WO2013135659A1 - Procédé pour réduire du dioxyde de carbone à haute température sur des catalyseurs sous forme oxydée comprenant du nickel et du ruthénium - Google Patents

Procédé pour réduire du dioxyde de carbone à haute température sur des catalyseurs sous forme oxydée comprenant du nickel et du ruthénium Download PDF

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WO2013135659A1
WO2013135659A1 PCT/EP2013/054946 EP2013054946W WO2013135659A1 WO 2013135659 A1 WO2013135659 A1 WO 2013135659A1 EP 2013054946 W EP2013054946 W EP 2013054946W WO 2013135659 A1 WO2013135659 A1 WO 2013135659A1
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catalyst
reaction
oxide
heating
carbon dioxide
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PCT/EP2013/054946
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German (de)
English (en)
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Daniel Gordon Duff
Alexander Karpenko
Emanuel Kockrick
Vanessa GEPERT
Albert TULKE
Leslaw Mleczko
Daniel Wichmann
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Bayer Intellectual Property Gmbh
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Publication of WO2013135659A1 publication Critical patent/WO2013135659A1/fr

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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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    • B01J37/06—Washing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for reducing carbon dioxide comprising the step of reacting carbon dioxide and hydrogen in the presence of a catalyst to form carbon monoxide and water.
  • the invention further relates to the use of such a catalyst in the reduction of carbon dioxide.
  • WGS water gas shift reaction
  • WO 00/43121 A1 discloses a catalyst, in particular for the steam reforming of hydrocarbons, which nickel and ruthenium metals in intimate mixture with lanthanum oxide and aluminum oxide on a preformed, preferably porous support.
  • the present invention has therefore set itself the task of providing a method for carrying out the RWGS reaction, which can be operated with a low-cost catalyst with high activity and selectivity and a long-term stability at high temperatures.
  • This object is achieved by a method for the reduction of carbon dioxide, comprising the step of the reaction of carbon dioxide and hydrogen in the presence of a catalyst to form carbon monoxide and water, wherein the reaction is carried out at a temperature of> 700 ° C and the catalyst oxide catalyst comprising Ni and Ru.
  • Ni and Ru content in the catalyst it is possible for Ni and / or Ru to be present in a metallic, optionally alloyed form. But it is also possible that they are present in oxidized form. A juxtaposition of metallic and oxidized form is also included according to the invention.
  • the catalysts used according to the invention or their conversion products under the prevailing reaction conditions are stable catalysts which are comparable with industrial benchmark systems in at least one respect.
  • the RWGS reaction can be selectively operated at the elevated temperatures according to the invention.
  • the present invention relates to the recovery of CO and H2O by RWGS reaction. This is in contrast to the WGS reaction, where possibly the back reaction also leads to CO and H 2 O.
  • the process according to the invention is preferably carried out such that the conversion of CO 2 after completion of the reaction (in particular after leaving a reactor such as, for example, an axial flow reactor) is more than 35 mol%, preferably more than 40 mol%, more preferably more than 45 mol% and most preferably above 50 mole%.
  • misch metal catalysts on high temperature stable oxides are suitable as carriers.
  • a synergistic effect is achieved in the catalyst by the two-component metal combinations. This means that the activity and / or the stability is in each case better than the additive combination of the pure monometallic catalysts. This is probably due to the formation of a stable and active intermetallic phase under the reaction conditions.
  • the catalysts to be used according to the invention can be prepared, inter alia, by physical (such as PVD) and chemical methods, the latter predominantly in the solid phase or liquid phase. Examples include precipitation, co-precipitation, sol-gel processes, impregnation, ignition / combustion methods, and further gas phase methods such as CVD.
  • reaction products includes the catalyst phases present under reaction conditions.
  • the gas mixture to which the catalyst is exposed during the reaction comprising carbon dioxide, hydrogen, carbon monoxide and water may contain these four components, for example, in a content of> 80% by weight, preferably> 90% by weight and more preferably> 95% by weight ,
  • a reaction temperature of> 700 ° C is provided.
