KR20150028329A - High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses - Google Patents
High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses Download PDFInfo
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- KR20150028329A KR20150028329A KR1020157002325A KR20157002325A KR20150028329A KR 20150028329 A KR20150028329 A KR 20150028329A KR 1020157002325 A KR1020157002325 A KR 1020157002325A KR 20157002325 A KR20157002325 A KR 20157002325A KR 20150028329 A KR20150028329 A KR 20150028329A
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- active composition
- catalyst
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- 238000000034 method Methods 0.000 title claims abstract description 79
- 230000008569 process Effects 0.000 title claims abstract description 61
- 238000002407 reforming Methods 0.000 title claims abstract description 43
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 33
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 26
- 239000001569 carbon dioxide Substances 0.000 title description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 50
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 27
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 239000004480 active ingredient Substances 0.000 claims description 16
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- 238000003786 synthesis reaction Methods 0.000 claims description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
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- 229910000457 iridium oxide Inorganic materials 0.000 description 3
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- 230000009467 reduction Effects 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
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- -1 platinum metals Chemical class 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
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- 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
본 발명은, 이리듐-함유 활성 조성물의 존재 하에서 탄화수소, 바람직하게 메탄의 CO2 개질을 위한 촉매적 고압 공정, 및 또한 Ir이 지르코늄 다이옥사이드-함유 지지체 물질 상에 미세하게 분산된 형태로 존재하는 바람직한 활성 조성물에 관한 것이다. 지르코늄 다이옥사이드의 대부분은 바람직하게 입방정계 및/또는 정방정계 구조를 갖고, 지르코늄 다이옥사이드는 더욱 바람직하게 하나 이상의 도핑 원소에 의해 안정화된다. 본 발명의 공정에서, 개질 가스는 5 bar 초과, 바람직하게 10 bar 초과 및 더욱 바람직하게 20 bar 초과의 압력 및 600 내지 1200 ℃ 범위, 바람직하게 850 내지 1100 ℃ 범위 및 특히 850 내지 950 ℃ 범위의 온도에서 접촉되고, 합성 가스로 전환된다. 본 발명의 공정은 단지 소량의 수증기를 포함하거나 수증기가 전혀 없는 개질 가스를 사용하여 수행된다. 공정에서, 공정 수행 동안 촉매 상의 탄소질 물질의 형성이 크게 억제되고, 그 결과 나타나는 활성에의 유의한 감소 없이 장시간에 걸쳐 공정이 수행될 수 있다.The present invention relates to a catalytic high-pressure process for the CO 2 reforming of hydrocarbons, preferably methane, in the presence of an iridium-containing active composition, and also to a process for the production of the desired activity present in finely dispersed form on the zirconium dioxide- ≪ / RTI > Most of the zirconium dioxide preferably has a cubic system and / or a tetragonal system, and the zirconium dioxide is more preferably stabilized by one or more doping elements. In the process of the present invention, the reforming gas has a pressure of greater than 5 bar, preferably greater than 10 bar and more preferably greater than 20 bar, and a temperature in the range of from 600 to 1200 ° C, preferably in the range of from 850 to 1100 ° C and especially in the range of from 850 to 950 ° C And is converted to syngas. The process of the present invention is carried out using a reformed gas that contains only a small amount of water vapor or no water vapor. In the process, the formation of the carbonaceous material on the catalyst during the process run is greatly suppressed, and the process can be performed for a long time without a significant decrease in the resulting activity.
Description
본 발명은 이리듐-함유 활성 조성물을 사용하는 탄화수소의 이산화탄소 개질을 위한 고압 공정에 관한 것이다.
The present invention relates to a high-pressure process for the carbon dioxide modification of hydrocarbons using an iridium-containing active composition.
화학 공정에서 시약으로서 이산화탄소를 사용하는 것은, 대기 중으로 이산화탄소의 배출을 감소시키기 위하여 경제적 및 산업적으로 매우 중요하다. The use of carbon dioxide as a reagent in chemical processes is very important both economically and industrially in order to reduce the emission of carbon dioxide into the atmosphere.
다양한 과학적 문헌 및 특허가 합성 가스 제조에 관련된 것이다. 귀금속-함유 촉매가(건조 개질로도 알려진) 메탄의 이산화탄소 개질을 위해 사용될 수 있다고 알려져 있다.A variety of scientific literature and patents are involved in the synthesis of syngas. It is known that noble metal-containing catalysts can be used for carbon dioxide reforming of methane (also known as dry reforming).
이하, 메탄의 이산화탄소 개질 분야에서의 선행 문헌들의 개요를 개시한다.An overview of the prior art in the field of carbon dioxide reforming of methane is presented below.
메탄의 이산화탄소 개질의 개요는 브래드포드 등에 의한 문헌에 개시되어 있다(M.C.J. Bradford, M.A. Vannice; Cataly. Rev.-Sci. Eng., 41 (1) (1999) p.1-42).An overview of the carbon dioxide reforming of methane is disclosed in Bradford et al. (M. C. Bradford, M. A. Vannice; Cataly. Rev.-Sci. Eng., 41 (1) (1999) p.1-42).
미국 특허 제6,749,828호는, 지르코늄-함유 종을 침전시키기 위하여 루테늄이 지르코늄 다이옥사이드 상에 증착되거나 루테늄 염이 추가된 촉매를 개시하고 있다. 상기 촉매는 이산화탄소를 포함하는 개질 가스의 전환에서 높은 수율을 도모하도록 한다. 또한, 오직 소량의 탄소질 증착물이 촉매 상에 생성된다. 실험적 실시예는 0.98 bar 및 4.9 bar의 압력에서 수행된 촉매작용 시험을 개시한다. 하나의 시험에서(즉, 실시예 6), 온도는 1000 ℃였다. 그외에는, 780 내지 800 ℃의 온도에서 시험이 수행되었다. 또한, 증기의 존재 하에서 촉매 시험이 수행되었으며, 이 때 0.1 내지 10의 증기/탄소 비가 통상적인 것으로 간주되었고 0.4 내지 4의 증기/탄소 비가 바람직하다고 개시되어 있다.U.S. Patent No. 6,749,828 discloses a catalyst in which ruthenium is deposited on zirconium dioxide or ruthenium salt is added to precipitate zirconium-containing species. The catalyst ensures a high yield in the conversion of the reformed gas containing carbon dioxide. Also, only small amounts of carbonaceous deposits are formed on the catalyst. The experimental example discloses a catalysis test carried out at pressures of 0.98 bar and 4.9 bar. In one test (i.e., Example 6), the temperature was 1000 占 폚. Otherwise, the test was carried out at a temperature of 780 to 800 ° C. Catalyst tests were also carried out in the presence of steam, wherein a steam / carbon ratio of 0.1 to 10 was considered common and a vapor / carbon ratio of 0.4 to 4 was preferred.
미국 특허공개 제2005/0169835호는, 지지체 물질로서 베타 형태를 갖는 50 중량% 초과의 규소 카바이드를 포함하는 촉매 상에서 개질 가스가 이산화탄소 및 메탄과 반응하는 공정을 기재한다. 규소 카바이드 지지체 물질을 제외하고, 촉매는 활성 성분으로서 0.1 내지 10%의 비율로 귀금속 또는 니켈을 추가로 포함할 수 있다. 가능한 귀금속은 Rh, Ru, Pt 또는 Ir 및 이들의 혼합물이다.U.S. Patent Publication No. 2005/0169835 describes a process wherein a reformed gas reacts with carbon dioxide and methane over a catalyst comprising more than 50% by weight of silicon carbide having a beta form as support material. Except for the silicon carbide support material, the catalyst may additionally contain noble metals or nickel in a proportion of 0.1 to 10% as active ingredient. Possible noble metals are Rh, Ru, Pt or Ir and mixtures thereof.
미국 특허 제5,753,143호는, 메탄의 존재 하에서 이산화탄소의 개질을 위한 촉매 공정으로서, 증기의 부재 하에서 수행될 수 있는 공정을 기재하고 있다. 활성 성분으로서 Rh를 갖는 제올라이트가 촉매로서 개시되어 있다.U.S. Patent No. 5,753,143 describes a process that can be carried out in the absence of steam as a catalytic process for the modification of carbon dioxide in the presence of methane. A zeolite having Rh as an active ingredient is disclosed as a catalyst.
미국 특허 제7,166,268호는, 촉매가 지지체로서 CeO2를 포함하는 결정 알루미나를 포함하고, 활성 성분으로서 루테늄과 코발트가 지지체 상에 분산된, 수소 또는 합성 가스의 제조를 위한 증기 개질 공정을 기재하고 있다. 공정은 또한 탄화수소의 이산화탄소 개질을 위해 사용될 수 있다.U.S. Patent No. 7,166,268 describes a steam reforming process for the production of hydrogen or syngas wherein the catalyst comprises crystalline alumina containing CeO 2 as a support and ruthenium and cobalt as active components are dispersed on a support . The process can also be used for carbon dioxide reforming of hydrocarbons.
유럽 특허 제1 380 341호는, 증기 개질 공정에 의한 탄화수소의 개질 공정을 기재하고 있다. 활성 성분은 Ru, Pt, Rh, Pd, Ir 및 Ni로 이루어진 군으로부터 선택된 원소이다. 활성 성분을 위한 지지체는 알루미나 및 5 내지 95 중량%의 망간 옥사이드를 포함한다.EP-A-1 380 341 describes a process for reforming hydrocarbons by a steam reforming process. The active ingredient is an element selected from the group consisting of Ru, Pt, Rh, Pd, Ir and Ni. The support for the active component comprises alumina and 5 to 95% by weight of manganese oxide.
미국 특허 제7,309,480호는, Ir이 분산된 형태로 존재하는 단사정계 지르코늄 옥사이드를 포함하는 촉매 지지체를 함유하는 수소 생산을 위한 촉매를 개시 및 청구하고 있다.
U.S. Patent No. 7,309,480 discloses and claims a catalyst for the production of hydrogen containing a catalyst support comprising a monoclinic zirconium oxide in which Ir is present in a dispersed form.
본 발명의 하나의 목적은, 종래에 알려진 공정에 비하여 높은 에너지 효율을 갖는 합성 가스의 제조를 위한 촉매 공정을 제공하는 것이다. 추가의 목적은 이산화탄소가 화학적으로 전환될 수 있는 촉매 공정을 제공하는 것이다. 본 발명의 목적은 적합한 촉매의 개발 및 적합한 개질 공정의 개발 모두와 관련된 것이다.It is an object of the present invention to provide a catalytic process for the production of syngas with high energy efficiency compared to processes known in the art. A further object is to provide a catalytic process in which the carbon dioxide can be chemically converted. The object of the present invention is both to develop suitable catalysts and to develop suitable reforming processes.
