3)2 6H2O)와 지르코늄옥시나이트레이트 (ZrO(NO3)2 xH2O)를 사용하여 졸-겔 방법으로 세륨-지르코늄산화물을 제조하는 방법을 제시한다. 상기한 지지체의 제조방법을 보다 더 구체적으로 설명하면, 먼저 40 ∼ 70 ℃에서 구연산과 에틸렌글리콜을 교반하면서 20 ∼ 50분 동안 금속 전구체를 녹이는 과정이 필요하다. 즉, 세륨 및 지르코늄 전구체 각각을 10 ∼ 30 mL의 물에 녹여 완전히 용해시킨 후, 상기 제조된 구연산과 에틸렌글리콜의 혼합용액에 천천히 첨가하여 세륨 함유 용액과 지르코늄 함유 용액을 제조한다. 그런 다음, 상기에서 제조된 세륨 함유 용액과 지르코늄 함유 용액을 혼합한 혼합용액을 50 ∼ 100 ℃에서 20 ∼ 50분 동안 교반한 후, 다시 120 ∼ 150 ℃에서 2 ∼ 5 시간 동안 가열시켜 주면서, 용액에 포함된 물을 완전히 제거하여 졸(sol) 용액을 제조한다. 상기 혼합용액은 120 ∼ 150 ℃에서 가열하는 것이 바람직한데, 가열온도가 120 ℃ 미만에서는 온도가 너무 낮아 물의 제거가 어렵고, 온도가 150 ℃를 초과하는 경우에는 고온에서의 물의 급격한 증발로 인하여 세륨-지르코늄 수화물의 입자가 고르게 합성되지 않는 단점이 있다. 상기에서 제조된 졸 용액은 3 ∼ 7 ℃/min의 승온 속도로 100, 150, 200, 300 ℃에서 각각 0.5 ∼ 2시간 동안 유지시켰으며, 지지체의 표면적을 최대한 살리기 위해서 350 ∼ 450 ℃에서는 2 ∼ 10시간 동안 유지시켰으며, 최종적으로 470 ∼ 550 ℃에서 3 ∼ 5시간 동안 유 지하는 단계적 소성과정을 거쳐 세륨-지르코늄산화물 지지체를 제조한다. 졸(Sol) 용액을 급격하게 소성 온도를 증가시키게 되면, 세륨-지르코늄산화물 전구체의 엉김 현상에 의하여 넓은 비표면적을 갖는 지지체를 얻을 수 없었으나, 본 발명이 제안한 바대로 순차적으로 온도를 승온하여 소성하게 되면 넓은 비표면적의 세륨-지르코늄산화물 지지체를 얻을 수 있게 된다. 상기의 방법으로 제조된 세륨-지르코늄산화물 지지체는 비표면적이 5 ∼ 50 ㎡/g의 영역을 지니게 되는데, 비표면적이 넓을수록 활성성분인 철과 증진제의 분산성이 좋아지게 되지만, 비표면적이 5 ㎡/g 미만인 경우에는 철의 분산성이 현격하게 감소하게 된다. 또한, 세륨-지르코늄산화물 지지체의 비표면적이 50 ㎡/g 초과인 경우에는 촉매의 강도가 감소하는 문제가 발생할 수 있으므로 본 발명의 지지체는 상기의 비표면적 영역을 유지할 필요성이 있다. 또한, 세륨-지르코늄산화물(CexZr1-xO2)에서 Ce/Zr의 금속 성분의 중량비는 0.05 ∼ 0.50의 범위를 유지하는 것이 바람직한데, Ce/Zr 금속의 중량비가 0.05 미만인 경우에는 ZrO2의 산점의 양이 증가하여 메탄 및 CO2 이외의 부산물의 선택성이 증가하는 문제점이 발생할 수 있으며, Ce/Zr 금속의 중량비가 0.5를 초과하는 경우에도 부산물 생성에 유리한 염기점의 생성이 증가하여 부산물의 생성이 증가하는 문제점이 발생할 수 있으므로 상기 영역의 Ce/Zr의 금속 중량비를 유지하는 것이 메탄 등의 부산물 생성이 억제됨과 동시에 촉매의 비활성화를 최대한 억제할 수 있게 된다. As the cerium and zirconium precursors used for preparing the support, an acetate, nitrate or chloride-based metal precursor compound may be used. In the present invention, as an embodiment, cerium-zirconium oxide by sol-gel method using cerium nitrate (Ce (NO 3 ) 2 6H 2 O) and zirconium oxynitrate (ZrO (NO 3 ) 2 xH 2 O) It presents a method of preparing. In more detail, the above-described method for preparing the support is required to dissolve the metal precursor for 20 to 50 minutes while stirring the citric acid and ethylene glycol at 40 to 70 ℃. That is, the cerium and zirconium precursors are dissolved in 10 to 30 mL of water to completely dissolve, and then slowly added to the mixed solution of citric acid and ethylene glycol, thereby preparing a cerium-containing solution and a zirconium-containing solution. Then, the mixed solution of the cerium-containing solution and zirconium-containing solution prepared above was stirred at 50 to 100 ° C. for 20 to 50 minutes, and then heated at 120 to 150 ° C. for 2 to 5 hours. By completely removing the water contained in Prepare a sol solution. Preferably, the mixed solution is heated at 120 to 150 ° C., but when the heating temperature is lower than 120 ° C., the temperature is too low to remove water. When the temperature exceeds 150 ° C., cerium- A disadvantage is that the particles of zirconium hydrate are not evenly synthesized. The sol solution prepared above was maintained at 100, 150, 200, and 300 ° C. for 0.5 to 2 hours at a heating rate of 3 to 7 ° C./min, respectively, at 350 to 450 ° C. at 2 to 3 ° C. to maximize the surface area of the support. It was maintained for 10 hours, and finally a cerium-zirconium oxide support was prepared through a stepwise firing process maintained at 470 to 550 ° C. for 3 to 5 hours. When the sol (Sol) solution was rapidly increased in firing temperature, a support having a large specific surface area could not be obtained due to entanglement of the cerium-zirconium oxide precursor, but firing was performed by sequentially raising the temperature as suggested by the present invention. In this case, a cerium-zirconium oxide support having a large specific surface area can be obtained. The cerium-zirconium oxide support prepared by the above method has a specific surface area of 5 to 50 m 2 / g. The larger the specific surface area, the better the dispersibility of the active ingredient iron and the enhancer, but the specific surface area is 5 If less than m 2 / g, the dispersibility of iron is greatly reduced. In addition, when the cerium-zirconium oxide support has a specific surface area of more than 50 m 2 / g, a problem of decreasing the strength of the catalyst may occur, so the support of the present invention needs to maintain the specific surface area. In addition, the weight ratio of the metal component of Ce / Zr in the cerium-zirconium oxide (Ce x Zr 1-x O 2 ) is preferably maintained in the range of 0.05 to 0.50. When the weight ratio of Ce / Zr metal is less than 0.05, ZrO the amount of acid sites of the second increase methane and may result in the increased problem that the selectivity of by-products other than CO 2, and the weight ratio of Ce / Zr metals increase the production of favorable base point to produce a by-product, even if it exceeds 0.5 Since the generation of by-products may increase, maintaining the metal weight ratio of Ce / Zr in the region may suppress generation of by-products such as methane and at the same time suppress the deactivation of the catalyst.