  • the reaction temperature is> 850 ° C, and more preferably> 900 ° C.
  • a hydrocarbon having 1 to 4 C atoms is added during the reaction.
  • Suitable hydrocarbons are, in particular, alkanes having 1 to 4 C atoms, methane being particularly suitable.
  • the addition of the hydrocarbon takes place at arbitrary positions along the longitudinal axis of the reactor. For example, hydrocarbon addition may occur at the reactor inlet, at the reactor outlet and / or at a position between inlet and outlet.
  • the hydrocarbon may, for example, in a proportion of> 0.01% by volume to ⁇ 20% by volume, preferably> 0.1% by volume to ⁇ 10% by volume and more preferably> 1% by volume to ⁇ 10% by volume , based on the total volume of the reaction gases, are added. Regardless, it is preferred that the concentration of the hydrocarbon after the reaction, especially at the outlet of a reactor in which the reaction is carried out, is ⁇ 20% by volume and preferably ⁇ 10% by volume.
  • the catalyst comprises Ni and Ru on Ce-Zr-Al oxide, on an oxide from the class of perovskites and / or on an oxide from the class of hexaaluminates.
  • the weight proportion of Ni and Ru is in each case> 0.01% by weight to ⁇ 25% by weight, based on the total weight of the catalyst. Preference is given to proportions of> 0.1% by weight to ⁇ 5% by weight.
  • An ideal perovskite structure is understood to mean a structure ABO 3 in which the cations A and the oxygen ions build up a cubic-dense sphere packing. Each fourth octahedral gap of the spherical packing is occupied by cations B. As there are as many octahedral gaps as packing particles in a dense spherical packing, the sum formula ABO3 results again. Deviations from this stoichiometry are also possible within the classical perovskite structure.
  • the perovskite structures include not only the classical cubic crystal lattices but also those with distorted lattices such as orthorhombic and rhombohedral crystal structures. Also other types with different stoichiometries belong to it, like the so-called Schichtperowskiten or Ruddlesden Popper phases with the general formula (AO) (1 - q) . (AB0 3 ) q .
  • LAI12O19 or LAI 11 O 18 can be considered. This may alternatively be L0 (A1 2 03) 6 or LOi ; 5 (Al 2 O 3 ) 5.5.
  • L are in particular Ba, Sr, Ca, La, ... and other metals of alkaline earth (Group 2) and rare earths (lanthanides) and mixtures thereof.
  • these simple hexaaluminate compositions may already have some basic activity for the RWGS or are suitable as high-temperature stable carriers which can be loaded with active metal particles in a post-preparation step.
  • M is typically transition metals of the first, second or third series, in particular the transition metals of the first series Cr, Mn, Fe, Co, Ni and the noble metals such as Ru, Rh, Pd and Pt.
  • Multiple catalytically active dopants may be combinations of different first-row transition metals, combinations of different precious metals, or combinations of one or more noble metals with one or more transition metals of the first series. Further substitutions at L and / or M posts, also apart from the already named element groups, are partly also possible. The thus substituted hexaaluminate can then be doped, loaded or mixed with further catalytic substances.
  • the formula can be postulated such that the ratio between LO and Al2O3, namely the parameter z in the structural formula LO supplemented by M (M ( y / z ) Al (2 - y / z ) 03) z , according to 4 ⁇ z ⁇ 9 is varied.
  • L can also stand for a mixture of several divalent and / or trivalent cations (L, L ', L ",).
  • Preferred catalysts with hexaaluminate substrate are those of the type Ba-Ni-Ru-Aln Oi 9 .
  • the reaction is carried out at a temperature of> 700 ° C to ⁇ 1300 ° C. More preferred ranges are> 800 ° C to ⁇ 1200 ° C and> 900 ° C to ⁇ 1100 ° C, especially> 850 ° C to ⁇ 1050 ° C.
  • the reaction is carried out at a pressure of> 1 bar to ⁇ 200 bar.
  • the pressure is> 2 bar to ⁇ 50 bar, more preferably> 10 bar to ⁇ 30 bar.