본원에 개시된 목적 및 개시되지 않은 추가의 목적은, CO2의 존재 하에서의 탄화수소, 바람직하게 메탄의 개질을 위한 개질 공정 및 촉매의 제공에 의해 달성되며, 첫째로 본 발명에 따른 촉매 및 이후 본 발명의 개질 공정을 하기에 보다 구체적으로 개시한다.
The objects disclosed and further disclosed herein are achieved by the provision of a catalyst and a reforming process for the modification of hydrocarbons, preferably methane, in the presence of CO 2 , wherein the catalyst according to the invention and, The reforming process will be described more specifically below.
도 1은 환원 처리 전에 촉매 샘플 S2 상에서 기록된 X선 회절 패턴을 나타낸다.
도 2는 환원되지 않은 형태의 촉매 샘플 S3 상에서 기록된 X선 회절 패턴을 나타낸다.Fig. 1 shows the X-ray diffraction pattern recorded on the catalyst sample S2 before the reduction treatment.
Fig. 2 shows the X-ray diffraction pattern recorded on the catalyst sample S3 in the non-reduced form.
I. 개질 촉매I. reforming catalyst
본 발명은, 활성 성분으로서 적어도 이리듐 및 지르코늄 다이옥사이드-함유 지지체 물질을 포함하는 활성 조성물을 갖는, 탄화수소, 바람직하게 메탄의 CO2 개질을 위한 촉매에 관한 것으로서,The present invention is directed to a catalyst for CO 2 reforming of hydrocarbons, preferably methane, having an active composition comprising at least an iridium and zirconium dioxide-containing support material as active ingredient,
a) Ir 함량은 지르코늄 다이옥사이드-함유 활성 조성물을 기준으로 0.01 내지 10 중량%, 바람직하게 0.05 내지 5 중량% 및 더욱 바람직하게 0.1 내지 1 중량% 범위이고,a) the Ir content is in the range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight and more preferably 0.1 to 1% by weight, based on the zirconium dioxide-
b) 지르코늄 다이옥사이드-함유 지지체 물질 내의 지르코늄 다이옥사이드는, X선 회절 분석법에 따라서, 대부분 입방정계 및/또는 정방정계 구조 형태로 존재하되, 입방정계 및/또는 정방정계 상의 비율은 50 중량% 초과, 더욱 바람직하게 70 중량% 초과 및 특히 90 중량% 초과이다.b) The zirconium dioxide in the zirconium dioxide-containing support material is present in the form of mostly cubic and / or tetragonal structures according to X-ray diffraction analysis, wherein the ratio of cubic system and / or tetragonal system is greater than 50% Preferably more than 70% by weight and especially more than 90% by weight.
본 발명 촉매의 바람직한 양태에서, 지르코늄 다이옥사이드-함유 활성 조성물은 5 m2/g 초과, 바람직하게 20 m2/g 초과, 더욱 바람직하게 50 m2/g 및 특히 80 m2/g 초과의 비표면적을 갖는다. 촉매의 비표면적 측정은 BET 방법을 사용한 가스 흡착법(ISO 9277:1995)으로 수행되었다.In a preferred embodiment of the catalyst of the present invention, the zirconium dioxide-containing active composition has a specific surface area of greater than 5 m 2 / g, preferably greater than 20 m 2 / g, more preferably greater than 50 m 2 / g and in particular greater than 80 m 2 / g Respectively. The specific surface area of the catalyst was measured by a gas adsorption method (ISO 9277: 1995) using the BET method.
이리듐은 지르코늄 다이옥사이드 지지체 상에서 미세하게 분산된 형태로 존재하는 것이, 낮은 함량의 Ir에서 높은 촉매 활성이 수득되므로 특히 유리하다.It is particularly advantageous that iridium is present in a finely dispersed form on the zirconium dioxide support since high catalytic activity is obtained in the low content of Ir.
본 발명 촉매의 바람직한 양태는, Ir이 지르코늄 다이옥사이드-함유 지지체 상에 존재하고, 후자가 추가의 원소로 도핑되는 것이다. 지르코늄 다이옥사이드 지지체의 도핑을 위하여, 바람직한 것은 주기율표의 희토류(즉, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu로 이루어진 군), IIa족(즉, Mg, Ca, Sr, Ba로 이루어진 군), IVa족(즉, Si로 이루어진 군), IVb족(즉, Ti, Hf로 이루어진 군), Vb족(즉, V, Nb, Ta로 이루어진 군)으로부터 선택된 원소 및 이들의 옥사이드이다.A preferred embodiment of the catalyst of the present invention is that Ir is present on a zirconium dioxide-containing support and the latter is doped with further elements. For doping of the zirconium dioxide support, preferred are rare earths (i.e., Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, (I.e., a group consisting of Mg, Ca, Sr and Ba), a Group IVa (i.e., a group consisting of Si), a Group IVb (i.e. a group consisting of Ti and Hf) Nb and Ta), and oxides thereof.
추가의 도핑 원소는, 그중에서도, Pt, Pd, Ru, Rh와 같은 백금 금속, Ni, Co 및 Fe와 같은 비금속(base metals), Mn과 같은 다른 금속 또는 당업자에게 알려진 다른 촉진제일 수 있다.Additional doping elements may be platinum metals such as Pt, Pd, Ru, Rh, base metals such as Ni, Co and Fe, other metals such as Mn, or other promoters known to those skilled in the art.
촉매가 Ir 및 지르코늄 다이옥사이드에 더하여 희토류 군으로부터의 하나 이상의 도핑 원소를 포함할 경우, 도핑 원소의 중량 비율은 촉매의 총 중량을 기준으로 0.01 내지 80 중량% 범위, 바람직하게 0.1 내지 50 중량% 범위 및 특히 1.0 내지 30 중량% 범위이다.When the catalyst comprises at least one doping element from the rare earth group in addition to Ir and zirconium dioxide, the weight ratio of the doping element is in the range of 0.01 to 80 wt.%, Preferably 0.1 to 50 wt.%, Especially from 1.0 to 30% by weight.
이론적 고찰에 의한 본 발명의 제한 없이, 상술된 하나 이상의 원소로 활성 조성물을 도핑하는 것이 지르코늄 다이옥사이드의 정방정계 또는 입방정계 상의 안정화를 도모하는 것으로 추정된다. 또한, 지르코늄 다이옥사이드 지지체의 이온-전도성 성질 또는 레독스(redox) 성질이 도핑에 의해 영향을 받는다는 것을 알 수 있다. 고온, 고압 및 매우 낮은 증기-대-메탄 비에서의 CO2 존재 하에서 메탄의 개질을 위한 촉매 활성에 미치는 이러한 성질의 영향은 유의한 것으로 보인다.Without the limitations of the present invention by theoretical considerations, it is believed that doping the active composition with one or more of the above-mentioned elements will stabilize the zirconium dioxide on the tetragonal or cubic system. It can also be seen that the ion-conducting or redox properties of the zirconium dioxide support are affected by doping. The effect of this property on the catalytic activity for the modification of methane in the presence of CO 2 at high temperature, high pressure and very low steam-to-methane ratio appears to be significant.
특히 바람직한 양태에서, 본 발명에 따른 활성 조성물은 이리듐 및 지르코늄 다이옥사이드 뿐만 아니라 추가의 도핑 원소로서 이트륨 또한 포함하고, 이 때 이트륨은 산화 형태로 존재한다. 이트륨 옥사이드의 함량은 ZrO2를 기준으로 바람직하게 0.01 내지 80 중량%, 더욱 바람직하게 0.1 내지 50 중량% 및 특히 더욱 바람직하게 1.0 내지 30 중량% 범위이다. 이트륨으로의 도핑은 ZrO2의 입방정계 또는 정방정계 상의 안정화를 도모한다.In a particularly preferred embodiment, the active composition according to the invention also comprises yttrium as an additional doping element as well as iridium and zirconium dioxide, wherein the yttrium is present in oxidized form. The content of yttrium oxide is preferably from 0.01 to 80% by weight, more preferably from 0.1 to 50% by weight, and particularly preferably from 1.0 to 30% by weight, based on ZrO 2 . Doping with yttrium stabilizes the cubic or tetragonal phase of ZrO 2 .
추가의 바람직한 양태에서, 본 발명에 따른 활성 조성물이 이리듐 및 지르코늄 다이옥사이드 뿐만 아니라 도핑 원소로서 희토류 군으로부터의 추가의 두 가지 원소를 포함한다. 도핑 원소의 함량은 ZrO2 함량을 기준으로 바람직하게 0.01 내지 80 중량%, 더욱 바람직하게 0.1 내지 50 중량% 및 특히 더욱 바람직하게 1.0 내지 30 중량% 범위이다. 특히 바람직한 것은 도핑 원소로서 란타늄(La) 및 세륨(Ce)을 사용하는 것이다.In a further preferred embodiment, the active composition according to the invention comprises two further elements from the rare earth group as doping elements as well as iridium and zirconium dioxide. The content of the doping element is preferably in the range of 0.01 to 80% by weight, more preferably 0.1 to 50% by weight, and particularly preferably 1.0 to 30% by weight, based on the ZrO 2 content. Particularly preferred is to use lanthanum (La) and cerium (Ce) as doping elements.
란타늄 및 세륨으로의 도핑은, 이트륨에 의한 안정화와 유사하게 ZrO2의 입방정계 또는 정방정계 상의 안정화를 도모하고, 이 때 La-Zr 옥사이드, Ce-Zr 옥사이드 및 Ce-La-Zr 옥사이드 상이 부분적으로 형성될 수 있다. 본 발명의 촉매에서, 입방정계 및 정방정계 지르코늄 다이옥사이드-함유 상의 총 비율은 존재하는 지르코늄 다이옥사이드를 기준으로 바람직하게 60 중량% 초과, 더욱 바람직하게 70 중량% 초과 및 특히 더욱 바람직하게 80 중량% 초과이다.Doping with lanthanum and cerium can stabilize the cubic or tetragonal phase of ZrO 2 similarly to the stabilization with yttrium where the La-Zr oxide, Ce-Zr oxide and Ce-La-Zr oxide phases are partially . In the catalyst of the present invention, the total proportion of the cubic system and the tetragonal zirconium dioxide-containing phase is preferably greater than 60 wt%, more preferably greater than 70 wt%, and even more preferably greater than 80 wt%, based on the zirconium dioxide present .