한편, 본 발명은 상기에서 설명한 바와 같은 제조방법으로 제조된 세륨-지르 코늄산화물 지지체를 이용하여 철계열의 피셔-트롭쉬 반응용 촉매를 제조하는 방법을 그 특징으로 한다.On the other hand, the present invention is characterized by a method for producing an iron-based catalyst for Fischer-Tropsch reaction using a cerium-zirconium oxide support prepared by the method described above.
즉, 철계열의 촉매를 제조하기 위해서는 구연산과 에틸렌글리콜의 혼합액에, 세륨 전구체 수용액을 첨가하여 세륨 함유액을 제조하는 단계와; 구연산과 에틸렌글리콜의 혼합액에, 지르코늄 전구체 수용액을 첨가하여 지르코늄 함유액을 제조하는 단계와; 상기 세륨 함유액과 지르코늄 함유액을 혼합한 혼합액을 50 ∼ 100 ℃에서 교반시킨 후, 120 ∼ 150 ℃에서 5 ∼ 10 시간 동안 가열시켜 혼합액에 포함된 물을 완전히 제거하여 졸(Sol)을 제조하는 단계와; 상기 졸을 3 ∼ 7 ℃/min의 승온 속도로 100, 150, 200, 300 ℃에서 각각 0.5 ∼ 2시간 동안 유지하고 350 ∼ 450 ℃에서는 2 ∼ 10시간 동안 유지하고, 최종적으로 470 ∼ 550 ℃에서 3 ∼ 5 시간 동안 유지하는 단계적 소성에 의해 세륨-지르코늄산화물 지지체를 제조하는 단계와; 및 상기 세륨-지르코늄산화물 지지체에, Fe 금속 전구체, Cu, Co 및 Mn 중에서 선택된 금속(M)의 전구체, 그리고 필요에 따라 K 금속 전구체를 함침법 또는 공침법으로 담지시켜 촉매를 얻는 단계; 를 포함하여 이루어지는 철계열의 피셔-트롭쉬 합성 반응용 촉매를 제조한다. That is, to prepare an iron-based catalyst, adding a cerium precursor solution to the mixed solution of citric acid and ethylene glycol to prepare a cerium-containing liquid; Preparing a zirconium-containing liquid by adding an aqueous solution of zirconium precursor to a mixed liquid of citric acid and ethylene glycol; The mixture containing the cerium-containing liquid and zirconium-containing liquid was stirred at 50 to 100 ° C., and then heated at 120 to 150 ° C. for 5 to 10 hours to completely remove water contained in the mixed liquid to prepare a sol. Steps; The sol is maintained at 100, 150, 200, and 300 ° C. for 0.5 to 2 hours at a heating rate of 3 to 7 ° C./min, and for 2 to 10 hours at 350 to 450 ° C., and finally at 470 to 550 ° C. Preparing a cerium-zirconium oxide support by step firing maintained for 3 to 5 hours; And supporting the cerium-zirconium oxide support with a Fe metal precursor, a precursor of a metal (M) selected from Cu, Co, and Mn, and a K metal precursor, if necessary, by impregnation or coprecipitation. To prepare a catalyst for the iron-based Fischer-Tropsch synthesis reaction comprising a.
촉매의 제조방법을 보다 더 구체적으로 설명하면, 상기한 방법으로 제조된 세륨-지르코늄산화물 지지체에, 활성금속으로서 Fe 금속 전구체, M 금속(Cu, Co 및/또는 Mn) 전구체, 필요에 따라 K 금속 전구체를 담지시켜 철계열의 피셔-트롭쉬 합성 반응용 촉매를 제조한다. Fe 금속 전구체는 지지체 100 중량부를 기준으로 철(Fe) 금속의 담지량이 5 ∼ 50 중량부가 유지되도록 사용하고, M 금속(Cu, Co 및/또는 Mn) 전구체는 지지체 100 중량부를 기준으로 금속(M)의 담지량이 0.25 ∼ 10 중량부가 유지되도록 사용하고, K 금속 전구체는 지지체 100 중량부를 기준으로 칼륨(K) 금속의 담지량이 0 ∼ 15 중량부, 바람직하게는 0.001 ∼ 15 중량부가 유지되도록 하는 함량범위로 사용한다. 이때, 주요 활성성분인 철(Fe)에 대하여 Cu, Co 및 Mn 중에서 선택된 금속(M)의 중량비인 M/Fe는 0.05 ∼ 0.20의 범위를 유지하도록 하며, 철(Fe)에 대하여 칼륨(K) 성분의 중량비인 K/Fe는 0.0 ∼ 0.3, 바람직하게는 0.01 ∼ 0.3의 범위를 유지하도록 하여 촉매를 제조한다.In more detail, the method for preparing the catalyst is described in the above-described cerium-zirconium oxide support, which is an active metal Fe metal precursor, M metal (Cu, Co and / or Mn) precursor, if necessary K metal The precursor was supported to prepare an iron catalyst for Fischer-Tropsch synthesis reaction. The Fe metal precursor is used to maintain 5 to 50 parts by weight of the iron (Fe) metal based on 100 parts by weight of the support, and the M metal (Cu, Co and / or Mn) precursor is based on 100 parts by weight of the metal (M ) Is used so that the supporting amount of 0.25 to 10 parts by weight, and the K metal precursor is such that the supporting amount of potassium (K) metal is 0 to 15 parts by weight, preferably 0.001 to 15 parts by weight based on 100 parts by weight of the support. Use as a range. At this time, M / Fe, which is the weight ratio of the metal (M) selected from Cu, Co, and Mn with respect to iron (Fe), which is a main active component, is maintained in the range of 0.05 to 0.20, and potassium (K) with respect to iron (Fe). K / Fe which is the weight ratio of a component is 0.0-0.3, Preferably it maintains the range of 0.01-0.3, and a catalyst is manufactured.
