KR20070028442A - A catalyst and process for the synthesis of c2-oxygenates by the hydrogenation of carbon monoxide - Google Patents

A catalyst and process for the synthesis of c2-oxygenates by the hydrogenation of carbon monoxide Download PDF

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KR20070028442A
KR20070028442A KR1020067027027A KR20067027027A KR20070028442A KR 20070028442 A KR20070028442 A KR 20070028442A KR 1020067027027 A KR1020067027027 A KR 1020067027027A KR 20067027027 A KR20067027027 A KR 20067027027A KR 20070028442 A KR20070028442 A KR 20070028442A
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catalyst
weight ratio
synthesis
impregnation
oxygenate
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홍위안 루오
윈지에 딩
홍메이 윈
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비피 피이. 엘. 시이.
달리안 인스티튜트 오브 케미컬 피직스
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Priority to KR1020067027027A priority Critical patent/KR20070028442A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

A catalyst is invented for the synthesis of C2-oxygenates by the hydrogenation of CO. The catalyst is composed of Rh-Mn-Fe-M1- M2/Si02, among them Mn, Fe, M1 and M2 and additives. M1 can be Li or Na while M2 can be Ru or Ir. The content of Rh is 0.1-3% by weight; the weight ratio of Mn/Rh is 0.5-12, the weight ratio of Fe/Rh is 0.01-0.5, the weight ratio of M1/Rh is 0.01-1 and the weight ratio of M2/Rh is 0.1-1.0. The catalyst is prepared by impregnation of the solution of corresponding compounds of each component in desired amount onto the carrier of Si02, which is followed by drying at 283-473 K. Before using, the catalyst is reduced by hydrogen or hydrogen-containing gas at 573-673 K for at least one hour after drying or after calcinations at 473-673 K for 2-20h. These catalysts can convert CO and H2 into ethanol, acetaldehyde, acetic acid and other C2-oxygenates at a high conversion and a high selectivity under mild conditions. ® KIPO & WIPO 2007

Description

일산화 탄소의 수소화에 의한 Ｃ2-옥시게네이트의 합성을 위한 방법 및 촉매{A CATALYST AND PROCESS FOR THE SYNTHESIS OF C2-OXYGENATES BY THE HYDROGENATION OF CARBON MONOXIDE}A method and catalyst for the synthesis of C2-oxygenate by hydrogenation of carbon monoxide {A CATALYST AND PROCESS FOR THE SYNTHESIS OF C2-OXYGENATES BY THE HYDROGENATION OF CARBON MONOXIDE}

본 발명은 CO의 수소화에 의한 C2-옥시게네이트의 합성용 촉매에 관한 것이다. 더 자세하게는, 본 발명은 에탄올, 아세트산, 아세트알데히드 및 아세트산 에스테르를 제조하는 CO 의 수소화를 위한 로듐 기재의 다중 성분 촉매에 관한 것이다. The present invention relates to a catalyst for the synthesis of C 2 -oxygenate by hydrogenation of CO. More particularly, the present invention relates to a rhodium based multicomponent catalyst for hydrogenation of CO to produce ethanol, acetic acid, acetaldehyde and acetic acid esters.

본 발명은 또한 경질(mild) 조건하에서 합성가스로부터 C2-옥시게네이트의 합성 방법 및 촉매의 합성 방법을 포함한다. The present invention also includes a process for synthesizing C 2 -oxygenate from syngas under mild conditions and a process for synthesizing a catalyst.