놀랍게도 이리듐이 지르코늄 다이옥사이드 상에 증착되어 있고 지르코늄 다이옥사이드 대부분이 정방정계 및/또는 입방정계 구조를 갖는 본 발명에 따른 촉매는, 다른 귀금속-함유 활성 성분을 갖는 대응 촉매 및 이리듐-함유 종이 단사정계 구조를 갖는 지르코늄 다이옥사이드와 접촉하는 대응 촉매에 비하여, 상당히 우수한 구동 수명 및 탄소질 증착물 형성에 대한 향상된 저항을 나타낸다는 점이 발견되었다.Surprisingly, the catalyst according to the invention, in which iridium is deposited on zirconium dioxide and most of the zirconium dioxide has a tetragonal and / or cubic system structure, can be prepared by reacting a corresponding catalyst with another noble metal- containing active component and an iridium- Lt; RTI ID = 0.0 > carbonitride < / RTI > deposition.
특히 바람직한 것은 지르코늄 다이옥사이드가 이트륨으로 도핑되거나 란타늄 및/또는 세륨으로 도핑된 Ir/ZrO2 활성 조성물을 포함하는 본 발명에 따른 촉매이다.Especially preferred is the catalyst according to the invention, the zirconium dioxide doped with yttrium or comprises a Ir / ZrO 2 active composition doped with lanthanum and / or cerium.
추가의 양태에서, 본 발명의 공정에서 사용되는 본 발명에 따른 활성 조성물은 추가적으로 촉진제 및/또는 추가의 금속 양이온을 포함하여 촉매의 효율을 추가로 증가시킨다.In a further embodiment, the active composition according to the invention used in the process of the invention additionally comprises an accelerator and / or further metal cations to further increase the efficiency of the catalyst.
바람직한 양태에서, 본 발명의 촉매 또는 활성 조성물은 Pt, Rh, Pd, Ru, Au로 이루어진 군으로부터의 하나 이상의 귀금속-함유 촉진제를 포함하되, 귀금속-함유 촉진제의 비율은 촉매를 기준으로 0.01 내지 5 중량% 및 더욱 바람직하게 0.1 내지 3 중량% 범위이다.In a preferred embodiment, the catalyst or active composition of the present invention comprises at least one noble metal-containing accelerator from the group consisting of Pt, Rh, Pd, Ru, Au, wherein the ratio of noble metal- By weight and more preferably from 0.1 to 3% by weight.
추가의 바람직한 양태에서, 촉매는 Ni, Co, Fe, Mn, Mo, W로 이루어진 군으로부터의 하나 이상의 비금속-함유 촉진제를 포함하되, 비금속-함유 촉진제의 비율은 촉매의 중량을 기준으로 0.1 내지 50 중량% 범위, 바람직하게 0.5 내지 30 중량% 범위 및 더욱 바람직하게 1 내지 20 중량% 범위이다.In a further preferred embodiment, the catalyst comprises at least one non-metal-containing accelerator from the group consisting of Ni, Co, Fe, Mn, Mo, W, wherein the ratio of non- By weight, preferably in the range of 0.5 to 30% by weight, and more preferably in the range of 1 to 20% by weight.
추가의 양태에서, 촉매는 추가적으로, 바람직하게 Mg, Ca, Sr, Ba, Ga, Be, Cr, Mn으로 이루어진 군으로부터 선택된 추가의 금속 양이온 비율을 포함하되, 이 때 Ca 및 Mg가 특히 바람직하다.In a further embodiment, the catalyst further comprises a further metal cation ratio selected from the group consisting of Mg, Ca, Sr, Ba, Ga, Be, Cr, Mn, with Ca and Mg being particularly preferred.
본 발명의 촉매에 존재하는 성분, 즉 상술된 귀금속, 알칼리 토금속, 도핑 원소, 촉진제 및 지지체 물질은 원소 및/또는 산화 형태로 존재할 수 있다.The components present in the catalyst of the present invention, i. E. The abovementioned noble metals, alkaline earth metals, doping elements, promoters and support materials, can be present in elemental and / or oxidized form.
본 발명은, 상세한 설명에 제시된 조합 및 수치 범위로 제한되어서는 안되고, 주된 청구항의 범위 내에서 성분들의 다른 조합 또한 생각할 수 있고 가능하다. The present invention should not be limited to the combinations and numerical ranges set forth in the detailed description, and other combinations of components within the scope of the main claims are conceivable and possible.
본 발명의 촉매는, 개별 성분으로 지지체 물질을 함침 코팅하여 제조될 수 있다. 제조 공정의 추가의 및 유리한 양태에서, 활성 성분은, 이후 적어도 부분적으로 혼련 및 압출되는 분말형 지지체 물질에 적용된다.The catalyst of the present invention can be prepared by impregnating a support material with the individual components. In a further and advantageous embodiment of the manufacturing process, the active ingredient is then applied to a powdery support material which is at least partially kneaded and extruded.
또한, 다른 제조 공정이 서로 조합될 수 있으며, 예를 들어, 활성 성분의 오직 일부가 분말형 지지체 물질에 적용되고 혼련된다. 예를 들어, 함침 코팅 방법에 의해 우선 출발 성분의 일부를 접촉시키고 이후 잔여 성분의 증착을 수행하기 위하여, 혼련 및 압출의 조합 또한 가능하다. In addition, other manufacturing processes can be combined with each other, for example, only a portion of the active ingredient is applied to the powdered support material and kneaded. For example, a combination of kneading and extrusion is also possible, in order to contact a portion of the starting component first by the impregnation coating method and then to perform the deposition of the remaining components.
본 발명에 따른 활성 조성물 제조를 위한 공정은 어떠한 방법으로도 제한되지 아니하지만, 매우 다른 공정 단계를 대신 사용하는 것은 가능하다. 따라서, 적용이라는 용어는 본원 개시 내용의 목적을 위한 그리고 활성 성분에 대한 제한으로서 고려되어서는 안된다. 따라서, 적용이라는 용어는 또한 출발 성분, 활성 성분 및 지르코늄-함유 종의 접촉을 포함한다. 지르코늄-함유 종은 또한 오직 합성 공정 동안에 본 발명에 따른 물질로 전환되는 전구체 물질로서 존재할 수 있다. Although the process for preparing the active composition according to the present invention is not limited in any way, it is possible to use very different process steps instead. Accordingly, the term application is not to be considered for the purposes of this disclosure and as a limitation on the active ingredient. Thus, the term application also includes the contact of the starting component, the active component and the zirconium-containing species. The zirconium-containing species may also be present only as a precursor material which is converted into the material according to the invention during the synthesis process.
예를 들어, 열 처리 공정과 결합된 활성 성분 및 지르코늄-함유 종의 공침에 의한 활성 조성물의 제조는 제외되지 않는다. 이러한 합성 공정의 경우, 오직 열 처리 동안에 지르코늄-함유 종이 입방정계 및/또는 정방정계 구조를 갖는 지르코늄 다이옥사이드로 전환될 수 있다. 합성 공정의 추가의 예는 불꽃-열분해 공정 또는 플라즈마 공정이다.For example, the preparation of an active composition by co-treatment of an active ingredient and a zirconium-containing species in combination with a heat treatment process is not excluded. In the case of such a synthesis process, zirconium-containing species can be converted to zirconium dioxide having a cubic system and / or tetragonal structure only during thermal processing. A further example of a synthesis process is a flame-pyrolysis process or a plasma process.
이러한 맥락에서, 지지체 물질 내의 지르코늄 다이옥사이드가 이미 입방정계 및/또는 정방정계 구조 형태로 존재할 경우, 지르코늄 다이옥사이드-함유 지지체 물질 상에 함침의 의미로서 활성 성분의 적용이 특히 바람직하다고 할 수 있다.In this context, the application of the active ingredient as a means of impregnation onto the zirconium dioxide-containing support material is particularly preferred when the zirconium dioxide in the support material is already present in the form of cubic and / or tetragonal structures.
지지체에 활성 성분을 적용하기 위하여, 바람직한 것은 용매에 가용성인 금속 화합물이다. 그중에서도, 바람직하게 사용되는 용매는 다음과 같다: 물, 산성 또는 알칼리 수용액, 메탄올, 에탄올, 프로판올, 아이소프로판올, 부탄올과 같은 알코올, 아세톤 또는 메틸 에틸 케톤과 같은 케톤, 톨루엔 또는 자일렌과 같은 방향족 용매, 사이클로헥산 또는 n-헥산과 같은 지방족 용매, 테트라하이드로퓨란, 다이에틸 에터 또는 다이글림과 같은 에터 및 폴리에터, 메틸 아세테이트 또는 에틸 아세테이트와 같은 에스터.To apply the active ingredient to the support, preferred are metal compounds that are soluble in the solvent. Among these, preferred solvents are: water, an acidic or alkaline aqueous solution, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ketones such as acetone or methyl ethyl ketone, aromatic solvents such as toluene or xylene , Aliphatic solvents such as cyclohexane or n-hexane, ethers and polyethers such as tetrahydrofuran, diethyl ether or diglyme, esters such as methyl acetate or ethyl acetate.
금속 화합물로서, 특히 바람직한 것은 가용성 염, 착물 또는 금속-유기 화합물을 사용하는 것이다. 염의 예로는, 그중에서도, 할라이드, 카보닐, 아세테이트, 나이트레이트, 카보네이트이다. 착물의 예로는, 그중에서도, 바이피리딜 착물, 아세토나이트릴 착물, 카보닐 착물, 아미노 산 또는 아민과의 착물, 폴리올 또는 폴리산과의 착물, 인화수소(phosphane)와의 착물이다. 금속-유기 화합물의 예로는, 그중에서도, 아세틸아세토네이트, 알콕사이드, 아마이드, 알킬 화합물, 사이클로펜타다이에닐 및 사이클로알칸이다.As the metal compound, particularly preferable ones are soluble salts, complexes or metal-organic compounds. Examples of salts include halides, carbonyls, acetates, nitrates, and carbonates. Among them, examples of the complex are bipyridyl complex, acetonitrile complex, carbonyl complex, complex with amino acid or amine, complex with polyol or polyacid, complex with phosphane. Examples of metal-organic compounds include, among others, acetylacetonates, alkoxides, amides, alkyl compounds, cyclopentadienyl and cycloalkanes.
또한, 금속 또는 산화 형태의 콜로이드 입자를 포함하는 졸이 출발 물질로서 사용된다. 이러한 콜로이드 입자는 안정화제 및/또는 특별한 처리 방법, 예를 들어 표면-활성화제에 의해 안정화될 수 있다.In addition, a sol containing metal or oxidized colloidal particles is used as a starting material. Such colloidal particles can be stabilized by stabilizers and / or by special treatment methods, such as surface-activators.
바람직한 양태에서, 촉매는 이트륨-안정화된 지르코늄 다이옥사이드 및 이리듐-함유 활성 성분을 포함하는 활성 조성물을 갖되, 이리듐-함유 활성 성분은 미세하게 분리된 형태로 존재하고 이리듐-함유 입자는 30 nm 미만, 바람직하게 20 nm 미만 및 더욱 바람직하게 10 nm 미만의 크기를 갖는다.In a preferred embodiment, the catalyst comprises an active composition comprising yttrium-stabilized zirconium dioxide and an iridium-containing active ingredient, wherein the iridium-containing active ingredient is present in finely divided form and the iridium- Lt; RTI ID = 0.0 > nm, < / RTI > and more preferably less than 10 nm.