본 발명의 촉매 제조방법으로서 함침법에 의한 철계열의 촉매 제조방법에서는 철 전구체, 증진제로 도입되는 M 금속(Cu, Co 및/또는 Mn) 전구체, 및 칼륨 전구체 각각은 동시에 또는 순차적인 방법으로 함침법을 이용하여 세륨-지르코늄산화물 지지체에 담지시켜 피셔-트롭쉬 합성반응용 촉매를 제조한다. 좀 더 자세하게는 상기 철 전구체로는 아이언 나이트레이트 수화물 (Fe(NO3)3 9H2O), 아이언 아세테이트 (Fe(CO2CH3)2), 아이언 옥살레이트 수화물 (Fe(C2O4)3 6H2O), 아이언 아세틸아세트네이트 (Fe(C5H7O2)3) 및 아이언 클로라이드 (FeCl3) 등으로 이루어진 Fe(Ⅱ) 및 Fe(Ⅲ) 전구체 중에서 선택된 1 종 또는 2종 이상의 혼합 전구체를 사용할 수 있다. 증진제로 사용되는 구리, 코발트 또는 망간 전구체는 아세테이트, 나이트레이트, 옥살레이트, 클로라이드와 같은 전구체 화합물을 사용할 수 있다. 칼륨 전구체로는 K2CO3, KOH 및 KHCO3 중에서 선택된 1 종 또는 2종 이상의 혼합 전구체를 사용할 수 있다.In the catalyst production method of the iron-based catalyst by the impregnation method of the present invention, the iron precursor, the M metal (Cu, Co and / or Mn) precursor introduced into the promoter, and the potassium precursor are each used simultaneously or sequentially. The catalyst for Fischer-Tropsch synthesis reaction was prepared by supporting the cerium-zirconium oxide support using the immersion method. More specifically, the iron precursor includes iron nitrate hydrate (Fe (NO 3 ) 3 9H 2 O), iron acetate (Fe (CO 2 CH 3 ) 2 ), iron oxalate hydrate (Fe (C 2 O 4 ) One or two or more selected from Fe (II) and Fe (III) precursors composed of 3 6H 2 O), iron acetylacetonate (Fe (C 5 H 7 O 2 ) 3 ), iron chloride (FeCl 3 ), and the like. Mixed precursors can be used. Copper, cobalt or manganese precursors used as enhancers may use precursor compounds such as acetates, nitrates, oxalates, chlorides. As the potassium precursor, one or two or more mixed precursors selected from K 2 CO 3 , KOH, and KHCO 3 may be used.
상기의 방법으로 제조된 철계열의 촉매는 100 ℃ 이상의 오븐에서 하루 정도 건조시킨 후에 피셔-트롭쉬 합성반응용 촉매로 사용하기 위하여 300 ∼ 700 ℃의 범위, 바람직하기는 400 ∼ 600 ℃의 범위에서 소성하여 사용하게 된다. 이때 상기 소성온도가 300 ℃ 미만이면 활성성분인 철과 증진제의 균일한 분산이 저하되어 반응성이 감소할 수 있으며, 소성온도가 700 ℃를 초과하는 경우에도 활성 성분의 응집에 의한 활성점이 감소하는 문제가 발생하여 반응성이 감소할 수 있으므로 상기의 영역을 유지할 필요성이 있다.The iron-based catalyst prepared by the above method is dried in an oven at 100 ° C. or higher for one day, and then used in a Fischer-Tropsch synthesis reaction catalyst in the range of 300 to 700 ° C., preferably in the range of 400 to 600 ° C. It is fired and used. In this case, when the firing temperature is less than 300 ℃, the uniform dispersion of the iron and the enhancer as the active ingredient may be lowered, the reactivity may be reduced, and even if the firing temperature exceeds 700 ℃ active point due to aggregation of the active ingredient is reduced There may be a need to maintain the above area since the reactivity may be reduced.
본 발명의 촉매 제조방법으로서 공침법에 의한 철계열의 촉매 제조방법에서는, 졸-겔 방법으로 제조된 세륨-지르코늄산화물의 슬러리 상에서 철 전구체, 칼륨 전구체 및 증진제로 도입되는 M 금속(Cu, Co 및/또는 Mn) 전구체를 혼합한 후에, pH가 7 ∼ 8의 영역이 되도록 수용액 하에서 공침시킨 후 40 ∼ 90 ℃의 영역에서 숙성하여 침전물을 여과 및 세척하여 제조할 수도 있다. 상기 공침시 pH 7 ∼ 8을 유지하기 위하여 염기성 침전제를 사용할 수 있으며, 상기 염기성 침전제는 구체적으로 탄산나트륨, 탄산칼슘 및 탄산암모늄 및 암모니아수를 사용하는 것이 바람직하다. 촉매의 숙성시간은 0.1 ∼ 10 시간 범위, 바람직하게는 0.5 ∼ 8시간으로 유지하는 것이 적절한데, 이는 제시된 숙성시간 영역에서 활성이 우수한 철계열의 촉매 형성에 도움이 되며, 상기 숙성 시간이 0.1 시간 미만이면 Fe-Cu (또는 Co 및 Mn) 성분의 분산성이 감소하여 피셔-트롭쉬 합성반응 면에서 불리하며, 10 시간을 초과하는 경우에는 Fe-Cu (또는 Co 및 Mn) 입자 사이즈가 증가하여 활성점이 감소하고 합성 시간이 증가하여 경제적이지 않으므로 적절하지 못하다. 상기의 공침법으로 제조된 Fe-Cu (또는 Co 및 Mn) 촉매에 대하여 칼륨 성분은 K/Fe는 0.0 ∼ 0.3의 영역을 유지하도록 철계열의 촉매를 제조하여 사용할 수 있다.In the catalyst preparation method of the iron series by the coprecipitation method of the present invention, the M metal (Cu, Co and Co) introduced into the iron precursor, the potassium precursor and the promoter on the slurry of cerium-zirconium oxide prepared by the sol-gel method And / or Mn) precursor may be prepared by coprecipitation under an aqueous solution so that the pH is in the range of 7 to 8, then aged in the range of 40 to 90 ° C., followed by filtration and washing of the precipitate. In the coprecipitation, a basic precipitant may be used to maintain pH 7 to 8, and the basic precipitant may specifically use sodium carbonate, calcium carbonate and ammonium carbonate and ammonia water. The aging time of the catalyst is appropriately maintained in the range of 0.1 to 10 hours, preferably 0.5 to 8 hours, which helps to form a catalyst of the iron-based catalyst having excellent activity in the range of aging time given, and the aging time is 0.1 hours. If less, the dispersibility of Fe-Cu (or Co and Mn) components decreases, which is disadvantageous in terms of the Fischer-Tropsch synthesis reaction, and if it exceeds 10 hours, the Fe-Cu (or Co and Mn) particle sizes increase. It is not suitable because the active point decreases and the synthesis time is increased, which is not economical. For the Fe-Cu (or Co and Mn) catalyst prepared by the co-precipitation method, the potassium component may be used by preparing an iron-based catalyst such that K / Fe is maintained in a range of 0.0 to 0.3.