세계적으로 오일 자원은 감소되고, 그 가격 및 소비는 증가되면서, 새로운 에너지 자원 개발이 전세계적으로 시급해지고 있다. C2-옥시게네이트 중에서, 에탄올이 가솔린에서 첨가제 및 높은 옥탄가 청정 연료로서 점점 더 중요해지고 있다. 따라서, 합성가스로부터 에탄올의 직접적인 합성이 전세계적인 이목을 끌고 있다. 최근에는 다중 촉진제와 함께 Rh-기재 촉매가 광범위하게 연구되고 있으며 다수의 특허가 공개되고 있다. 특허 GB1501891 에서는 Rh-Fe 기재 지 지 촉매(supported catalyst); J6148437 및 J62148438 에서는 Mg 또는 Ir 및 Li로 촉진된 Rh-Mn 기재 촉매; J59227831 의 특허에서는 Rh-Mn-Ir-Li 기재 촉매; J6032733 특허에서는 Rh, Mn, Fe, Li 기재 촉매; 및 Li 또는 Na 에 의해 촉진된 Rh-Mn-Fe 기재 촉매가 그 예이다. 상기 촉매의 공통적인 특징은 Rh 가 고하중인 점이다. 이에 따라 단위 로듐 당 C2-옥시게네이트의 낮은 시공(time space) 생산성 및 고가의 촉매 합성으로 인해 촉매의 산업적 적용이 제한된다. As oil resources are reduced globally and their prices and consumption increase, the development of new energy resources is urgent worldwide. Among the C 2 -oxygenates, ethanol is becoming increasingly important as an additive and high octane clean fuel in gasoline. Thus, the direct synthesis of ethanol from syngas has attracted worldwide attention. Recently, Rh-based catalysts with multiple promoters have been extensively studied and many patents have been published. Patent GB1501891 describes Rh-Fe based supported catalysts; J6148437 and J62148438 include Rh-Mn based catalysts promoted with Mg or Ir and Li; J59227831 patent discloses a catalyst based on Rh-Mn-Ir-Li; J6032733 patent discloses catalysts based on Rh, Mn, Fe, Li; And Rh-Mn-Fe based catalysts promoted by Li or Na. A common feature of these catalysts is that Rh is loading. This limits the industrial application of the catalyst due to the low time space productivity of C 2 -oxygenate per unit rhodium and expensive catalyst synthesis.

본 발명은 CO 의 수소화에 의한 C2-옥시게네이트의 합성 방법 및 촉매를 제공하는 것이다. The present invention provides a method and catalyst for synthesizing C 2 -oxygenate by hydrogenation of CO.

본 발명의 다른 목적은 촉매 합성 방법을 제공하는 것이다. Another object of the present invention is to provide a method for the synthesis of catalysts.

본 발명의 촉매는 저하중의 로듐을 갖고 고활성을 가진다. 로듐 중량 단위 당 상기 촉매 성능은 매우 높다. 본 발명의 촉매는 Rh-Mn-Fe-M1-M2/SiO2 으로 이루어지고 이들 중에서 M1 은 Li 또는 Na 와 같은 알칼리 금속 원소이고, M2 는 Ru 또는 Ir 이다. 본 발명에서 설명되는 바와 같이, 로듐의 중량 하중은 0.1 ~ 3%, 바람직하게는 0.3 ~ 2 %, 더욱 바람직하게는 0.7 ~ 1.5% 이다. Mn/Rh 의 중량비는 0.5 ~ 12, 바람직하게는 0.5 ~ 10, 더욱 바람직하게는 1 ~ 8 이다. Fe 의 중량 하중은 0.01 ~ 0.5, 바람직하게는 0.02 ~ 0.3, 더욱 바람직하게는 0.04 ~ 0.2 이다. M1/Rh 의 중량비는 0.01 ~ 1, 바람직하게는 0.02 ~ 0.5, 더욱 바람직하게는 0.04 ~ 0.2 이다. M2/Rh 의 중량비는 0.1 ~ 1.0, 바람직하게는 0.2 ~ 0.8, 더욱 바람직하게는 0.3 ~ 0.7 이다. 본 발명의 바람직한 구현예에 따르면, 본 발명의 촉매는 Ag 및/또는 Zr 과 같은 첨가제를 포함하지 않는다. The catalyst of the present invention has rhodium in the lowering phase and has high activity. The catalyst performance per unit of rhodium weight is very high. The catalyst of the present invention consists of Rh-Mn-Fe-M 1 -M 2 / SiO 2 , wherein M 1 is an alkali metal element such as Li or Na, and M 2 is Ru or Ir. As explained in the present invention, the weight load of rhodium is 0.1 to 3%, preferably 0.3 to 2%, more preferably 0.7 to 1.5%. The weight ratio of Mn / Rh is 0.5-12, Preferably it is 0.5-10, More preferably, it is 1-8. The weight load of Fe is 0.01 to 0.5, preferably 0.02 to 0.3, more preferably 0.04 to 0.2. The weight ratio of M 1 / Rh is 0.01 to 1, preferably 0.02 to 0.5, and more preferably 0.04 to 0.2. The weight ratio of M 2 / Rh is 0.1 to 1.0, preferably 0.2 to 0.8, and more preferably 0.3 to 0.7. According to a preferred embodiment of the invention, the catalyst of the invention does not comprise additives such as Ag and / or Zr.