본 발명은 또한, 하나 이상의 귀금속, 특히 바람직하게 이리듐이, 입방정계 및/또는 정방정계 지르코늄 다이옥사이드, 및 희토류 군으로부터 선택되는 하나 이상의 도핑 원소, 특히 바람직하게 이트륨을 포함하는 지지체 물질에 적용되는, 본 발명의 촉매 제조를 위한 공정을 제공한다.The present invention also relates to a process for the preparation of a zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide or zirconium oxide, To provide a process for the production of the catalyst of the invention.
활성 성분을 지지체 물질에 적용하기 위한 공정으로서, 촉매 제조 분야에서 당업자에게 알려진 모든 공정을 사용하는 것이 가능하다. 예를 들어, 함침 용액으로의 함침, 공극 용적에의 함침, 함침 용액의 분사(spraying-on), 워시코팅(washcoating) 및 침전이 본 발명에 언급될 수 있다. 공극 용적에의 함침에서, 지지체 물질의 공극 용적을 채우기에 충분하고 건조 상태의 외관으로 지지체 물질을 남기는 함침 용액의 정해진 양이 지지체 물질에 추가된다.As the process for applying the active component to the support material, it is possible to use all processes known to the person skilled in the art of catalyst production. For example, impregnation with impregnation solution, impregnation with pore volume, spraying-on, washcoating and precipitation of impregnation solution can be mentioned in the present invention. In impregnation into the pore volume, a defined amount of impregnating solution is added to the support material that is sufficient to fill the pore volume of the support material and leaves the support material in a dry appearance.
유리한 양태에서, 활성 성분, 또한 선택적으로 촉진제 및 추가의 금속 양이온이 우선 분말형 지지체 물질에 적어도 부분적으로 적용되고, 혼련되며 이후 압출된다. 활성 성분과 함께 지지체 물질의 혼련 및 압출은 당업자에게 알려진 기구를 이용하여 수행된다.In an advantageous embodiment, the active ingredient, optionally also an accelerator and further metal cations are first at least partially applied to the powdered support material, kneaded and then extruded. The kneading and extrusion of the support material with the active ingredient is carried out using a device known to those skilled in the art.
분말형 원료 물질로부터 성형체의 제조는 당업자에게 알려진 방법, 예를 들어 정제화, 응집 또는 압출, 그중에서도 문헌[Handbook of Heterogeneous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp.414-417]에 개시된 방법에 의해 수행될 수 있다.The preparation of shaped bodies from powdery raw materials can be carried out by methods known to those skilled in the art, for example, tableting, flocculation or extrusion, among which Handbook of Heterogeneous Catalysis, Vol. 1, VCH Verlagsgesellschaft Weinheim, 1997, pp.414-417.
보조제가 합성 시스템에 추가될 수 있다. 보조제의 추가는, 예를 들어 성형 동안 또는 활성 성분의 지지체로의 적용 동안 수행될 수 있다. 사용될 수 있는 보조제는, 예를 들어, 결합제, 윤활제 및/또는 용매이다. 합성 시스템에 추가되는 보조제는 이후 열 처리에 의해 추가의 성분을 형성할 수 있는 다른 구성 성분으로 전환된다. 상기 추가의 성분은 일반적으로 산화 물질이고, 이들의 일부가 결합 지점으로 작용하여 성형체 또는 개별 입자의 기계적 안정성을 향상시키는데 기여할 수 있다. 결합제는, 예를 들어, 알루미늄 하이드록사이드, 규소 하이드록사이드 또는 마그네슘 하이드록사이드를 포함하는 종을 포함할 수 있다.Adjuvants may be added to the synthesis system. The addition of adjuvants can be carried out, for example during molding or during application of the active component to the support. Adjuvants which can be used are, for example, binders, lubricants and / or solvents. The adjuvants added to the synthesis system are then converted to other constituents that can form additional constituents by thermal treatment. The additional component is generally an oxidizing material, and some of them may act as attachment points to contribute to improving the mechanical stability of the molded article or individual particles. The binder may include, for example, a species comprising aluminum hydroxide, silicon hydroxide or magnesium hydroxide.
이리듐-함유 활성 조성물은 또한 지지체, 모노리스(monolith) 또는 허니컴(honeycomb) 바디에 적용될 수 있다. 모노리스 또는 허니컴 바디는 금속 또는 세라믹을 포함할 수 있다. 활성 조성물의 몰딩 또는 활성 조성물의 지지체 또는 지지체 바디로의 적용은 본 발명의 촉매 적용 분야에서 기술적으로 매우 중요하다. 입자 크기 및 반응기 패킹에 따라, 입자의 형태는 고정된 촉매 베드에 의해 야기되는 압력 강하에 영향을 미친다. The iridium-containing active composition may also be applied to a support, a monolith or a honeycomb body. The monolith or honeycomb body may comprise metal or ceramic. The molding of the active composition or application of the active composition to the support or support body is technically of great importance in the catalytic applications of the present invention. Depending on the particle size and the reactor packing, the shape of the particles affects the pressure drop caused by the fixed catalyst bed.
CO2의 존재 하에서 탄화수소, 바람직하게 메탄의 개질을 위한 본 발명의 공정 특성은, 상대적으로 적은 함량의 Ir을 가짐에도 불구하고 높은 촉매 효율을 갖는 ZrO2-함유 활성 조성물을 사용할 수 있다는 것이다. 따라서, 예를 들어, 오직 1 중량% 또는 1 중량% 미만의 Ir을 갖는 활성 조성물을 사용하여 예컨대, 높은 전환 또한 얻을 수 있다.
The process characteristic of the present invention for the modification of hydrocarbons, preferably methane, in the presence of CO 2 is that ZrO 2 -containing active compositions with high catalytic efficiency can be used despite having a relatively low content of Ir. Thus, for example, high conversion can also be achieved, for example, using an active composition having only 1 wt.% Or less than 1 wt.% Ir.
II. CO2 개질 공정II. CO 2 reforming process
본 발명은, 탄화수소, 바람직하게 메탄을 이산화탄소 개질하여 합성 가스를 제조하기 위한 촉매성 고압 공정으로서, The present invention is a catalytic high-pressure process for the production of syngas by reforming a hydrocarbon, preferably methane,
(i) CO2-함유 개질 가스를 이리듐-함유 활성 조성물에 접촉시키되, 개질 가스 내의 탄화수소, 바람직하게 CH4, 및 CO2의 총 함량이 80 부피% 초과, 바람직하게 85 부피% 초과 및 더욱 바람직하게 90 부피% 초과이고,(i) contacting the iridium-containing active composition with a CO 2 -containing reformed gas, wherein the total content of hydrocarbons, preferably CH 4 , and CO 2 , in the reformed gas is greater than 80%, preferably greater than 85% By volume, more than 90% by volume,
(ii) 활성 조성물과 접촉하는 개질 가스의 압력은 5 내지 500 bar 범위, 바람직하게 10 내지 250 bar 범위 및 더욱 바람직하게 20 내지 100 bar 범위이고, 활성 조성물과 접촉하는 개질 가스의 온도는 600 내지 1200 ℃ 범위, 바람직하게 850 내지 1100 ℃ 범위 및 특히 850 내지 950 ℃ 범위이고,(ii) the pressure of the reforming gas in contact with the active composition ranges from 5 to 500 bar, preferably from 10 to 250 bar, and more preferably from 20 to 100 bar, and the temperature of the reforming gas in contact with the active composition is from 600 to 1200 Lt; 0 > C, preferably 850 to 1100 < 0 > C and especially 850 to 950 &
(iii) 공정에서의 GHSV는 500 내지 100000 h-1 범위, 바람직하게 500 내지 50000 h-1 범위이고,The GHSV in the step (iii) ranges from 500 to 100000 h -1 , preferably from 500 to 50000 h -1 ,
(iv) 제조된 합성 가스는 0.4 내지 1.8 범위, 더욱 바람직하게 0.5 내지 1.4 범위 및 특히 0.8 내지 1.2 범위의 H2/CO 비를 갖는, 촉매성 고압 공정을 제공한다.(iv) the produced synthesis gas has a catalytic high-pressure process having a H 2 / CO ratio in the range of 0.4 to 1.8, more preferably in the range of 0.5 to 1.4 and in particular in the range of 0.8 to 1.2.
공정의 바람직한 양태에서, 이리듐은 이리듐-함유 활성 조성물 내의 지르코늄 다이옥사이드와 결합하여 존재하고, Ir 함량은 ZrO2를 기준으로 0.01 내지 10 중량%, 바람직하게 0.05 내지 5 중량% 및 더욱 바람직하게 0.1 내지 1 중량% 범위이다.In a preferred embodiment of the process, iridium is present in association with zirconium dioxide in the iridium-containing active composition and the Ir content is from 0.01 to 10 wt%, preferably from 0.05 to 5 wt%, and more preferably from 0.1 to 1 wt%, based on ZrO 2 Weight%.
공정의 바람직한 양태에서, 활성 조성물은 지지체 물질로서 지르코늄 다이옥사이드를 포함하되, 상기 지르코늄 다이옥사이드 대부분이 입방정계 및/또는 정방정계 구조를 갖고, 입방정계 및/또는 정방정계 상의 비율은 50 중량% 초과, 더욱 바람직하게 70 중량% 초과 및 특히 90 중량% 초과이다.In a preferred embodiment of the process, the active composition comprises zirconium dioxide as a support material, wherein the majority of the zirconium dioxide has a cubic system and / or a tetragonal system, the ratio of cubic system and / or tetragonal system is more than 50% Preferably more than 70% by weight and especially more than 90% by weight.
본 발명의 촉매 및 본 발명의 공정의 특징은, CO2의 존재 하에서 탄화수소, 바람직하게 메탄의 이산화탄소 개질에 대한 높은 활성이다. 본 발명 공정의 추가의 특성은, 매우 극한 반응 조건 하에서의 탄소질 증착물 형성에 대한 우수한 저항성이다. 극한 반응 조건과 관련하여, 낮은 증기-대-탄소 비(S/C)에서의 고압 및 온도 저항성에 관해 특히 언급할 수 있다. 이로써 유발되는 기술적 효과는 본 발명의 공정을 수행 시 촉매의 높은 구동 수명을 야기한다.The catalyst of the present invention and process features of the present invention are highly active for carbon dioxide reforming of hydrocarbons, preferably methane, in the presence of CO 2 . A further feature of the present process is the excellent resistance to carbonaceous deposit formation under very extreme reaction conditions. With respect to the extreme reaction conditions, particular mention can be made of high pressure and temperature resistance at low steam-to-carbon ratio (S / C). The technical effect caused thereby leads to a high driving life of the catalyst in carrying out the process of the present invention.