상기의 방법으로 제조된 피셔-트롭쉬 합성반응용 촉매는 고정층, 유동층 및 슬러리 반응기에서 200 ∼ 700 ℃의 영역에서 수소 분위기에서 환원한 후에 반응에 사용하게 되며, 환원된 촉매는 일반적인 피셔-트롭쉬 합성반응과 유사한 반응 조건에서 수행되는 바, 구체적으로 반응 온도는 250 ∼ 400 ℃, 반응 압력은 5 ∼ 60 kg/㎠와 공간속도는 500 ∼ 10000 h-1에서 수행하는 것이 좋으나, 이에 한정되는 것은 아니다. Fischer-Tropsch synthesis catalyst prepared by the above method is used in the reaction after reducing in a hydrogen atmosphere in the region of 200 ~ 700 ℃ in a fixed bed, fluidized bed and slurry reactor, the reduced catalyst is a general Fischer-Tropsch The reaction is carried out under similar reaction conditions as the synthesis reaction. Specifically, the reaction temperature is 250 to 400 ° C., the reaction pressure is preferably performed at 5 to 60 kg / cm 2 and the space velocity is 500 to 10000 h −1 , but is not limited thereto. no.
이상의 제조방법으로 제조된 철계열의 촉매는 피셔-트롭쉬 합성반응용 촉매로서 유용하게 사용될 수 있다. 이를 구체적으로 설명하면, 반응온도 300 ℃, 반응압력 10 kg/㎠, 공간속도 2000 L/kgcathr의 조건에서 반응물인 일산화탄소:수소:아르곤(내부 표준물질)의 몰비를 31.7:63.3:5.0의 비율로 고정하여 피셔-트롭쉬 반응을 수행하는 경우에 일산화탄소 전환율은 90 카본 몰% 이상이고, C5+ 탄화수소, 구체적으로 나프타, 디젤, 중간 유분, 중유 및 왁스 등의 수율이 30 카본 몰% 이상이며, 주요 부산물인 메탄(C1)으로의 선택성은 10 카본 몰% 이하의 범위를 나타낸다.The iron-based catalyst prepared by the above method may be usefully used as a catalyst for Fischer-Tropsch synthesis reaction. Specifically, the molar ratio of carbon monoxide: hydrogen: argon (internal standard) as a reactant at a reaction temperature of 300 ° C., a reaction pressure of 10 kg / cm 2, and a space velocity of 2000 L / kg cat hr is 31.7: 63.3: 5.0. When the Fischer-Tropsch reaction is carried out at a fixed rate, the carbon monoxide conversion is at least 90 carbon mol%, and the yield of C 5+ hydrocarbons, specifically naphtha, diesel, middle oil, heavy oil and wax, is at least 30 carbon mol%. The selectivity to methane (C 1 ), a major byproduct, is in the range of 10 carbon mole% or less.
이와 같은 본 발명은 하기의 실시예에 의거하여 구체적으로 설명하는 바, 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다.Such the present invention will be described in detail based on the following examples, but the present invention is not limited by the following examples.
실시예 1. 20Fe-2Cu-4K/Ce0.05Zr0.95O2 촉매 제조Example 1 Preparation of 20Fe-2Cu-4K / Ce 0.05 Zr 0.95 O 2 Catalyst
1) 세륨-지르코늄산화물 지지체의 제조1) Preparation of Cerium-zirconium Oxide Support
세륨-지르코늄산화물 지지체는 졸-겔법에 의해 제조하였다.The cerium-zirconium oxide support was prepared by the sol-gel method.
우선 60 ℃에서 구연산(Citric acid) 12.1 g과 에틸렌글리콜(Ethylene glycol) 14.3 g을 교반하면서 30분 동안 녹인 다음, 세륨 전구체로 사용한 세륨나이트레이트 수화물(Ce(NO3)2 6H2O) 2.5 g을 30 mL 이하의 최소량의 물에 녹여 완전히 용해시킨 후, 미리 제조된 구연산과 에틸렌글리콜의 혼합 용액(A)에 천천히 첨가하였다. 이때, 구연산은 세륨-지르코늄 금속 몰수의 10배로 사용하였으며, 에틸렌글리콜은 세륨-지르코늄 금속 몰수의 40배로 사용하였다. 같은 방법으로 60 ℃에서 구연산 351.9 g과 에틸렌글리콜 417.8 g을 교반하면서 30분 동안 녹인 다음, 지르코늄(Ⅳ) 옥시클로라이드 전구체(ZrCl2O 8H2O; zirconium(Ⅳ) oxychloride octahydrate) 38.9 g을 30 mL 이하의 물에 녹여 완전히 용해시킨 후 미리 제조된 구연산과 에틸렌글리콜의 혼합 용액(B)에 천천히 첨가하였다. 상기 용액 A와 B를 혼합하여 60 ℃에서 30분 동안 교반시켜 준 후, 용액을 120 ∼ 130 ℃에서 5 시간 동안 가열시켜 주어 용액에 포함된 물을 완전히 제거하였다. 상기 방법으로 제조된 졸 상태의 물질은 5 ℃/min의 승온속도로 100, 150, 200, 300 ℃에서 각각 1시간 동안 유지시켰으며, 지지체의 표면적을 최대한 살리기 위해 서 400 ℃에서는 2시간 동안 유지시켰으며, 최종 온도는 500 ℃에서 4시간 동안 유지하면서 소성하였다. 이때, 상기의 졸-겔법으로 제조된 세륨-지르코늄산화물의 조성은 금속기준으로 5중량%Ce-95중량%Zr이었으며 Ce0.05Zr0.95O2로 표기하였다.First, dissolve 12.1 g of citric acid and 14.3 g of ethylene glycol at 60 ° C. for 30 minutes while stirring, and then 2.5 g of cerium nitrate hydrate (Ce (NO 3 ) 2 6H 2 O) used as a cerium precursor. It was dissolved in a minimum amount of water of 30 mL or less to completely dissolve, and then slowly added to the prepared solution (A) of citric acid and ethylene glycol. At this time, citric acid was used 10 times the number of moles of cerium-zirconium metal, ethylene glycol was used at 40 times the number of moles of cerium-zirconium metal. In the same manner, dissolve 351.9 g of citric acid and 417.8 g of ethylene glycol at 60 ° C. for 30 minutes while stirring, and then 30 mL of 38.9 g of zirconium (IV) oxychloride precursor (ZrCl 2 O 8H 2 O; zirconium (IV) oxychloride octahydrate). It was dissolved in the following water to completely dissolve, and then slowly added to the prepared solution (B) of citric acid and ethylene glycol. The solution A and B were mixed and stirred at 60 ° C. for 30 minutes, and then the solution was heated at 120 to 130 ° C. for 5 hours to completely remove the water contained in the solution. The sol material prepared by the above method was maintained at 100, 150, 200, and 300 ° C. for 1 hour at a temperature increase rate of 5 ° C./min, and maintained at 400 ° C. for 2 hours to maximize the surface area of the support. The final temperature was calcined while maintaining at 500 ° C. for 4 hours. At this time, the composition of the cerium-zirconium oxide prepared by the sol-gel method was 5% by weight Ce-95% by weight Zr based on the metal and is expressed as Ce 0.05 Zr 0.95 O 2 .