촉매 제조 방법은 하기에 기술된다:The catalyst preparation method is described below:

촉매는 함침(impregnation) 방법에 의해 제조된다. 바람직한 방법은 공함침(co-impregnation)일 것이나, 단계식 함침이 또한 가능하다. 촉매내 성분의 전구체는 클로라이드, 니트레이트 또는 기타 분해가능 화합물, 예컨대 암모니아 배위결합된 클로라이드, 카르보닐기 배위결합된 것 등일 수 있다. 용매는 물 또는 메탄올과 같은 비수성 용매일 수 있다. The catalyst is prepared by an impregnation method. The preferred method will be co-impregnation, but stepwise impregnation is also possible. Precursors of components in the catalyst may be chlorides, nitrates or other degradable compounds such as ammonia coordinated chloride, carbonyl group coordinated and the like. The solvent can be water or a non-aqueous solvent such as methanol.

공함침 방법이 촉매 제조에 사용되는 경우, 전구체 화합물이 용매에 용해된다. 이어서 일정 농도의 용액이 실리카 겔 지지체 상으로 함침된다. 최소량의 함침 용액이 실리카 겔의 지지체 전부를 잠수시키는 데 요구된다. 단계식 함침의 방법이 사용되는 경우에는, 해당 화합물이 일정 농도를 지닌 용액으로 혼화되며 상기 용액은 단계적으로 실리카 겔의 촉매 지지체 상으로 함침되거나 또는 여러 화합물이 혼합 용액에 혼화되는데 이는, 해당 화합물의 나머지 용액에 우선하여 함침된다. When the co-impregnation method is used to prepare the catalyst, the precursor compound is dissolved in the solvent. A solution of a certain concentration is then impregnated onto the silica gel support. A minimum amount of impregnation solution is required to submerge all of the support of silica gel. When the stepwise impregnation method is used, the compound is blended into a solution having a certain concentration and the solution is impregnated onto the catalyst support of silica gel step by step or several compounds are mixed into the mixed solution. The remaining solution is impregnated preferentially.

건조 온도는 283 ~ 473 K 이고, 건조 시간은 2 시간 내지 20 일이다. 건조 시간은 선택한 건조 온도에 연관된다. 건조 온도가 373 ~ 393 K 인 경우에는, 건조 절차는 4 내지 12 시간 지속될 수 있다. 건조된 촉매는 2 내지 20 시간 동안 473 ~ 673 K 에서 하소될 수 있으나, 또한 촉매 전구체로서 직접 사용될 수도 있다. 상기 촉매 전구체는 순수 수소 또는 수소 함유 기체 중에 환원될 필요가 있다. 본 발명의 촉매는 C2-옥시게네이트에 대해서 높은 공시 수율을 나타낸다. The drying temperature is 283-473 K and the drying time is 2 hours to 20 days. The drying time is related to the drying temperature selected. If the drying temperature is 373-393 K, the drying procedure can last 4 to 12 hours. The dried catalyst may be calcined at 473-673 K for 2-20 hours, but may also be used directly as catalyst precursor. The catalyst precursor needs to be reduced in pure hydrogen or a hydrogen containing gas. The catalyst of the present invention exhibits high disclosure yields for C 2 -oxygenate.

합성가스 유래의 C2-옥시게네이트 합성을 위한 촉매는 SV = 100 ~ 5000 h-1, 바람직하게는 500 ~ 2000 h-1; T = 500 ~ 750 K, 바람직하게는 573 ~ 673 K; P = 0.1 ~ 1.0 MPa, 바람직하게는 0.1 ~ 0.5 MPa 에서 H2 유동 중 원위치에서 우선 활성된다. 상기의 Rh 기재 촉매를 이용한 합성가스로부터 C2-옥시게네이트 합성 방법은 하기 조건 하에서 실행된다: T = 473 ~ 723 K, 바람직하게는 473 ~ 623 K; P = 1.0 ~ 12.0 MPa, 바람직하게는 2.0 ~ 8.0 MPa; H2/CO 의 부피비 = 1.0 ~ 3.0, 바람직하게는 2.0 ~ 2.5; 공간 속도 = 1000 ~ 50000 h-1; 바람직하게는 10000 ~ 25000 h-1. The catalyst for synthesizing C 2 -oxygenate derived from syngas is preferably SV = 100 to 5000 h −1 , preferably 500 to 2000 h −1 ; T = 500-750 K, preferably 573-673 K; P = 0.1 to 1.0 MPa, preferably 0.1 to 0.5 MPa, which is first activated in situ in the H 2 flow. The C 2 -oxygenate synthesis process from syngas using the above Rh based catalyst is carried out under the following conditions: T = 473-723 K, preferably 473-623 K; P = 1.0 to 12.0 MPa, preferably 2.0 to 8.0 MPa; Volume ratio of H 2 / CO = 1.0 to 3.0, preferably 2.0 to 2.5; Space velocity = 1000 to 50000 h -1 ; Preferably from 10000 to 25000 h -1.