추가의 바람직한 양태에서, 활성 조성물은 이리듐 및 지르코늄 다이옥사이드 뿐만 아니라 희토류(Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) 군으로부터 선택된 하나 이상의 도핑 원소, 특히 바람직하게 이트륨 역시 포함하되, 그 함량은 ZrO2를 기준으로 0.01 내지 80 중량%, 바람직하게 0.1 내지 50 중량% 및 더욱 바람직하게 1.0 내지 30 중량% 범위이다.In a further preferred embodiment, the active composition comprises iridium and zirconium dioxide as well as rare earths (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) , Particularly preferably yttrium, the content of which is in the range of 0.01 to 80% by weight, preferably 0.1 to 50% by weight and more preferably 1.0 to 30% by weight, based on ZrO 2 .
개질 반응에서의 성능 특성을 증가시키기 위하여, 본 발명의 공정에서 사용되는 촉매는 추가적으로 귀금속-함유 촉진제, 비금속-함유 촉진제 및 또한 추가의 금속 양이온을 포함할 수 있다.To increase the performance characteristics in the reforming reaction, the catalyst used in the process of the present invention may additionally comprise a noble metal-containing accelerator, a non-metal-containing promoter and also further metal cations.
귀금속 촉진제는 Pt, Rh, Pd, Ru, Au로 이루어진 군으로부터 선택되되, 귀금속-함유 촉진제의 비율은 촉매의 중량을 기준으로 0.01 내지 5 중량% 범위 및 더욱 바람직하게 0.1 내지 3 중량% 범위이다.The noble metal promoter is selected from the group consisting of Pt, Rh, Pd, Ru, and Au, wherein the ratio of the noble metal-containing promoter is in the range of 0.01 to 5 wt%, and more preferably 0.1 to 3 wt%, based on the weight of the catalyst.
비금속-함유 촉진제는 Ni, Co, Fe, Mn, Mo, W로 이루어진 군으로부터 선택되되, 비금속-함유 촉진제의 비율은 촉매의 중량을 기준으로 0.1 내지 50 중량% 범위, 바람직하게 0.5 내지 30 중량% 범위 및 더욱 바람직하게 1 내지 20 중량% 범위이다.The non-metal-containing accelerator is selected from the group consisting of Ni, Co, Fe, Mn, Mo, and W, wherein the ratio of the non-metal-containing accelerator is in the range of 0.1 to 50 wt%, preferably 0.5 to 30 wt% And more preferably in the range of 1 to 20% by weight.
금속 양이온은 바람직하게 Mg, Ca, Sr, Ga, Be, Cr 및 Mn으로 이루어진 군으로부터 선택되는 하나 이상의 원소이고, 이 때 특히 바람직한 것은 Ca 및/또는 Mg이다.The metal cation is preferably at least one element selected from the group consisting of Mg, Ca, Sr, Ga, Be, Cr and Mn, with Ca and / or Mg being particularly preferred.
본 발명 공정의 다른 이점은, 본 발명의 공정이 소량의 증기를 갖거나 증기를 전혀 갖지 않는 공급 유체를 사용하여 수행될 수 있다는 것이다. 바람직한 양태에서, 개질 가스 내의 증기/탄소 비는 0.2 미만, 더욱 바람직하게 0.1 미만 및 특히 바람직하게 0.05 미만이다.Another advantage of the process of the present invention is that the process of the present invention can be carried out using a feed fluid having a small amount of steam or no steam at all. In a preferred embodiment, the vapor / carbon ratio in the reforming gas is less than 0.2, more preferably less than 0.1, and particularly preferably less than 0.05.
또한, 본 발명의 공정 및 개질 가스를 위한 특히 바람직한 특정 양태와 관련하여, 대체로 물 없이 또는 물이 전혀 사용되지 않는 것 역시 가능하다.It is also possible, with regard to particular preferred embodiments of the process and reforming gas of the present invention, that there is generally no water or no water at all.
낮은 물 함량에서 본 발명의 공정을 수행하는 것은 공정의 고 에너지 효율, 및 본 발명의 공정이 사용되는 공장의 공정 흐름도의 단순화라는 이점을 제공한다.Performing the process of the present invention at low water content provides the advantages of high energy efficiency of the process and simplification of the process flow diagram of the plant in which the process of the present invention is used.
본 발명의 공정이 수행될 때, 공정이 5 내지 500 bar 범위, 바람직하게 10 내지 250 bar 범위 및 더욱 바람직하게 20 내지 100 bar 범위의 압력과 600 내지 1200 ℃, 바람직하게 850 내지 1100 ℃ 및 더욱 바람직하게 850 내지 950 ℃ 범위의 온도에서 수행되기 때문에, 이리듐-함유 활성 성분은 극한 물리적 및 화학적 스트레스에 놓이게 된다. 비록 공정이 매우 극한 공정 조건 하에서 수행되어도, 본 발명에 따른 물질의 특정 성질로 인하여 촉매 상의 탄소질 물질의 증착은 대체로 배제될 수 있고, 이는 또한 본 발명 공정의 이점을 나타낸다.When the process of the present invention is carried out, it is preferred that the process be carried out at a pressure in the range of 5 to 500 bar, preferably in the range of 10 to 250 bar and more preferably in the range of 20 to 100 bar and at a temperature of 600 to 1200 ° C, preferably 850 to 1100 ° C, Lt; RTI ID = 0.0 > 850-950 C, < / RTI > the iridium-containing active ingredient is subjected to extreme physical and chemical stresses. Although the process is carried out under very extreme process conditions, the deposition of the carbonaceous material on the catalyst can be largely eliminated owing to the specific nature of the material according to the invention, which also represents the advantage of the process of the invention.
낮은 수준의 탄소질 증착물 때문에, 본 발명의 공정은 긴 시간에 걸쳐 수행될 수 있고, 이는 다시 말해 공정 효율적 측면에서의 이점이다.
Because of the low level of carbonaceous deposits, the process of the present invention can be performed over a long period of time, which is an advantage in terms of process efficiency.
III. 실시예III. Example
본 발명을 설명하기 위하여, 본 발명의 개질 촉매의 제조 및 사용에 대한 다수의 실시예를 제공한다. 또한, 종래 기술에 대응하고 따라서 본 발명에 따른 특징을 갖지 않는 비교예를 개시한다.
In order to illustrate the present invention, a number of embodiments for the preparation and use of the reforming catalysts of the present invention are provided. In addition, a comparative example corresponding to the prior art and thus having no feature according to the present invention is disclosed.
1. 이리듐-함유 촉매의 제조1. Preparation of iridium-containing catalysts
본 발명에 따른 촉매(S2)를 제조하기 위하여, 198g의 이트륨-안정화된 지르코늄 다이옥사이드를 수성 이리듐 클로라이드 용액으로 함침시켰다. 이리듐 클로라이드 용액을 제조하기 위하여, 3.84g의 IrCl4*H2O를 우선 20 ml의 증류수에 용해시켰으며 용액에 물을 채웠다. 물의 양은 지지체 옥사이드의 자유 공극 용적의 90%가 용액으로 채워질 수 있도록 선택되었다. 자유 공극 용적은 0.2 cm3/g이었다. 이트륨-안정화된 지르코늄 다이옥사이드는 8 중량%의 이트륨 옥사이드(Y2O3) 함량을 가졌고, 0.5 내지 1.0 mm 범위의 입자 크기를 갖는 으깨진 물질로서 존재하였다.In order to prepare the catalyst (S2) according to the invention, 198 g of yttrium-stabilized zirconium dioxide was impregnated with an aqueous iridium chloride solution. To prepare the iridium chloride solution, 3.84 g of IrCl 4 * H 2 O was first dissolved in 20 ml of distilled water and the solution was filled with water. The amount of water was chosen such that 90% of the free pore volume of the support oxide could be filled with the solution. The free pore volume was 0.2 cm 3 / g. The yttrium-stabilized zirconium dioxide had an yttrium oxide (Y 2 O 3 ) content of 8 wt% and was present as a cracked material with a particle size in the range of 0.5 to 1.0 mm.
안정화된 지지체 옥사이드로 구성된 으깨진 물질을 함침 드럼에 위치시키고, 드럼을 회전시키면서 이리듐 클로라이드 용액으로 분사-함침시켰다. 함침 이후, 물질을 추가의 10분 동안 회전시켰고, 이후 16시간 동안 대류 건조 오븐에서 120 ℃에서 건조시켰다. 건조 물질의 하소는 550 ℃에서 2시간 동안 수행되었다.The broken material consisting of the stabilized support oxide was placed in the impregnation drum and spray-impregnated with the iridium chloride solution while rotating the drum. After impregnation, the material was spun for an additional 10 minutes and then dried at 120 [deg.] C in a convection drying oven for 16 hours. The calcination of the dried material was carried out at 550 DEG C for 2 hours.
이 방법으로 수득된 이리듐-함유 촉매 S2는, 100g의 촉매 당 1.0g의 이리듐 함량을 가졌다.
The iridium-containing catalyst S2 obtained by this method had an iridium content of 1.0 g per 100 g of catalyst.
2. 비교 백금 촉매의 제조2. Preparation of comparative platinum catalysts
지지체 옥사이드로서 세륨/란타늄-도핑된 지르코늄 다이옥사이드를 사용하여, 이리듐 촉매 S2와 동일한 방법으로, 백금-함유 비교 촉매 CE5를 제조하였다. 상기 지지체 옥사이드는 0.21 cm3/g의 자유 공극 용적 및 22 중량%의 La 옥사이드 및 Ce 옥사이드의 희토류 함량을 가졌다. 0.5 내지 1.0 mm 범위의 입자 크기를 갖는 으깨진 물질의 형태의 100g의 지지체 옥사이드를 함침을 위하여 사용하였다. 함침을 수행하기 위하여, 6.37g의 백금 나이트레이트 염(15.7 중량%의 백금 포함)을 물에 용해시켰고, 이후 용액을 분사 드럼에서 지지체 옥사이드 상에 분사시켰다. 함침 후 수득된 비교 촉매 CE5는 100g의 촉매 당 1.0g의 Pt의 Pt 함량을 가졌다.A platinum-containing comparison catalyst CE5 was prepared in the same manner as the iridium catalyst S2, using cerium / lanthanum-doped zirconium dioxide as the support oxide. The support oxide had a free pore volume of 0.21 cm 3 / g and a rare earth content of 22 wt% La oxide and Ce oxide. 100 g of support oxide in the form of a crushed material having a particle size in the range of 0.5 to 1.0 mm was used for impregnation. To carry out the impregnation, 6.37 g of platinum nitrate salt (including 15.7% by weight of platinum) was dissolved in water, after which the solution was sprayed onto the support oxide in the injection drum. The comparative catalyst CE5 obtained after impregnation had a Pt content of 1.0 g Pt per 100 g of catalyst.