2) 20Fe-2Cu-4K/Ce0.05Zr0.95O2 촉매의 제조2) Preparation of 20Fe-2Cu-4K / Ce 0.05 Zr 0.95 O 2 Catalyst
상기 제조된 분말상의 세륨-지르코늄산화물 지지체 3 g을 사용하고, 철, 구리, 칼륨 전구체로는 각각 아이언 나이트레이트 수화물 (Fe(NO3)3 H2O) 4.41 g, 구리 나이트레이트 수화물 (Cu(NO3)2 H2O) 0.29 g, 탄산칼륨 (K2CO3) 0.21 g을 동시에 60 mL의 3차 증류수에 녹인 후 혼합하고 60 ℃에서 6시간 이상 교반하고 감압증류장치를 이용하여 물을 제거하였다. 이후에 105 ℃에서 12시간 이상 건조한 후에 500 ℃의 공기 분위기에서 5시간 동안 소성 처리하여 철-구리-칼륨/세륨-지르코늄산화물이 포함된 피셔-트롭쉬 합성반응용 촉매를 제조하였다. 이때, 상기 피셔-트롭쉬 합성 반응용 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Cu 2 중량부, K 4 중량부인 "20Fe-2Cu-4K/Ce0.05Zr0.95O2 촉매"이었다.Using 3 g of the powdered cerium-zirconium oxide support, iron, copper, and potassium precursors were 4.41 g of iron nitrate hydrate (Fe (NO 3 ) 3 H 2 O), and copper nitrate hydrate (Cu ( NO 3 ) 2 H 2 O) 0.29 g and potassium carbonate (K 2 CO 3 ) were dissolved in 60 mL of tertiary distilled water at the same time, mixed and stirred at 60 ° C for at least 6 hours. Removed. Thereafter, after drying at 105 ° C. for 12 hours or more, the product was calcined in an air atmosphere at 500 ° C. for 5 hours to prepare a catalyst for Fischer-Tropsch synthesis reaction containing iron-copper-potassium / cerium-zirconium oxide. At this time, the composition of the catalyst for Fischer-Tropsch synthesis reaction is based on 100 parts by weight of cerium-zirconium oxide, 20 parts by weight of Fe, 2 parts by weight of Cu, 4 parts by weight of "20Fe-2Cu-4K / Ce 0.05 Zr 0.95 O 2 Catalyst ".
제조된 촉매를 사용하여 반응을 시작하기 전에 1/2인치 스테인레스 고정층 반응기에 0.3 g의 촉매를 장입하였다. 450 ℃의 수소 (5 부피% H2/He)분위기 하에서 12시간 환원 처리한 후에 반응온도 300 ℃, 반응압력 10 kg/㎠, 공간속도 2000 L/kgcathr의 조건에서 반응물인 일산화탄소:수소:아르곤(내부 표준물질)의 몰비를 31.7:63.3:5.0의 비율로 고정하여 반응기로 주입하여 피셔-트롭쉬 반응을 수행하였다. 상기 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다. 0.3 g of catalyst was charged to a 1/2 inch stainless fixed bed reactor before starting the reaction using the prepared catalyst. Carbon monoxide as a reactant at a reaction temperature of 300 ° C., reaction pressure of 10 kg / cm 2, space velocity of 2000 L / kg cat hr after 12 hours reduction treatment at 450 ° C. hydrogen (5 vol% H 2 / He) atmosphere. The Fischer-Tropsch reaction was carried out by injecting the molar ratio of argon (internal standard) into the reactor at a fixed ratio of 31.7: 63.3: 5.0. The reaction results are shown in the following Table 1 using an average value of 10 hours after the
실시예 2. 20Fe-2Cu-4K/Ce0.08Zr0.92O2 촉매 제조Example 2. Preparation of 20Fe-2Cu-4K / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr이 되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하였으며, 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Cu 2 중량부, K 4 중량부인 "20Fe-2Cu-4K/Ce0.08Zr0.92O2 촉매"이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, and the final catalyst composition was based on 100 parts by weight of cerium-zirconium oxide. 20 parts by weight, 2 parts by weight of Cu and 4 parts by weight of "20Fe-2Cu-4K / Ce 0.08 Zr 0.92 O 2 catalyst".
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
실시예 3. 20Fe-2Cu-4K/Ce0.15Zr0.85O2 촉매 제조Example 3. Preparation of 20Fe-2Cu-4K / Ce 0.15 Zr 0.85 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 15중량%Ce-85중량%Zr이 되도록 제조하여 Ce0.15Zr0.85O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하였으며, 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Cu 2 중량부, K 4 중량부인 "20Fe-2Cu-4K/Ce0.15Zr0.85O2 촉매"이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 15 wt% Ce-85 wt% Zr based on the metal, and was expressed as Ce 0.15 Zr 0.85 O 2 . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, and the final catalyst composition was based on 100 parts by weight of cerium-zirconium oxide. 20 parts by weight, 2 parts by weight of Cu, and 4 parts by weight of "20Fe-2Cu-4K / Ce 0.15 Zr 0.85 O 2 catalyst".
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
실시예 4. 20Fe-2Cu-4K/Ce0.50Zr0.50O2 촉매 제조Example 4 Preparation of 20Fe-2Cu-4K / Ce 0.50 Zr 0.50 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 50중량%Ce-50중량%Zr이 되도록 제조하여 Ce0.50Zr0.50O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하였으며, 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Cu 2 중량부, K 4 중량부인 "20Fe-2Cu-4K/Ce0.50Zr0.50O2 촉매"이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 50 wt% Ce-50 wt% Zr based on the metal, and was expressed as Ce 0.50 Zr 0.50 O 2 . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, and the final catalyst composition was based on 100 parts by weight of cerium-zirconium oxide. 20 parts by weight, 2 parts by weight of Cu, and 4 parts by weight of "20Fe-2Cu-4K / Ce 0.50 Zr 0.50 O 2 catalyst".