실시예Example 1: 촉매 제조 방법 1: catalyst production method

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, LiNO3, Fe(NO3)2, H2IrCl6 의 수용액 일정량으로 함침하고, 이어서 383 K 에서 6 시간 동안 건조시켰다. 수득한 촉 매는 1 % Rh = 1 % Mn - 0.05 % Fe - 0.075 % Li - 0.5 % Ir/SiO2(중량비)의 화학 조성을 가졌다. The silica support was RhCl 3 . An amount of an aqueous solution of xH 2 O, Mn (NO 3 ) 2 , LiNO 3 , Fe (NO 3 ) 2 , H 2 IrCl 6 was impregnated, followed by drying at 383 K for 6 hours. The resulting catalyst had a chemical composition of 1% Rh = 1% Mn-0.05% Fe-0.075% Li-0.5% Ir / SiO 2 (weight ratio).

실시예Example 2: 촉매 합성 방법 2: catalyst synthesis method

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, LiNO3, Fe(NO3)2, H2IrCl6 의 수용액 일정량으로 함침하고 383 K 에서 6 시간 동안 건조했다. 이에 따라 1 % Rh - 1 % Mn - 0.1 % Fe - 0.075 % Li - 0.5 % Ir/SiO2 (중량비) 의 촉매를 수득했다.The silica support was RhCl 3 . An aqueous solution of xH 2 O, Mn (NO 3 ) 2 , LiNO 3 , Fe (NO 3 ) 2 , H 2 IrCl 6 was impregnated with a certain amount and dried at 383 K for 6 hours. This gave a catalyst of 1% Rh-1% Mn-0.1% Fe-0.075% Li-0.5% Ir / SiO 2 (weight ratio).

실시예Example 3: 3:

지지된 실리카를 RhCl3 .xH2O, Mn(NO3)2, LiNO3, Fe(NO3)2, H2IrCl6 의 수용액 일정량으로 함침하고 383 K 에서 6 시간 동안 건조했다. 이에 따라 1 % Rh - 1 % Mn - 0.05 % Fe - 0.1 % Li - 0.5 % Ir/SiO2 (중량비)의 촉매를 수득했다. Supported silica was replaced with RhCl 3 . An aqueous solution of xH 2 O, Mn (NO 3 ) 2 , LiNO 3 , Fe (NO 3 ) 2 , H 2 IrCl 6 was impregnated with a certain amount and dried at 383 K for 6 hours. This gave a catalyst of 1% Rh-1% Mn-0.05% Fe-0.1% Li-0.5% Ir / SiO 2 (weight ratio).

실시예Example 4: 4:

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, NaNO3, Fe(NO3)2, H2IrCl6 의 수용액 일정량으로 함침하고 383 K 에서 6 시간 동안 건조했다. 이에 따라 1 % Rh - 1 % Mn - 0.05 % Fe - 0.1 % Na - 0.5 % Ir/SiO2 (중량비)의 촉매를 수득했다. The silica support was RhCl 3 . An aqueous solution of xH 2 O, Mn (NO 3 ) 2 , NaNO 3 , Fe (NO 3 ) 2 , H 2 IrCl 6 was impregnated with a certain amount and dried at 383 K for 6 hours. This gave a catalyst of 1% Rh-1% Mn-0.05% Fe-0.1% Na-0.5% Ir / SiO 2 (weight ratio).

실시예Example 5: 5:

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, LiNO3, Fe(NO3)2, RuCl3 의 수용액 일정량으로 함침하고 383 K 에서 6 시간 동안 건조했다. 이에 따라 1 % Rh - 1 % Mn - 0.1 % Fe - 0.075 % Li - 0.5 % Ru/SiO2 (중량비)의 촉매를 수득했다. The silica support was RhCl 3 . An aqueous solution of xH 2 O, Mn (NO 3 ) 2 , LiNO 3 , Fe (NO 3 ) 2 , RuCl 3 was impregnated with a certain amount and dried at 383 K for 6 hours. This gave a catalyst of 1% Rh-1% Mn-0.1% Fe-0.075% Li-0.5% Ru / SiO 2 (weight ratio).