실험된 활성 조성물의 개요를 하기 표 1에 개시하였다. 표에 개시된 모든 활성 조성물은 회전 함침 드럼을 사용한 함침 공정에 의해 실험실에서 제조되었다. A summary of the active compositions tested is set forth in Table 1 below. All active compositions disclosed in the Tables were prepared in the laboratory by an impregnation process using a spin-impregnated drum.
도 1은 환원 처리 전에 촉매 샘플 S2 상에서 기록된 X선 회절 패턴을 나타낸다. 도면의 상부에, 이리듐-함유 상을 나타낼 수 있는 반사를 강조하기 위하여 25°(2θ) 내지 65°(2θ) 각도 범위를 확장하였다.Fig. 1 shows the X-ray diffraction pattern recorded on the catalyst sample S2 before the reduction treatment. At the top of the figure, an angular range of 25 [deg.] To 65 [deg.] (2 [Theta]) was extended to emphasize reflections that could indicate an iridium-containing phase.
도 2는 환원되지 않은 형태의 촉매 샘플 S3 상에서 기록된 X선 회절 패턴을 나타낸 것으로서, 이리듐-옥사이드 함유 상의 반사가 발견되지 않아야 한다.Fig. 2 shows the X-ray diffraction pattern recorded on the catalyst sample S3 in the non-reduced form, and no reflection of the iridium-oxide containing phase should be found.
X선 회절 패턴의 평가에 의하여 이리듐 입자의 평균 입자 크기를 측정하였다. (이트륨에 의해 안정화된) 1 중량%의 이리듐이 로딩된 촉매 샘플 S2에서, 이리듐 옥사이드 입자(IrO2)는 8.0 nm의 평균 결정 크기를 가졌다. XRD 데이터의 평가를 하기 도 1에 나타내었다. 여기서, 환원되지 않은 형태의 촉매의 XRD 분석이 수행되었기 때문에, 이리듐 입자는 산화 형태로 존재하였다. 도 2에 나타난 회절 패턴의 평가는 이리듐 옥사이드 상을 검출할 수 없었음을 나타낸다. 이는 이리듐 입자가 1 또는 2 nm보다 작음을 보여주는데, 그렇지 않으면 대응하는 반사가 XRD에서 발견될 수 있었어야 했기 때문이다.The average particle size of the iridium particles was measured by evaluation of the X-ray diffraction pattern. In 1 wt% of the iridium loaded catalyst sample S2 (stabilized by yttrium), the iridium oxide particles (IrO 2 ) had an average crystal size of 8.0 nm. Evaluation of the XRD data is shown in Fig. Here, since the XRD analysis of the catalyst in the non-reduced form was carried out, the iridium particles existed in an oxidized form. The evaluation of the diffraction pattern shown in Fig. 2 indicates that the iridium oxide phase could not be detected. This shows that the iridium particle is smaller than 1 or 2 nm, otherwise the corresponding reflection should have been detectable in XRD.
XRD 분석은, 반사 모드에서 쎄타-2쎄타 기하 구조(브레그-브렌타노 기하구조(Bragg-Brentano geometry)) 및 CuK-알파 소스(40 kV 및 40 mA에서 0.154 nm의 파장을 가짐)를 이용하여, 브루커(Bruker)/AXS로부터의 D8 어드밴스 시리즈 2로 수행되었다. 측정은, 4.8 초/단계에서 0.02°단계, 5 내지 80°(2θ) 측정 범위에서 수행되었다. 개별 상의 평균 결정 크기를 측정하기 위하여, 구조 분석 소프트웨어 TOPAS(브루커 AXS)가 사용되었다.
XRD analysis was performed using a theta-2 theta geometry (Bragg-Brentano geometry) in reflective mode and a CuK-alpha source (having a wavelength of 405 nm at 40 kV and 40 mA) D8 advance series 2 from Bruker / AXS. The measurements were carried out in the 0.02 degree step at 4.8 seconds / step and the 5 to 80 degree (2?) Measurement range. Structural analysis software TOPAS (Bruker AXS) was used to measure the average crystal size of the individual phases.
촉매 연구Catalyst Research
CO2의 존재 하에서 탄화수소-함유 가스의 개질에 대한 촉매 연구가 병렬로 연결된 6개의 반응기가 구비된 촉매 시험 세트-업(set-up)에 의해 수행되었다. 연구를 준비하기 위하여, 개별 반응기를 20 ml의 촉매 샘플로 채웠다.Catalyst studies on the modification of hydrocarbon-containing gases in the presence of CO 2 were carried out by catalytic test set-up with six reactors connected in parallel. To prepare the study, individual reactors were charged with 20 ml of catalyst sample.
수행한 촉매 연구의 개요를 하기 표 2 및 3에 나타내었다. 우선, 촉매로 채워진 반응기는 제어된 방식으로 운반 가스 대기 하에서 25 ℃로부터 목표 온도까지 가열되었다. 질소가 운반 가스로서 사용되었다. (환원 가스 대기의 존재 하에서 가열을 수행하는 것도 생각할 수 있다.) 반응기를 가열하기 위하여 10 ℃/분의 가열 속도가 선택되었다. 촉매를 갖는 반응기가 0.5시간 동안 질소 흐름에서 목표 온도로 유지된 이후, 개질 가스를 공급하였다.A summary of the conducted catalyst studies is shown in Tables 2 and 3 below. First, the reactor filled with catalyst was heated from 25 占 폚 to the target temperature under a carrier gas atmosphere in a controlled manner. Nitrogen was used as the carrier gas. (It is also conceivable to carry out heating in the presence of a reducing gas atmosphere.) A heating rate of 10 [deg.] C / min was selected to heat the reactor. After the reactor with the catalyst was maintained at the target temperature in the nitrogen flow for 0.5 hour, the reforming gas was supplied.
촉매 연구에서, 개별 샘플은 일련의 상이한 시험 조건 하에 놓였다. 첫번째 두 실험 조건에서, 촉매는 950 ℃에서 유지되었고, 개질 가스의 수증기 함량은 10 부피%로부터 0 부피%로 단계적으로 감소시켰다. 하기 표에서, 950 ℃에서 10 부피% 및 0 부피%의 수증기의 존재 하에 수행된 연구는 접미사 c1 및 c2로 표시하였다(즉, c1은 950 ℃에서 10 부피%의 수증기에 대응하고, c2는 950 ℃에서 0 부피%의 수증기에 대응한다). 0 부피%의 수증기의 존재 하에 850 ℃에서 시험된 샘플은 표 3에서 접미사 c3로 표시하였다. 10 부피% 수증기의 존재 하의 실험 조건의 경우(c1), 샘플은, 공급 유체에 수증기가 없는 실험 조건의 경우(c2 및 c3)보다 낮은 공간 속도에 놓였다.In catalytic studies, individual samples were placed under a series of different test conditions. In the first two experimental conditions, the catalyst was maintained at 950 ° C and the water vapor content of the reforming gas was stepwise reduced from 10% by volume to 0% by volume. In the following table, the work carried out in the presence of 10 vol.% And 0 vol.% Water vapor at 950 DEG C is indicated by the suffixes c1 and c2 (i.e. c1 corresponds to 10 vol% steam at 950 DEG C and c2 corresponds to 950 0 < / RTI > vol.% Water vapor). Samples tested at 850 占 폚 in the presence of 0 vol.% Water vapor are designated as suffix c3 in Table 3. For the experimental conditions (c1) in the presence of 10 vol% steam, the sample was placed at a lower space velocity than the experimental conditions (c2 and c3) without steam in the feed fluid.
모든 촉매 연구는 내부 표준으로서 5 부피%의 아르곤의 존재 하에서 수행되었다; 이는, 물질의 회수율을 모니터하기 위하여 분석적인 이유 때문에 공급 유체에 추가되었다.All catalyst studies were carried out in the presence of 5 vol% argon as internal standard; It was added to the feed fluid for analytical reasons to monitor the recovery of the material.
여기서 선택된 시험 조건은, 물리 화학적 조건의 측면에서 매우 까다로와서, 오직 본 발명에 따른 촉매 샘플에 의해서만 장기간에 걸쳐 높은 전환 및 안정된 성능을 달성할 수 있었다(표 2). 이는, 이리듐이 알파-알루미늄 옥사이드 상에 존재하고, 이리듐 로딩량이 0.5 내지 2 중량% 범위인 비교 샘플 CE1, CE3 및 CE4가, 공급물 내 10 부피%의 H2O에서 몇 시간 안에 완전히 불활성되거나 코크스화되는 점으로부터 알 수 있다. 유사하게, 공급물 내 10 부피%의 H2O의 존재 하에서의 빠른 불활성화 또는 코크스화는 또한, 도핑되지 않은 단사정계 지르코늄 다이옥사이드 상에 1 중량%의 이리듐이 존재하는 비교 샘플 CE2에서도 관찰되었다. 1 중량%의 Pt를 갖고 그외에 나머지 성분 조성은 S1 및 S4과 동일한 비교 샘플 CE5는 850 ℃ 및 공급물 내 10 부피%의 H2O에서 안정된 성능 특성을 나타내었지만, 43 시간을 넘어서 매우 극심하게 불활성되었고, 이후 물 함량이 0 부피%로 감소되었다(표 3).The test conditions chosen here were very difficult in terms of physicochemical conditions, and only high conversion and stable performance over a long period of time could be achieved only by the catalyst samples according to the invention (Table 2). This is because comparative samples CE1, CE3 and CE4, in which iridium is present on alpha-aluminum oxide and the iridium loading is in the range of 0.5 to 2 wt%, are completely inactive within a few hours at 10 vol% H 2 O in the feed, Can be known from the point of becoming. Similarly, rapid deactivation or coking in the presence of 10 vol% H 2 O in the feed was also observed in Comparative Sample CE2 where 1 wt% of iridium was present on undoped monoclinic zirconium dioxide. 1% by weight of Pt, and the rest of the composition of the components was comparable to S1 and S4. Comparative sample CE5 showed stable performance characteristics at 850 ° C and 10% by volume of H 2 O in the feed, but exceeded 43 hours very extreme Inactivated, after which the water content was reduced to 0% by volume (Table 3).