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
실시예 5. 5Fe-0.5Cu-1K/Ce0.08Zr0.92O2 촉매 제조Example 5. Preparation of 5Fe-0.5Cu-1K / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr이 되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하되 활성금속 성분인 Fe, Cu 및 K의 함유량을 변화하여 촉매를 제조하였으며, 제조된 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 5 중량부, Cu 0.5 중량부, K 1 중량부인 "5Fe-0.5Cu-1K/Ce0.08Zr0.92O2 촉매"이었다. 이때 제조된 촉매의 비표면적은 35.6 ㎡/g 이었으며, 평균 기공의 크기는 13.2 nm 이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the catalyst was changed by changing the content of Fe, Cu and K as active metal components. The composition of the final catalyst prepared was "5Fe-0.5Cu-1K / Ce 0.08 Zr 0.92 O 2 catalyst" having 5 parts by weight of Fe, 0.5 parts by weight of Cu, and 1 part by weight of K based on 100 parts by weight of cerium-zirconium oxide. . In this case, the specific surface area of the prepared catalyst was 35.6 m 2 / g, and the average pore size was 13.2 nm.
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
실시예 6. 30Fe-3Cu-6K/Ce0.08Zr0.92O2 촉매 제조Example 6. Preparation of 30Fe-3Cu-6K / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr이 되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하되 활성금속 성분인 Fe, Cu 및 K의 함유량을 변화하여 촉매를 제조하였으며, 제조된 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 30 중량부, Cu 3 중량부, K 6 중량부인 "30Fe-3Cu-6K/Ce0.08Zr0.92O2 촉매"이었다. 이때 제조된 촉매의 비표면적은 29.6 ㎡/g 이었으며, 평균 기공의 크기는 12.9 nm 이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the catalyst was changed by changing the content of Fe, Cu and K as active metal components. It was prepared, and the composition of the prepared final catalyst was "30Fe-3Cu-6K / Ce 0.08 Zr 0.92 0 2 catalyst" which is 30 parts by weight of Fe, 3 parts by weight of Cu, and 6 parts by weight of K based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 29.6 m 2 / g, and the average pore size was 12.9 nm.
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
실시예 7. 40Fe-4Cu-8K/Ce0.08Zr0.92O2 촉매 제조Example 7. Preparation of 40Fe-4Cu-8K / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr이 되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하되 활성금속 성분인 Fe, Cu 및 K의 함유량을 변화하여 촉매를 제조하였으며, 제조된 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 40 중 량부, Cu 4 중량부, K 6 중량부인 "40Fe-4Cu-6K/Ce0.08Zr0.92O2 촉매"이었다. 이때 제조된 촉매의 비표면적은 19.3 ㎡/g 이었으며, 평균 기공의 크기는 16.5 nm 이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the catalyst was changed by changing the content of Fe, Cu and K as active metal components. The prepared final catalyst had a composition of “40Fe-4Cu-6K / Ce 0.08 Zr 0.92 O 2 catalyst” which is about 40 parts by weight of Fe, 4 parts by weight of Cu, and 6 parts by weight of K based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 19.3 m 2 / g, and the average pore size was 16.5 nm.
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
실시예 8. 20Fe-2Cu/Ce0.08Zr0.92O2 촉매 제조Example 8 Preparation of 20Fe-2Cu / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr이 되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하되 활성금속 성분인 Fe 및 Cu만을 포함하고 K 성분을 포함하지 않는 촉매를 제조하였으며, 제조된 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Cu 2 중량부인 "20Fe-2Cu/Ce0.08Zr0.92O2 촉매"이었다. 이때 제조된 촉매의 비표면적은 24.6 ㎡/g 이었으며, 평균 기공의 크기는 15.5 nm 이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . Fischer-Tropsch synthesis catalyst is prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but includes only active metal components Fe and Cu and no K component. A catalyst was prepared, and the composition of the prepared final catalyst was “20Fe-2Cu / Ce 0.08 Zr 0.92 O 2 catalyst” which is 20 parts by weight of Fe and 2 parts by weight of Cu based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 24.6 m 2 / g, and the average pore size was 15.5 nm.
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
실시예 9. 20Fe-2Mn-4K/Ce0.08Zr0.92O2 촉매 제조Example 9 Preparation of 20Fe-2Mn-4K / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr이 되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하되 활성금속 성분인 Fe 및 K 성분을 포함하되 증진제로 사용된 금속성분 중에서 망간 나이트레이트 수화물 (Mn(NO3)2 6H2O)을 이용하여 촉매를 제조하였으며, 제조된 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Mn 2 중량부인 "20Fe-2Mn/Ce0.08Zr0.92O2 촉매"이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . A catalyst for Fischer-Tropsch synthesis reaction was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the active metals included Fe and K, but the metal used as an enhancer. A catalyst was prepared using manganese nitrate hydrate (Mn (NO 3 ) 2 6H 2 O) among the components, and the composition of the prepared final catalyst was 20 parts by weight of Fe and 100 parts by weight of Mn 2 based on 100 parts by weight of cerium-zirconium oxide. "20Fe-2Mn / Ce 0.08 Zr 0.92 O 2 Catalyst".
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
실시예 10. 20Fe-2Co-4K/Ce0.08Zr0.92O2 촉매 제조Example 10 Preparation of 20Fe-2Co-4K / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr이 되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하되 활성금속 성분인 Fe 및 K 성분을 포함하되 증진제로 사용된 금속성분 중에서 코발트 나이트레이트 수화물 (Co(NO3)2 H2O)을 이용하여 촉매를 제조하였으며, 제조된 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Co 2 중량부, K 4 중량부인 "20Fe-2Co-4K/Ce0.08Zr0.92O2 촉매"이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . A catalyst for Fischer-Tropsch synthesis reaction was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the active metals included Fe and K, but the metal used as an enhancer. A catalyst was prepared using cobalt nitrate hydrate (Co (NO 3 ) 2 H 2 O) among the components, and the composition of the prepared final catalyst was 20 parts by weight of Fe and 100 parts by weight of Co 2 based on 100 parts by weight of cerium-zirconium oxide. , K 4 parts by weight of "20Fe-2Co-4K / Ce 0.08 Zr 0.92 O 2 catalyst".