  • the catalyst is applied to a support and the support is selected from the group comprising oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • the support is selected from the group comprising oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • An example of this is SiC. Further preferred is cordierite.
  • the reaction is operated in autothermal mode.
  • This can be achieved, for example, both by the addition of oxygen in the educt gas, as well as that hydrogen-rich residual gases such as anode residual gas, PSA residual gas, natural gas (preferably methane) and / or additional hydrogen in the presence of CO 2 fuel gas sources.
  • Another object of the present invention is the use of a catalyst comprising a mixed metal oxide in the reaction of carbon dioxide and hydrogen to form carbon monoxide and water, the catalyst being an oxide catalyst comprising Ni and Ru.
  • the catalyst comprises Ni and Ru on Ce-Zr-Al oxide, on an oxide of the class of perovskites, and / or on an oxide of the class of hexaaluminates.
  • the catalyst is applied to a support and the support is selected from the group comprising oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • the support is selected from the group comprising oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium.
  • An example of this is SiC.
  • Further preferred is cordierite.
  • FIG. 1 shows schematically an expanded view of a reactor for carrying out the method according to the invention.
  • FIG. 2-4 show turnover curves for CO 2 in various RWGS experiments.
  • FIG. 5 shows the particle size distribution after laser diffraction of an aqueous suspension of the uncalcined catalyst precursor dried at 90 ° C., (1) without ultrasonic treatment in the laser diffraction apparatus, (2) after 60 s ultrasonic treatment in the laser diffraction apparatus
  • FIG. Figure 6 shows the powder X-ray diffractogram of the calcined catalyst.
  • the positions marked with asterisks are the diffraction reflections expected for the rhombohedral perovskite, LaNi03.
  • FIG. FIG. 7 shows the CO 2 conversion (X (CO 2)) on the LaNio, 95Ruo, osO 3 catalyst produced by co-precipitation on a larger scale as a function of the reaction time t.
  • the reaction can be carried out in a flow reactor which, viewed in the flow direction of the reaction gases, comprises a plurality of heating levels 100, 101, 102, 103, which are electrically heated by means of heating elements 110, 111, 112, 113, heating levels 100, 101, 102, 100 are flowed through by the reaction gases, wherein at least one heating element 110, 111, 112, 113, the catalyst is arranged and is heated there and at least once an intermediate level 200, 201, 202 between two Heating levels 100, 101, 102, 103 is arranged, wherein the intermediate level 200, 201, 202 is also flowed through by the reaction gases.
  • the reactor has a plurality of (four in the present case) heating levels 100, 101, 102, 103, which are electrically heated by means of corresponding heating elements 110, 111, 112, 113.
  • the heating levels 100, 101, 102, 103 are flowed through by the reaction gases in the operation of the reactor and the heating elements 110, 111, 112, 113 are contacted by the reaction gases.
  • At least one heating element 110, 111, 112, 113, the catalyst is arranged and is heated there.
  • the catalyst may be directly or indirectly connected to the heating elements 110, 111, 112, 113 so that these heating elements constitute the catalyst support or a support for the catalyst support.
  • the heat supply of the reaction takes place electrically and is not introduced from the outside by means of radiation through the walls of the reactor, but directly into the interior of the reaction space. It is realized a direct electrical heating of the catalyst.
  • the heating elements 110, 111, 112, 113 are preferably Schuleiterlegtechniken such as FeCrAl alloys used.
  • At least one ceramic intermediate level 200, 201, 202 (which is preferably supported by a ceramic or metal support plane) is arranged between two heating levels 100, 101, 102, 103, the intermediate level (s) being 200, 201, 202 or the contents 210, 211, 212 of an intermediate level 200, 201, 202 are also flowed through during operation of the reactor from the reaction gases. This has the effect of homogenizing the fluid flow. It is also possible that additional catalyst is present in one or more intermediate levels 200, 201, 202 or other isolation elements in the reactor. Then an adiabatic reaction can take place.
  • the material forms an Al 2 O 3 protective layer by the action of temperature in the presence of air / oxygen.
  • This passivation layer can serve as the basis of a washcoat which acts as a catalytically active coating.