비교 샘플과 달리, 본 발명의 공정과 결합되어 사용되고 10 부피% 및 최종적으로 0 부피%의 수증기의 존재 하에서 시험된, 실시예 S1 내지 S4의 본 발명에 따른 촉매는 불활성화가 나타나지 않았으며 CO2 및 CH4의 매우 높은 전환을 나타내었다.Unlike the comparative samples, the catalysts according to the invention of Examples S1 to S4, used in combination with the process of the present invention and tested in the presence of 10 vol.% And finally 0 vol.% Water vapor, showed no deactivation and CO 2 And CH4. ≪ / RTI >
본 발명에 따른 촉매는, 촉매 S3의 시험 결과로부터 명확히 알 수 있듯이, 매우 까다로운 조건 하에서 높은 촉매 활성을 나타내었고, 485 시간(누적)을 초과하여 매우 긴 시간 이후에도 유지되었다는 점에서 주목할 만한 것이다(도 4).The catalyst according to the present invention exhibited high catalytic activity under very severe conditions, as can be clearly seen from the test results of Catalyst S3, and is remarkable in that it was maintained after a very long time exceeding 485 hours (cumulative) 4).
촉매 시험 이후, 반응기로부터 제거된 촉매를 탄소질 물질의 양을 측정하기 위하여 분석하였다. 본 발명에 따른 촉매는 촉매작용 시험 후에도 탄소질 증착물이 없었다. 이는, 본 발명의 촉매의 높은 탄화 저항을 입증하였다.After the catalyst test, the catalyst removed from the reactor was analyzed to determine the amount of carbonaceous material. The catalyst according to the present invention was free of carbonaceous deposits even after the catalytic activity test. This proved the high carbonization resistance of the catalyst of the present invention.
S1 내지 S4의 모든 연구에서, 1 이하의 H2/CO 비를 갖는 합성 가스가 제조되었다. 개질 가스 내에 수증기 함량이 적을수록, CH4 전환에 대한 CO2 전환이 높아진다. 특히 건조 개질에서, 합성 가스는 0.9 미만, 및 또한 때때로 0.8 미만의 H2/CO비를 가졌다.In all of the studies of S1 to S4, synthesis gas having a H 2 / CO ratio of 1 or less was produced. The lower the water vapor content in the reforming gas, the higher the CO 2 conversion to CH 4 conversion. Particularly in the dry reforming, syngas had a H 2 / CO ratio of less than 0.9, and sometimes less than 0.8.
표 1은 시험된 활성 조성물의 조성 및 금속 함량의 개요를 나타낸다. Table 1 gives an overview of the composition and metal content of the active composition tested.
[표 1][Table 1]
표 2는, 수증기 함량에 대한 상이한 실험 조건 하에서, CH4의 CO2 개질에서 수득된 생성물 스트림의 화학적 구성을 나타낸다. 사용된 개질 가스는 내부 표준으로서 5 부피%의 아르곤, 및 등몰 비의 CH4 및 CO2를 가졌다. 모든 실험은 950 ℃의 온도 및 20 bar의 반응기 압력에서 수행되었다. "개시"로 표시된 값이 각 실험의 시작 시 즉시 기록되었다; "종료"로 표시된 값은 43 시간의 TOS(스트림 상 시간(time on stream)) 이후에 기록되었다. (*) 표시는 수증기 함량의 감소 후 샘플 상에 형성되고 반응기의 폐색/고장을 야기하는 탄소질 증착물을 나타낸다.Table 2 shows the chemical composition of the product stream obtained in CO 2 reforming of CH 4 under different experimental conditions for water vapor content. The reformed gas had a 5% by volume as an internal standard argon, and an equimolar ratio of CH 4 and CO 2 used. All experiments were carried out at a temperature of 950 ° C and a reactor pressure of 20 bar. Values marked "onset" were immediately recorded at the beginning of each experiment; The value marked "end" was recorded after 43 hours of TOS (time on stream). (*) Indicates carbonaceous deposits that are formed on the sample after reduction of the water vapor content and cause clogging / failure of the reactor.
[표 2][Table 2]
표 3은 시험 조건 c3 하에서의 촉매 샘플 S2 및 CE5에 대한 연구에서 수득된 결과를 나타낸다. "개시"로 표시된 값이 각 실험의 시작 시 즉시 기록되었다; "종료"로 표시된 값은 43 시간의 TOS(스트림 상 시간) 이후에 기록되었다. 촉매적 측정은 850 ℃에서 수행되었다.Table 3 shows the results obtained in the study on catalyst samples S2 and CE5 under test condition c3. Values marked "onset" were immediately recorded at the beginning of each experiment; The value marked "end" was recorded after 43 hours of TOS (time on stream). Catalytic measurements were carried out at 850 ° C.
[표 3][Table 3]
표 4는, 시험 조건 c1(10 부피%의 H2O) 및 c2(0 부피%의 H2O) 하에서 235 시간 및 254 시간의 TOS(스트림 상 시간) 이후, 촉매 샘플 S3에 대한 연구에서 수득된 결과를 나타낸다. 촉매적 측정은 950 ℃의 온도 및 20 bar의 압력에서 수행되었다.Table 4 summarizes the results obtained in a study on catalyst sample S3 after 235 hours and 254 hours of TOS (stream phase time) under test conditions c1 (10 vol% H 2 O) and c2 (0 vol% H 2 O) Lt; / RTI > The catalytic measurements were carried out at a temperature of 950 DEG C and a pressure of 20 bar.
[표 4][Table 4]
Claims (15)
a) 이리듐 함량이 활성 조성물의 함량을 기준으로 0.01 내지 10 중량%, 바람직하게 0.05 내지 5 중량% 및 더욱 바람직하게 0.1 내지 1 중량% 범위이고,
b) 지르코늄 다이옥사이드-함유 지지체 물질 내의 지르코늄 다이옥사이드 대부분이 입방정계 및/또는 정방정계 구조 형태를 갖되, 입방정계 및/또는 정방정계 상의 비율이 50 중량% 초과, 더욱 바람직하게 70 중량% 초과 및 특히 90 중량% 초과인,
탄화수소의 CO2 개질을 위한 촉매.A catalyst for CO 2 modification of hydrocarbons having an active composition comprising an iridium-containing active ingredient and a zirconium dioxide-containing support material,
a) the iridium content is in the range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight and more preferably 0.1 to 1% by weight, based on the content of the active composition,
b) the majority of the zirconium dioxide in the zirconium dioxide-containing support material has a cubic system and / or tetragonal structure, wherein the ratio of cubic system and / or tetragonal system is greater than 50 wt%, more preferably greater than 70 wt% More than% by weight,
Catalyst for CO 2 reforming of hydrocarbons.
지르코늄 다이옥사이드-함유 지지체가 추가의 성분을 포함하고,
정방정계 및/또는 입방정계 지르코늄 다이옥사이드의 비율이 지지체 총 중량을 기준으로 80 중량% 초과, 바람직하게 90 중량% 초과 및 더욱 바람직하게 95 중량% 초과인,
탄화수소의 CO2 개질을 위한 촉매.The method according to claim 1,
Wherein the zirconium dioxide-containing support comprises an additional component,
Wherein the proportion of tetragonal and / or cubic zirconium dioxide is greater than 80 wt%, preferably greater than 90 wt%, and more preferably greater than 95 wt%, based on the total weight of the support,
Catalyst for CO 2 reforming of hydrocarbons.
지르코늄 다이옥사이드-함유 활성 조성물이 5 m2/g 초과, 바람직하게 10 m2/g 초과, 더욱 바람직하게 20 m2/g 초과, 더더욱 바람직하게 50 m2/g 초과 및 특히 80 m2/g 초과의 비표면적을 갖는,
탄화수소의 CO2 개질을 위한 촉매.3. The method according to claim 1 or 2,
Zirconium dioxide-containing active composition is 5 m 2 / g greater than, and preferably 10 m 2 / g greater than, more preferably 20 m 2 / g greater than, even more preferably 50 m 2 / g greater than, and in particular 80 m 2 / g greater than Lt; / RTI >
Catalyst for CO 2 reforming of hydrocarbons.
활성 조성물이 희토류(Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), IIa족(Mg, Ca, Sr, Ba), IVb족(Ti, Hf), Vb족 (V, Nb, Ta) 및/또는 규소의 군으로부터 선택되는 하나 이상의 원소를 갖는 도판트를 포함하되,
도핑 원소의 비율이 활성 조성물의 양을 기준으로 0.01 내지 80 중량% 범위, 바람직하게 0.1 내지 50 중량% 범위 및 특히 1.0 내지 30 중량% 범위인,
활성 조성물을 갖는 탄화수소의 CO2 개질을 위한 촉매.4. The method according to any one of claims 1 to 3,
Wherein the active composition is selected from the group consisting of rare earths (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) A dopant having at least one element selected from the group consisting of Group IVb (Ti, Hf), Group Vb (V, Nb, Ta) and / or silicon,
Wherein the proportion of the doping element is in the range of 0.01 to 80% by weight, preferably in the range of 0.1 to 50% by weight and in particular in the range of 1.0 to 30% by weight,
Catalyst for CO 2 reforming of hydrocarbons with active composition.
활성 조성물이 희토류(Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) 군으로부터의 하나 이상의 원소를 갖는 도판트를 포함하되,
도핑 원소의 비율이 활성 조성물의 비율을 기준으로 0.01 내지 80 중량% 범위, 바람직하게 0.1 내지 50 중량% 범위 및 특히 1.0 내지 30 중량% 범위인,
활성 조성물을 갖는 탄화수소의 CO2 개질을 위한 촉매.5. The method according to any one of claims 1 to 4,
Wherein the active composition comprises a dopant having at least one element from the group of rare earths (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) ,
Wherein the proportion of the doping element is in the range of 0.01 to 80% by weight, preferably in the range of 0.1 to 50% by weight and in particular in the range of 1.0 to 30% by weight,
Catalyst for CO 2 reforming of hydrocarbons with active composition.
지지체 물질이 도핑 원소로서 이트륨을 포함하거나, 지지체 물질이 도핑 원소로서 La 및/또는 Ce를 포함하는,
활성 조성물을 갖는 탄화수소의 CO2 개질을 위한 촉매.6. The method according to any one of claims 1 to 5,
Wherein the support material comprises yttrium as the doping element, or the support material comprises La and / or Ce as the doping element.
Catalyst for CO 2 reforming of hydrocarbons with active composition.
활성 조성물이, 0.01 내지 5 중량% 범위, 더욱 바람직하게 0.1 내지 3 중량% 범위의 양으로 존재하는, Pt, Rh, Pd, Ru 및 Au로 이루어진 군으로부터 선택되는 하나 이상의 귀금속-함유 촉진제를 포함하는,
활성 조성물을 갖는 탄화수소의 CO2 개질을 위한 촉매.7. The method according to any one of claims 1 to 6,
Wherein the active composition comprises at least one noble metal-containing accelerator selected from the group consisting of Pt, Rh, Pd, Ru and Au, present in an amount ranging from 0.01 to 5 wt%, more preferably from 0.1 to 3 wt% ,
Catalyst for CO 2 reforming of hydrocarbons with active composition.