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
비교예 1. 20Fe-2Cu-4K/ZrO2 촉매 제조Comparative Example 1. Preparation of 20Fe-2Cu-4K / ZrO 2 catalyst
상기의 실시예 1과는 다르게 금속산화물 지지체로서 Kanto 사의 지르코니아(ZrO2)를 사용하였으며, 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하였으며, 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Cu 2 중량부, K 4 중량부인 "20Fe-2Cu-4K/ZrO2 촉매"이었다.Unlike Example 1, zirconia (ZrO 2 ) manufactured by Kanto was used as the metal oxide support, and the catalyst for Fischer-Tropsch synthesis reaction was prepared in the same manner as in the catalyst production method of Example 1, and the final catalyst composition Silver was "20Fe-2Cu-4K / ZrO 2 catalyst" which was 20 parts by weight of Fe, 2 parts by weight of Cu, and 4 parts by weight of K based on 100 parts by weight of cerium-zirconium oxide.
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
비교예 2. 20Fe/Ce0.08Zr0.92O2 촉매 제조Comparative Example 2. Preparation of 20Fe / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr이 되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하되 활성 성분으로는 Fe 성분만을 포함하도록 제조하여, 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부가 담지된 "20Fe/Ce0.08Zr0.92O2 촉매"이었다. 이때 제조된 촉매의 비표면적은 37.8 ㎡/g 이었으며, 평균 기공의 크기는 13.8 nm 이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . The catalyst for Fischer-Tropsch synthesis reaction was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the active component was prepared to include only the Fe component, thereby preparing the final catalyst. It was a "20Fe / Ce 0.08 Zr 0.92 O 2 catalyst" loaded with 20 parts by weight of Fe based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 37.8 m 2 / g, and the average pore size was 13.8 nm.
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
비교예 3. 20Fe-4K/Ce0.08Zr0.92O2 촉매 제조Comparative Example 3. Preparation of 20Fe-4K / Ce 0.08 Zr 0.92 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하였으며, 제조된 지지체의 조성은 금속기준으로 8중량%Ce-92중량%Zr되도록 제조하여 Ce0.08Zr0.92O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하되 활성 성분으로는 Fe 성분과 K 성분만을 포함하도록 제조하여, 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, K 4 중량부인 "20Fe-4K/Ce0.08Zr0.92O2 촉매"이었다. 이때 제조된 촉매의 비표면적은 42.4 ㎡/g 이었으며, 평균 기공의 크기는 14.8 nm 이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, and the composition of the prepared support was prepared to be 8 wt% Ce-92 wt% Zr based on metal, and was expressed as Ce 0.08 Zr 0.92 O 2 . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, but the active ingredient was prepared to include only the Fe component and the K component. The composition of the catalyst was “20Fe-4K / Ce 0.08 Zr 0.92 O 2 catalyst” which is 20 parts by weight of Fe and K 4 parts by weight based on 100 parts by weight of cerium-zirconium oxide. At this time, the specific surface area of the prepared catalyst was 42.4 m 2 / g, and the average pore size was 14.8 nm.
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
비교예 4. 20Fe-2Cu-4K/Ce0.92Zr0.08O2 촉매 제조Comparative Example 4. Preparation of 20Fe-2Cu-4K / Ce 0.92 Zr 0.08 O 2 Catalyst
상기의 실시예 1과 동일한 방법으로 세륨-지르코늄산화물을 제조하되, 지지체의 Ce/Zr 비를 변경하여 제조하였으며, 제조된 지지체의 조성은 금속기준으로 92중량%Ce-8중량%Zr이 되도록 제조하여 Ce0.92Zr0.08O2로 표기하였다. 상기 방법으로 제조된 세륨-지르코늄산화물을 이용하여 상기 실시예 1의 촉매제조 방법과 동일하게 피셔-트롭쉬 합성반응용 촉매를 제조하였으며, 최종 촉매의 조성은 세륨-지르코늄 산화물 100 중량부를 기준으로 Fe 20 중량부, Cu 2 중량부, K 4 중량부인 "20Fe-2Cu-4K/Ce0.92Zr0.08O2 촉매"이었다.Cerium-zirconium oxide was prepared in the same manner as in Example 1, but was prepared by changing the Ce / Zr ratio of the support, the composition of the prepared support to be 92% by weight Ce--8% by weight Zr based on the metal Ce 0.92 Zr 0.08 O 2 . Fischer-Tropsch synthesis catalyst was prepared in the same manner as in the catalyst preparation method of Example 1 using the cerium-zirconium oxide prepared by the above method, and the final catalyst composition was based on 100 parts by weight of cerium-zirconium oxide. 20 parts by weight, 2 parts by weight of Cu and 4 parts by weight of "20Fe-2Cu-4K / Ce 0.92 Zr 0.08 O 2 catalyst".
상기 촉매상에서 실시예 1과 동일한 반응 조건에서 피셔-트롭쉬 합성반응을 수행하였으며, 반응 결과는 촉매의 활성이 안정화되어 유지되는 반응시간 60시간 이후에 10 시간의 평균값을 사용하여 다음 표 1에 나타내었다.Fischer-Tropsch synthesis reaction was carried out in the same reaction conditions as in Example 1 on the catalyst, the reaction results are shown in Table 1 using the average value of 10 hours after the
구 분
division
(중량부)Catalyst composition
(Parts by weight)
(중량비)Ce / (Ce + Zr)
(Weight ratio)
수율C 5+
yield
CeZrO220Fe-2Cu-4K /
CeZrO2
CeZrO220Fe-2Cu-4K /
CeZrO2
CeZrO2 20Fe-2Cu-4K /
CeZrO 2
CeZrO2 20Fe-2Cu-4K /
CeZrO 2
CeZrO2 5Fe-0.5Cu-1K /
CeZrO 2
CeZrO2 30Fe-3Cu-6K /
CeZrO 2
CeZrO2 40Fe-4Cu-8K /
CeZrO 2
CeZrO2 20Fe-2Cu /
CeZrO 2
CeZrO2 20Fe-2Mn-4K /
CeZrO 2
CeZrO2 20Fe-2Co-4K /
CeZrO 2
ZrO2 20Fe-2Cu-4K /
ZrO 2
CeZrO2 20Fe /
CeZrO 2
CeZrO2 20Fe-4K /
CeZrO 2
CeZrO2 20Fe-2Cu-4K /