  • the direct resistance heating of the catalyst or the heat supply of the reaction is realized directly through the catalytic structure.
  • the formation of other protective layers such as Si-OC systems.
  • the pressure in the reactor can take place via a pressure-resistant steel jacket. Using suitable ceramic insulation materials it can be achieved that the pressure-bearing steel is exposed to temperatures of less than 200 ° C and, if necessary, less than 60 ° C. By appropriate devices can be taken to ensure that no dew condensation of water on the steel jacket takes place at dew point.
  • the electrical connections are shown in FIG. 1 only shown very schematically. They can be conducted in the cold region of the reactor within an insulation to the ends of the reactor or laterally out of the heating elements 110, 111, 112, 113, so that the actual electrical connections can be provided in the cold region of the reactor.
  • the electrical heating is done with direct current or alternating current.
  • the use of the electrically heated elements in the inlet region of the reactor also has a positive effect with regard to the cold start and starting behavior, in particular with regard to rapid heating to the reaction temperature and better controllability.
  • the catalyst can in principle be present as a loose bed, as a washcoat or else as a monolithic shaped body on the heating elements 110, 111, 112, 113. However, it is preferred that the catalyst is connected directly or indirectly to the heating elements 110, 111, 112, 113, so that these heating elements constitute the catalyst support or a support for the catalyst support.
  • heating levels 100, 101, 102, 103 heating elements 110, 111, 112, 113 are arranged, which are constructed in a spiral, meandering, grid-shaped and / or reticulated manner.
  • the (for example ceramic) intermediate levels 200, 201, 202 or their contents 210, 211, 212 comprise a material resistant to the reaction conditions, for example a ceramic foam. They serve for mechanical support of the heating levels 100, 101, 102, 103 and for mixing and distribution of the gas stream. At the same time an electrical insulation between two heating levels is possible. It is preferred that the material of the content 210, 211, 212 of an intermediate level 200, 201, 202 comprises oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium. An example of this is SiC. Further preferred is cordierite.
  • the intermediate level 200, 201, 202 may include, for example, a loose bed of solids. These solids themselves may be porous or solid, so that the fluid flows through gaps between the solids. It is preferred that the material of the solids Oxides, carbides, nitrides, phosphides and / or borides of aluminum, silicon and / or zirconium. An example of this is SiC. Further preferred is cordierite.
  • the intermediate plane 200, 201, 202 comprises a one-piece porous solid.
  • the fluid flows through the intermediate plane via the pores of the solid.
  • honeycomb monoliths as used for example in the exhaust gas purification of internal combustion engines.
  • the average length of a heating level 100, 101, 102, 103 is viewed in the direction of flow of the fluid and the average length of an intermediate level 200, 201, 202 in the direction of flow of the fluid is in a ratio of> 0.01: 1 to ⁇ 100: 1 to each other. Even more advantageous are ratios of> 0.1: 1 to ⁇ 10: 1 or 0.5: 1 to ⁇ 5: 1.
  • At least one heating element 110, 111, 112, 113 can have a different amount and / or type of catalyst from the other heating elements 110, 111, 112, 113.
  • the heating elements 110, 111, 112, 113 are arranged so that they can each be electrically heated independently of each other. Accordingly, in the method according to the invention, the individual heating elements 110, 111, 112, 113 can be operated with a different heating power.
  • the individual heating levels can be individually controlled and regulated.
  • inlet area can be dispensed with a catalyst in the heating levels as needed, so that only the heating and no reaction takes place in the inlet area. This is particularly advantageous in terms of starting the reactor.
  • a temperature profile adapted for the respective reaction can be achieved. With regard to the application for endothermic equilibrium reactions, this is, for example, a temperature profile which reaches the highest temperatures and thus the highest conversion at the reactor.
  • the reactor can be modular.
  • a module may include, for example, a heating level, an intermediate level, the electrical contact and the corresponding further insulation materials and thermal insulation materials.
  • Example 1 Synthesis of Ni and Ni-Ru catalysts on Ce-Zr-Al mixed oxide support by postsynthetic loading
  • Na 2 CO 3 (2.65 g) was placed in 31 ml of water.