활성 조성물이, 0.1 내지 50 중량% 범위, 더욱 바람직하게 0.5 내지 30 중량% 범위 및 더욱 바람직하게 1 내지 20 중량% 범위로 존재하는, Ni, Co, Fe, Mn, Mo 및 W로 이루어지는 군으로부터 선택되는 하나 이상의 비금속-함유 촉진제를 포함하는,
활성 조성물을 갖는 탄화수소의 CO2 개질을 위한 촉매.8. The method according to any one of claims 1 to 7,
Selected from the group consisting of Ni, Co, Fe, Mn, Mo and W, wherein the active composition is present in the range of 0.1 to 50 wt%, more preferably in the range of 0.5 to 30 wt% and more preferably in the range of 1 to 20 wt% Lt; RTI ID = 0.0 > non-metal < / RTI >
Catalyst for CO 2 reforming of hydrocarbons with active composition.
활성 조성물이 적어도 추가의 금속 양이온 종을 포함하되,
상기 금속 양이온 종은 바람직하게 Mg, Ca, Sr, Ga, Be, Cr 및 Mn으로 이루어진 군으로부터, 더욱 바람직하게 Ca 및/또는 Mg로 이루어진 군으로부터 선택되는,
활성 조성물을 갖는 탄화수소의 CO2 개질을 위한 촉매.9. The method according to any one of claims 1 to 8,
Wherein the active composition comprises at least an additional metal cation species,
The metal cation species is preferably selected from the group consisting of Mg, Ca, Sr, Ga, Be, Cr and Mn, more preferably selected from the group consisting of Ca and /
Catalyst for CO 2 reforming of hydrocarbons with active composition.
(i) 개질 가스 내의 탄화수소, 바람직하게 CH4, 및 CO2의 총 함량이 80 부피% 초과, 바람직하게 85 부피% 초과 및 더욱 바람직하게 90 부피% 초과이고,
(ii) 활성 조성물과 접촉하는 개질 가스의 압력은 5 내지 500 bar 범위, 바람직하게 10 내지 250 bar 범위 및 더욱 바람직하게 20 내지 100 bar 범위이고, 활성 조성물과 접촉하는 개질 가스의 온도가 600 내지 1200 ℃ 범위, 바람직하게 850 내지 1100 ℃ 범위 및 특히 850 내지 950 ℃ 범위이고,
(iii) 공정에서의 GHSV는 500 내지 100000 h-1 범위, 바람직하게 500 내지 50000 h-1 범위이고,
(iv) 제조된 합성 가스가 0.4 내지 1.8 범위, 더욱 바람직하게 0.5 내지 1.4 범위 및 특히 0.8 내지 1.2 범위의 H2/CO 비를 갖는, 고압 공정.A high pressure process for contacting a reforming gas with a catalyst comprising an iridium-containing active composition to produce syngas by reforming the hydrocarbon, preferably methane, with CO 2 ,
(i) the total content of hydrocarbons, preferably CH 4 , and CO 2 , in the reforming gas is greater than 80% by volume, preferably greater than 85% by volume, and more preferably greater than 90%
(ii) the pressure of the reforming gas in contact with the active composition is in the range of from 5 to 500 bar, preferably in the range of from 10 to 250 bar and more preferably in the range of from 20 to 100 bar, Lt; 0 > C, preferably 850 to 1100 < 0 > C and especially 850 to 950 &
The GHSV in the step (iii) ranges from 500 to 100000 h -1 , preferably from 500 to 50000 h -1 ,
(iv) the synthesis gas produced has a H 2 / CO ratio in the range of 0.4 to 1.8, more preferably in the range of 0.5 to 1.4 and in particular in the range of 0.8 to 1.2.
이리듐-함유 활성 조성물이 ZrO2와 결합하여 존재하되, Ir 함량이 ZrO2를 기준으로 0.01 내지 10 중량%, 바람직하게 0.05 내지 5 중량% 및 더욱 바람직하게 0.1 내지 1 중량% 범위이고/이거나,
지르코늄 다이옥사이드-함유 지지체 물질 내의 지르코늄 다이옥사이드 대부분이 입방정계 및/또는 정방정계 구조를 갖되, 입방정계 및/또는 정방정계 상의 비율이 50 중량% 초과, 더욱 바람직하게 70 중량% 초과 및 특히 90 중량% 초과인, 고압 공정.11. The method of claim 10,
Wherein the iridium-containing active composition is present in association with ZrO 2 , wherein the Ir content ranges from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight and more preferably from 0.1 to 1% by weight, based on ZrO 2 ,
Most of the zirconium dioxide in the zirconium dioxide-containing support material has a cubic system and / or tetragonal structure, wherein the ratio of cubic system and / or tetragonal system is greater than 50 wt%, more preferably greater than 70 wt% and especially greater than 90 wt% Phosphorous, high pressure process.
제 1 항에 따른 이리듐-함유 ZrO2를 포함하는 활성 조성물이 희토류 군으로부터의 하나 이상의 원소를 포함하되, 상기 희토류 원소가 바람직하게 Ce 및/또는 La로 이루어진 군으로부터 선택되고, 더욱 바람직하게 안정화 원소 Y인, 고압 공정.The method according to claim 10 or 11,
The active composition comprising iridium-containing ZrO 2 according to claim 1 comprises at least one element from the rare earth group, wherein the rare earth element is preferably selected from the group consisting of Ce and / or La, Y, high pressure process.
개질 가스가 단지 소량의 H2O를 포함하되, 개질 가스 내의 증기/탄소 비가 0.2 미만, 더욱 바람직하게 0.1 미만 및 특히 바람직하게 0.05 미만인, 고압 공정.13. The method according to any one of claims 10 to 12,
Wherein the reforming gas contains only a small amount of H 2 O, wherein the vapor / carbon ratio in the reforming gas is less than 0.2, more preferably less than 0.1, and particularly preferably less than 0.05.
이리듐-함유 활성 조성물이 촉진제와 함께 제공되는, 고압 공정.14. The method according to any one of claims 10 to 13,
Wherein the iridium-containing active composition is provided with an accelerator.
사용되는 개질 가스는 H2O가 없는, 고압 공정.15. The method according to any one of claims 10 to 14,
The reforming gas used is H 2 O-free, high pressure process.
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| EP12174258 | 2012-06-29 | ||
| EP12174258.9 | 2012-06-29 | ||
| PCT/EP2013/063455 WO2014001423A1 (en) | 2012-06-29 | 2013-06-27 | High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses |
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| JP (1) | JP2015525668A (en) |
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| US20170354962A1 (en) * | 2014-12-01 | 2017-12-14 | Sabic Global Technologies B.V. | Synthesis of trimetallic nanoparticles by homogeneous deposition precipitation, and application of the supported catalyst for carbon dioxide reforming of methane |
| JP6212065B2 (en) * | 2015-03-02 | 2017-10-11 | 株式会社ノリタケカンパニーリミテド | Ceria zirconia composite oxide particles and production method thereof |
| CN107405602B (en) * | 2015-03-05 | 2020-08-21 | 国际壳牌研究有限公司 | Methane oxidation catalyst, method of making and method of using the same |
| KR102056384B1 (en) | 2016-08-05 | 2020-01-22 | 한국과학기술원 | Metal Oxide Supported Catalyst for Dry Reforming and Method of Preparing Syngas Using the Same |
| JP7015298B2 (en) | 2016-08-31 | 2022-02-15 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Methane oxidation catalyst, the process of preparing it, and how to use it |
| SG11201901346YA (en) | 2016-08-31 | 2019-03-28 | Shell Int Research | Methane oxidation catalyst, process to prepare the same and method of using the same |
| CN108940381A (en) * | 2017-05-27 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of tetragonal phase zirconium oxide carrier, the catalyst containing the carrier and its application in the reaction of methane dry reforming |
| CN109718799A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas |
| GB2568564B (en) | 2018-07-17 | 2020-01-01 | Omnagen Ltd | Carbon dioxide conversion using combined fuel cell and electrolysis cell |
| RU2719176C1 (en) * | 2019-09-13 | 2020-04-17 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Synthetic gas production method |
| CN114713223A (en) * | 2021-01-04 | 2022-07-08 | 中国科学院大连化学物理研究所 | Method for preparing tetragonal-phase zirconia in one step, copper-based supported catalyst and application thereof |
| WO2024003354A1 (en) | 2022-07-01 | 2024-01-04 | Basf Se | Cobalt-based catalyst for the conversion of hydrocarbons to synthesis gas |
| WO2024003347A1 (en) | 2022-07-01 | 2024-01-04 | Basf Se | Cobalt- and strontium-based catalyst for the conversion of hydrocarbons to synthesis gas |
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| US5753143A (en) | 1996-03-25 | 1998-05-19 | Northwestern University | Process for the CO2 reforming of methane in the presence of rhodium zeolites |
| DE69927032T2 (en) | 1998-06-09 | 2006-03-02 | Idemitsu Kosan Co. Ltd. | METHOD FOR AUTOTHERMIC REFORMATION OF A HYDROCARBON INGREDIENT |
| ID28037A (en) * | 1998-06-30 | 2001-05-03 | Shell Internat Res Maatschaapp | CATALYTIC PARTIAL OXIDATION WITH TWO CATALYTIC ACTIVE METALS |
| EP1338335A4 (en) | 2000-11-08 | 2005-01-19 | Idemitsu Kosan Co | Catalyst for hydrocarbon reforming and method of reforming hydrocarbon with the same |
| JP4409833B2 (en) | 2001-03-29 | 2010-02-03 | 出光興産株式会社 | Hydrocarbon reforming catalyst and method for producing the same, and hydrocarbon reforming method using the catalyst |
| FR2864528B1 (en) | 2003-12-31 | 2006-12-15 | Total France | PROCESS FOR TREATING METHANE / CARBON DIOXIDE MIXTURES |
| US7309480B2 (en) | 2004-04-16 | 2007-12-18 | H2Gen Innovations, Inc. | Catalyst for hydrogen generation through steam reforming of hydrocarbons |
| GB0510514D0 (en) * | 2005-05-24 | 2005-06-29 | Johnson Matthey Plc | Steam reforming |
| WO2008135581A1 (en) * | 2007-05-08 | 2008-11-13 | Basf Se | Iridium catalysts for converting hydrocarbons in the presence of water vapour and especially for the steam dealkylation of alkyl-substituted aromatic hydrocarbons |
| CN101289166B (en) * | 2008-06-13 | 2011-09-14 | 清华大学 | Process and device for preparing H2 and CO by co-transformation of CH4 and CO2 |
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- 2013-06-27 JP JP2015519083A patent/JP2015525668A/en active Pending
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