CeZrO 2
상기 표 1에서 살펴본 바와 같이, 본 발명이 제안한 바대로 지지체로서는 졸-겔 방법으로 제조된 세륨-지르코늄산화물(CexZr1-xO2) 지지체로서 Ce/Zr의 금속 성분의 중량비가 0.05 ∼ 0.50 범위이며, 상기 지지체 100 중량부를 기준으로 담지되는 금속의 함량이 Fe 5 ∼ 50 중량부, K 0 ∼ 15 중량부, 증진제인 Cu, Co 및 Mn 중에서 선택된 1종의 금속 0.25 ∼ 10 중량부인 철계열의 촉매 (실시예 1 ∼ 실시예 10)는 피셔-트롭쉬 합성 반응에 사용되어 일산화탄소 전환율은 90.4 카본 몰% 이상, C5+ 탄화수소 수율이 32.3 카본 몰% 이상, 부산물로서 메탄의 선택도가 9.6 카본 몰% 이하로서 우수한 촉매 활성을 보여주었다. 이에 반하여, 세륨-지르코늄산화물 지지체를 사용하지 않은 경우 (비교예 1) 및 증진제인 Cu, Co 및 Mn 중에서 선택된 1종의 금속원소가 포함되지 않은 경우 (비교예 2 및 3)의 경우에는 C5+ 탄화수소 수율이 낮게 나타났으며, 세륨-지르코늄산화물(CexZr1-xO2)의 Ce/Zr의 금속 성분의 중량비가 0.92인 경우 (비교예 4)에도 촉매의 활성이 낮게 관찰되었다.As shown in Table 1, the weight ratio of the metal component of Ce / Zr as the support is a cerium-zirconium oxide (Ce x Zr 1-x O 2 ) support prepared by the sol-gel method, as proposed by the present invention. It is in the range of 0.50 and the content of the metal supported on the basis of 100 parts by weight of the iron is from 5 to 50 parts by weight of Fe, from 0 to 15 parts by weight of K, 0.25 to 10 parts by weight of one kind of metal selected from the promoters Cu, Co and Mn. A series of catalysts (Examples 1-10) were used in Fischer-Tropsch synthesis reactions with a carbon monoxide conversion of at least 90.4 carbon mole%, a C 5+ hydrocarbon yield of at least 32.3 carbon mole%, and selectivity of methane as a byproduct. It showed excellent catalytic activity with 9.6 carbon mole% or less. On the other hand, cerium - if not using zirconium oxide support (Comparative Example 1) and when enhancers of Cu, that does not contain the first metal element selected from among Co and Mn (Comparative Examples 2 and 3), C 5 + The yield of hydrocarbon was low, and the activity of the catalyst was low even when the weight ratio of the metal component of Ce / Zr of cerium-zirconium oxide (Ce x Zr 1-x O 2 ) was 0.92 (Comparative Example 4).
또한, 첨부도면 도 1에는 상기 실시예 1, 실시예 2, 비교예 1, 및 비교예 4에서 제조된 촉매하에서 반응온도 300 ℃, 반응압력 10 kg/㎠, 공간속도 2000 L/kgcathr의 조건에서 반응물인 일산화탄소:수소:아르곤(내부 표준물질)의 몰비를 31.7:63.3:5.0의 비율로 고정하여 피셔-트롭쉬 합성 반응한 경우, 반응시간에 따른 일산화탄소의 전환율을 시간에 따라서 도시한 그래프이다. 도 1에 의하면, 세륨-지르코늄산화물을 지지체로 사용한 본 발명의 촉매(실시예 1, 2)는, 지르코늄산화물을 지지체로 사용한 비교예 1의 촉매와 비교할 때 촉매의 비활성화가 현격하게 억제됨을 확인할 수 있다. In addition, Figure 1 shows the reaction temperature of 300 ℃,
따라서, 본 발명에서 제시한 바대로 지지체로서 Ce/Zr의 금속 중량비가 한정되고 졸-겔 방법으로 제조된 세륨-지르코늄산화물을 사용하여 제조된 철계열의 촉매는, 피셔-트롭쉬 합성 반응용 촉매로 사용되어 반응 시간에 따른 촉매의 비활성화가 매우 적으면서도 부산물인 메탄의 생성이 억제되는 효과를 확보할 수 있는 것을 확인할 수 있어서, 상기의 촉매를 사용하는 경우에는 안정적인 공정 확보에 도움이 될 수 있음을 본 발명을 통하여 확인할 수 있었다.Therefore, the iron-based catalyst prepared by using a cerium-zirconium oxide prepared by the sol-gel method with a metal weight ratio of Ce / Zr as a support as suggested in the present invention is a catalyst for Fischer-Tropsch synthesis reaction. It can be used to ensure that the deactivation of the catalyst according to the reaction time is very small, but the effect of suppressing the production of by-product methane can be secured, it can be helpful to secure a stable process when using the catalyst It could be confirmed through the present invention.
최근의 급변하는 유가 상승 문제에 대처하면서 석유화학의 기초원료인 경질올레핀 (light olefins) 및 청정연료 제조를 위한 고비점의 탄화수소를 선택적으로 생산하기 위한 촉매 기술 개발이 효율적인 피셔-트롭쉬 공정 개발에 있어서 경쟁력 확보를 위한 중요한 요소가 될 수 있다. 특히, 피셔-트롭쉬 반응용 촉매의 개선에 따라 전체 공정의 열효율 및 카본활용 효율을 향상할 수 있다.In response to the recent rapidly rising oil price problem, the development of catalyst technology to selectively produce light olefins, which are the basic raw materials of petrochemicals, and high-boiling hydrocarbons for the manufacture of clean fuels, has led to the development of efficient Fischer-Tropsch processes. Therefore, it can be an important factor for securing competitiveness. In particular, according to the improvement of the Fischer-Tropsch reaction catalyst can improve the thermal efficiency and carbon utilization efficiency of the entire process.
본 발명이 제안하고 있는 세륨-지르코늄산화물을 지지체로 사용하는 철계열의 피셔-트롭쉬 촉매는, 일산화탄소 전환율 향상과 주요 부산물인 메탄으로의 선택성을 감소시켜서 고비점의 탄화수소 및 경질올레핀으로의 수율을 향상시키는 효과가 탁월하여, 향후의 경제적인 피셔-트롭쉬 공정 개발에 크게 기여할 수 있을 것으로 판단된다.The iron-based Fischer-Tropsch catalyst proposed by the present invention using a cerium-zirconium oxide as a support improves carbon monoxide conversion and reduces selectivity to methane, a major by-product, and thus yields high yields of hydrocarbons and light olefins. The improved effect is expected to greatly contribute to the future development of the Fischer-Tropsch process.
도 1은 실시예 1, 실시예 2 및 비교예 1, 비교예 4에서 제조된 촉매를 사용하여 피셔-트롭쉬 (Fischer-Tropsch) 합성 반응을 수행하였을 때, 반응시간에 따른 일산화탄소의 전환율을 도시한 그래프이다.FIG. 1 shows the conversion rate of carbon monoxide according to reaction time when Fischer-Tropsch synthesis reaction was carried out using the catalysts prepared in Examples 1, 2, and 1 and 4 One graph.
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