  • La (NO 3 ) 3 .6H 2 O (4.33 g) and Ni (NO 3 ) 2 .6H 2 O (2.91 g) were dissolved in 40 ml of water.
  • the metal salt solution was added to the sodium carbonate solution with rapid stirring. After adding the last drops of metal salt solution, the mixture was allowed to age for 1 hour with slow stirring. The precipitate was then filtered off and washed several times on the filter with fresh water. It was then dried in a vacuum drying oven at 90 ° C. overnight. Thereafter, the catalyst was crushed and calcined at 600 ° C for 2 h in a stream of air in a muffle furnace.
  • the catalyst was crushed and calcined at 1300 ° C for 5 hours under air atmosphere.
  • a quantity of Na 2 CO 3 743.4 g was placed in 7159.8 g of water in a 30 liter kettle.
  • Quantities of La (NO 3 ) 3 .6H 2 O 1000.2g
  • Ni (NO 3 ) 2 .6H 2 O 637.0g
  • RuCl 3 32.77g
  • the mixture was stirred at 320 rpm with a stirrer (2 crossbeams and at the lower end a "T-piece") .
  • the reaction mixture was further stirred for 1 h at the same speed
  • the press was washed twice and filtered off between the two filter runs, the precipitate was mashed with a rotor-stator mixer of the brand Ultraturrax and allowed to stand overnight
  • the conductivity after the last washing was 141.8 ⁇ 8 / ⁇ in the wash water was dried in a vacuum drying oven overnight at 90 ° C. After drying, the median diameter of the volume-weighted particle size distribution, d.sub.50, determined was 6.9 ⁇ m.The size distribution is shown in FIG 5.
  • the catalyst then became 5 at 1000.degree calcined under an air atmosphere for a long time he Brunauer-Emmett part method was 5.7 m 2 / g.
  • ICP-OES measurements according to DIN-ISO 17025 gave a sample composition of 0.065% sodium, 2.3% ruthenium, 22% nickel and 54% lanthanum.
  • the X-ray diffraction pattern as shown in FIG. 5 shows the main phase as the perovskite phase of NiLa0 3 and as minor phases NiO and Ni 3 La 4 Oio, or each diffraction-like structures.
  • Example 6 Comparison between a Ni-containing and a Ni-Ru-containing catalyst on Ce-Zr-Al oxide as support
  • the following table summarizes the results of the catalyst comparison in the RWGS reaction for the catalysts from Example 1.
  • X7.5h (C02) [%] means the conversion of CO2, here after 7.5 hours, expressed in mole percent.
  • the term “r e ff, 7.5 h (C02)” indicates the corresponding average reaction rate of CO2 and "X7.5h (C02) / X3h (C02)” is the quotient of the CC conversion after 7.5 hours and after 3 hours.
  • Example 7 Comparison between LaNiQ 3 and LaNio.95Ruo.osO3 (co-precipitation)
  • the following table summarizes the results of catalyst comparison in the RWGS reaction for the catalysts of Examples 2 and 3.
  • the term "X7, sh (C02) [%]” means the conversion of CO2, here after 7.5 hours, expressed in mole percent.
  • the term "r e ff, 7.5 h (C02)” indicates the corresponding average reaction rate of CO2 and "X7.5h (CO 2) / X 3h (CO 2)” is the quotient of the CO conversion to 7.5 Hours and after 3 hours.
  • Example 8 Comparison between Ni and Ni-Ru containing barium hexaaluminate catalysts
  • Example 9 Catalytic properties of larger scale co-precipitated LaNio gsRup osOT catalyst in the RWGS reaction.
  • the following table summarizes the catalyst assay results in the RWGS reaction for the catalyst of Example 5.
  • X7.5h (C02) [%] means the conversion of CO2, here after 7.5 hours, expressed in mole percent.
  • the indication "r e ff; 7,5 h (C02)” gives the corresponding average reaction rate of CO2 and "X50h (CO2) / X3h (CO2)” is the quotient of the CO2 conversion after 50 hours and after 3 hours.