실시예Example 6: 6:

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, NaNO3, Fe(NO3)2, RuCl3 의 수용액 일정량으로 함침하고 383 K 에서 6 시간 동안 건조했다. 이에 따라 1 % Rh - 2 % Mn - 0.05 % Fe - 0.1 % Na - 0.5 % Ru/SiO2 (중량비)의 촉매를 수득했다. The silica support was RhCl 3 . An aqueous solution of xH 2 O, Mn (NO 3 ) 2 , NaNO 3 , Fe (NO 3 ) 2 , RuCl 3 was impregnated with a certain amount and dried at 383 K for 6 hours. This gave a catalyst of 1% Rh-2% Mn-0.05% Fe-0.1% Na-0.5% Ru / SiO 2 (weight ratio).

실시예Example 7: 7:

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, LiNO3, Fe(NO3)2, H2IrCl6 의 수용액 일정량으로 함침하고 383 K 에서 6 시간 동안 건조했다. 이에 따라 1.5 % Rh - 1.5 % Mn - 0.12 % Fe - 0.11 % Li - 0.5 % Ir/SiO2 (중량비)의 촉매를 수득했다.The silica support was RhCl 3 . An aqueous solution of xH 2 O, Mn (NO 3 ) 2 , LiNO 3 , Fe (NO 3 ) 2 , H 2 IrCl 6 was impregnated with a certain amount and dried at 383 K for 6 hours. This gave a catalyst of 1.5% Rh-1.5% Mn-0.12% Fe-0.11% Li-0.5% Ir / SiO 2 (weight ratio).

비교예Comparative example 1: One:

실리카 지지체를 RhCl3 .xH2O 의 수용액 일정량으로 함침한 후 383 K 에서 6 시간 동안 건조했다. 수득한 촉매는 1% Rh/SiO2 (중량비)로 이루어졌다. The silica support was RhCl 3 . It was impregnated with a certain amount of an aqueous solution of xH 2 O and then dried at 383 K for 6 hours. The obtained catalyst consisted of 1% Rh / SiO 2 (weight ratio).

비교예Comparative example 2: 2:

실리카 지지체를 RhCl3 .xH2O 및 Mn(NO3)2 의 수용액 일정량으로 함침한 후 383 K 에서 6 시간 동안 건조했다. 이에 따라 1 % Rh - 1 % Mn/SiO2 (중량비)의 촉매를 수득했다. The silica support was RhCl 3 . It was impregnated with an amount of an aqueous solution of xH 2 O and Mn (NO 3 ) 2 and then dried at 383 K for 6 hours. This gave a catalyst of 1% Rh-1% Mn / SiO 2 (weight ratio).

비교예Comparative example 3: 3:

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, LiNO3, H2IrCl6 의 수용액 일정량으로 함침한 후 383 K 에서 6 시간 동안 건조했다. 수득한 촉매의 화학 조성은 1 % Rh - 1 % Mn - 0.075 % Li - 0.5 % Ir/SiO2 (중량비)였다. The silica support was RhCl 3 . An aqueous solution of xH 2 O, Mn (NO 3 ) 2 , LiNO 3 , H 2 IrCl 6 was impregnated with a certain amount, and then dried at 383 K for 6 hours. The chemical composition of the obtained catalyst was 1% Rh-1% Mn-0.075% Li-0.5% Ir / SiO 2 (weight ratio).

비교예Comparative example 4: 4:

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, Fe(NO3)2 의 수용액 일정량으로 함침한 후 383 K 에서 6 시간 동안 건조했다. 수득한 촉매의 화학 조성은 1 % Rh - 1 % Mn - 0.05 % Fe/SiO2 (중량비)였다. The silica support was RhCl 3 . The solution was impregnated with a predetermined amount of xH 2 O, Mn (NO 3 ) 2 , and Fe (NO 3 ) 2 , and then dried at 383 K for 6 hours. The chemical composition of the obtained catalyst was 1% Rh-1% Mn-0.05% Fe / SiO 2 (weight ratio).