  • FIG. 7 shows the CO2 conversion curve over the reaction time for the larger scale Ru-substituted perovskite catalyst (curve "LaNio.gsRuo.osOs”).
  • the thermodynamic limitation at about 60% conversion is indicated by "TD”.

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Abstract

L'invention concerne un procédé pour réduire du dioxyde de carbone. Ce procédé comprend l'étape consistant à faire réagir du dioxyde de carbone et de l'hydrogène en présence d'un catalyseur avec formation de monoxyde de carbone et d'eau. Ce procédé est caractérisé en ce que la réaction se déroule à une température supérieure ou égale à 700 °, et en ce que le catalyseur est un catalyseur sous forme oxydée comprenant du Ni et du Ru.
PCT/EP2013/054946 2012-03-13 2013-03-12 Procédé pour réduire du dioxyde de carbone à haute température sur des catalyseurs sous forme oxydée comprenant du nickel et du ruthénium WO2013135659A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
WO2000043121A1 (fr) 1999-01-21 2000-07-27 Imperial Chemical Industries Plc Support d'un catalyseur a base de nickel, ruthenium et lanthane
DE10023410A1 (de) * 2000-05-12 2001-11-15 Linde Gas Ag Verfahren zur Erzeugung eines CO- und H2-haltigen Behandlungsgases für die Wärmebehandlung von metallischem Gut, Gasgenerator und Wärmebehandlungsanlage
WO2002046676A1 (fr) * 2000-12-05 2002-06-13 Texaco Development Corporation Appareil et procede de chauffage d'un catalyseur lors du demarrage d'un convertisseur de combustible compact
EP1495802A1 (fr) * 2002-03-29 2005-01-12 Kyushu Electric Power Co., Inc. Composition de catalyseur de modification
WO2009129356A2 (fr) * 2008-04-16 2009-10-22 Basf Catalysts Llc Catalyseurs d'iridium et de ruthénium stabilisés
US20100113263A1 (en) * 2006-02-07 2010-05-06 Samsung Sdi Co., Ltd. Non-pyrophoric shift reaction catalyst and method of preparing the same

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Publication number Priority date Publication date Assignee Title
WO2000043121A1 (fr) 1999-01-21 2000-07-27 Imperial Chemical Industries Plc Support d'un catalyseur a base de nickel, ruthenium et lanthane
DE10023410A1 (de) * 2000-05-12 2001-11-15 Linde Gas Ag Verfahren zur Erzeugung eines CO- und H2-haltigen Behandlungsgases für die Wärmebehandlung von metallischem Gut, Gasgenerator und Wärmebehandlungsanlage
WO2002046676A1 (fr) * 2000-12-05 2002-06-13 Texaco Development Corporation Appareil et procede de chauffage d'un catalyseur lors du demarrage d'un convertisseur de combustible compact
EP1495802A1 (fr) * 2002-03-29 2005-01-12 Kyushu Electric Power Co., Inc. Composition de catalyseur de modification
US20100113263A1 (en) * 2006-02-07 2010-05-06 Samsung Sdi Co., Ltd. Non-pyrophoric shift reaction catalyst and method of preparing the same
WO2009129356A2 (fr) * 2008-04-16 2009-10-22 Basf Catalysts Llc Catalyseurs d'iridium et de ruthénium stabilisés

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JIANGUO ZHANG ET AL: "Kinetic Studies of Carbon Dioxide Reforming of Methane over Ni-Co/Al-Mg-O Bimetallic Catalyst", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 48, no. 2, 21 January 2009 (2009-01-21), pages 677 - 684, XP055064671, ISSN: 0888-5885, DOI: 10.1021/ie801078p *
S. YASYERLI ET AL: "Ru incorporated Ni-MCM-41 mesoporous catalysts for dry reforming of methane: Effects of Mg addition, feed composition and temperature", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 36, no. 8, 1 April 2011 (2011-04-01), pages 4863 - 4874, XP055064698, ISSN: 0360-3199, DOI: 10.1016/j.ijhydene.2011.01.120 *

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