비교예Comparative example 5: 5:

실리카 지지체를 RhCl3 .xH2O, Mn(NO3)2, LiNO3, H2IrCl6 의 수용액 일정량으로 함침한 후 383 K 에서 6 시간 동안 건조했다. 수득한 촉매의 화학 조성은 1 % Rh - 1 % Mn - 0.075 % Li - 0.5 % Ir/SiO2 (중량비)였다. The silica support was RhCl 3 . An aqueous solution of xH 2 O, Mn (NO 3 ) 2 , LiNO 3 , H 2 IrCl 6 was impregnated with a certain amount, and then dried at 383 K for 6 hours. The chemical composition of the obtained catalyst was 1% Rh-1% Mn-0.075% Li-0.5% Ir / SiO 2 (weight ratio).

일련의 비교 성능 시험을 실시예 촉매 (20 ~ 40 mesh) 의 0.4 g (~ 0.8 ml) 시료로 수행했다. 시험 기기는 외부 가열 시스템을 갖춘 소형 고정층 튜블러 반응기로 이루어지고, 이는 길이가 340 mm, 내경이 4.6 mm 인 316 L 스테인레스 스틸로 조직되어 있다. 촉매는 시험 전에 H2 유동 중 원위치 환원되었다. 온도는 실온에서부터 2K/분으로 623 K까지 상승시키고 이어서 1 시간 동안 일정하게 유지시켰다. H2 유속은 대기압에서 4l/시였다. 이어서 촉매를 523 K 로 냉각 후 합성가스(H2/CO=2)로 이동시키고 T = 593 K, P = 3.0 MPa, SV = 13000 h-1 4시간의 공정 조건 하에서 반응시켰다. 유출액을 옥시게네이트 생성물을 포획하는 150 ml 탈이온수로 가득찬 응축기를 통과시켰다. 수득한 옥시게네이트를 함유하는 수용액을, FID 검출기 및 1-펜탄올을 내부 표준물로서 이용해 FFAP 컬럼인 Varian CP-3800 기체 크로마토그래피로 오프라인 분석했다. 폐가스(tail gas)를 TCD 검출기 및 Porapak QS 컬럼이 장착된 Varian CP-3800 GC로 온라인 분석했다. A series of comparative performance tests were performed with 0.4 g (-0.8 ml) samples of the example catalyst (20-40 mesh). The test equipment consists of a small fixed bed tubular reactor with an external heating system, which consists of 316 L stainless steel with a length of 340 mm and an internal diameter of 4.6 mm. The catalyst was reduced in situ in the H 2 flow prior to testing. The temperature was raised from room temperature to 623 K at 2K / min and then held constant for 1 hour. H 2 flow rate was 4 l / hr at atmospheric pressure. The catalyst was then cooled to 523 K and transferred to syngas (H 2 / CO = 2) and reacted under process conditions of T = 593 K, P = 3.0 MPa, SV = 13000 h -1 4 hours. The effluent was passed through a condenser filled with 150 ml deionized water capturing the oxygenate product. The obtained aqueous solution containing oxygenate was analyzed offline by Varian CP-3800 gas chromatography which is an FFAP column using a FID detector and 1-pentanol as internal standards. Tail gas was analyzed online with a Varian CP-3800 GC equipped with a TCD detector and a Porapak QS column.

실시예 촉매 및 비교예 촉매의 촉매 성능을 표 1 에 기재하였다. The catalytic performances of the example catalysts and the comparative example catalysts are listed in Table 1.

표에서 나타낸 결과는, 로듐 하중이 더 낮고 촉매 합성 방법이 간단하나, 에탄올, 아세트산 및 아세트알데히드의 합성을 위한 실시예 촉매의 활성 및 선택도가 더 높음을 보인다. 실시예 촉매의 로듐 효율은 분명히 비교예 촉매보다 더 높아 산업 용도로 장래성이 있다. The results shown in the table show that the rhodium loading is simple and the method of catalyst synthesis is simple, but the activity and selectivity of the example catalyst for the synthesis of ethanol, acetic acid and acetaldehyde is higher. The rhodium efficiency of the example catalyst is clearly higher than that of the comparative catalyst and is promising for industrial use.

Figure 112006095289362-PCT00001
Figure 112006095289362-PCT00001

Claims (12)

실리카 상 지지된 Rh-Mn-Fe-M1-M2 성분으로 이루어진 CO 의 수소화에 의한 C2-옥시게네이트의 합성용 촉매로, 여기서 M1 은 Li 및/또는 Na일 수 있고, M2 는 Ru 및/또는 Ir 일 수 있으며, Rh 는 총 촉매 중량을 기준으로 0.1 내지 3 중량% 이며,Catalyst for the synthesis of C 2 -oxygenate by hydrogenation of CO consisting of Rh-Mn-Fe-M 1 -M 2 supported on silica, wherein M 1 can be Li and / or Na, M 2 May be Ru and / or Ir, Rh is 0.1 to 3% by weight based on the total catalyst weight, Mn/Rh 의 중량비: 0.5 ~ 12,Weight ratio of Mn / Rh: 0.5-12, Fe/Rh 의 중량비: 0.01 ~ 0.5, Weight ratio of Fe / Rh: 0.01 to 0.5, M1/Rh 의 중량비 : 0.01 ~ 1,M 1 / Rh weight ratio: 0.01 ~ 1, M2/Rh 의 중량비: 0.1 ~ 1.0 인 촉매. Catalyst having a weight ratio of M 2 / Rh: 0.1 to 1.0. 목적하는 양으로 해당 성분의 화합물을 용매 중에 용해시켜 수득된 용액 제조, 상기 용액을 실리카 겔 촉매 지지체 상으로 함침 후, 283 ~ 473 K 에서 2 시간 내지 20 일 동안 건조를 포함하는 제 1 항에 따른 촉매의 제조 방법. Preparation of a solution obtained by dissolving a compound of the component in a desired amount in a solvent, the impregnation of the solution onto a silica gel catalyst support, followed by drying at 283-473 K for 2 to 20 days. Process for preparing a catalyst. 제 2 항에 있어서, 사용된 화합물이 분해가능 클로라이드 또는 니트레이트이고 용매는 물 또는 비수성 용매인 방법. The process of claim 2 wherein the compound used is degradable chloride or nitrate and the solvent is water or a non-aqueous solvent. 제 2 항 또는 제 3 항에 있어서, 실리카 겔이 졸 가공에 이어서 염기성 용액 중에서 가열한 후 건조 및/또는 하소에 의해 제조되는 방법. The process according to claim 2 or 3, wherein the silica gel is prepared by sol processing followed by heating in basic solution followed by drying and / or calcination. 제 2 항 내지 제 4 항 중 어느 한 항에 있어서, 사용된 화합물이 암모니아 배위결합된 클로라이드 또는 카르보닐기 배위결합된 화합물인 방법. The method according to any one of claims 2 to 4, wherein the compound used is ammonia coordinated chloride or carbonyl group coordinated compound. 제 2 항 내지 제 5 항 중 어느 한 항에 있어서, 용매가 메탄올인 방법. The process according to any of claims 2 to 5, wherein the solvent is methanol. 제 2 항 내지 제 6 항 중 어느 한 항에 있어서, 촉매가 573 내지 673 K 에서 1 시간 이상 동안 순수 수소 또는 수소 함유 기체 중 원위치에서 환원되는 방법. The process according to claim 2, wherein the catalyst is reduced in situ in pure hydrogen or hydrogen containing gas at 573 to 673 K for at least 1 hour. 제 2 항 내지 제 7 항 중 어느 한 항에 있어서, 함침이 모든 성분의 공함침 또는 단계적 함침으로 수행되는 방법. 8. Process according to any one of claims 2 to 7, wherein the impregnation is carried out by co-impregnation or step impregnation of all components. 제 8 항에 있어서, 단계적 함침이 임의 순서로 실시되는 방법. The method of claim 8, wherein the stepwise impregnation is performed in any order. 제 2 항 내지 제 9 항 중 어느 한 항에 따른 방법에 의해 수득가능한 C2-옥시게네이트의 합성용 촉매. A catalyst for the synthesis of C 2 -oxygenate obtainable by the process according to any one of claims 2 to 9. 합성 가스로부터 C2-옥시게네이트의 합성을 위한 제 1 항 또는 제 9 항 중 어느 한 항에 따른 촉매의 용도. Use of a catalyst according to any one of claims 1 to 9 for the synthesis of C 2 -oxygenate from synthesis gas. 제 11 항에 있어서, 옥시게네이트가 주로 에탄올, 아세트알데히드 및 아세트산인 용도. Use according to claim 11, wherein the oxygenate is mainly ethanol, acetaldehyde and acetic acid.
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