EP1124635A1 - Katalysator zur umwandlung von kohlenwasserstoffen - Google Patents

Katalysator zur umwandlung von kohlenwasserstoffen

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Publication number
EP1124635A1
EP1124635A1 EP99948601A EP99948601A EP1124635A1 EP 1124635 A1 EP1124635 A1 EP 1124635A1 EP 99948601 A EP99948601 A EP 99948601A EP 99948601 A EP99948601 A EP 99948601A EP 1124635 A1 EP1124635 A1 EP 1124635A1
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EP
European Patent Office
Prior art keywords
oxide
nickel
catalyst
temperature
synthesis gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99948601A
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English (en)
French (fr)
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EP1124635A4 (de
Inventor
Graeme John Millar
Jonathan James Gamman
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University of Queensland UQ
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University of Queensland UQ
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Publication of EP1124635A1 publication Critical patent/EP1124635A1/de
Publication of EP1124635A4 publication Critical patent/EP1124635A4/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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

  • This invention relates to catalysts for the production of a mixture of hydrogen and carbon monoxide by carbon dioxide reforming of a hydrocarbon feedstock, and to precursors of such catalysts.
  • the invention also relates to processes for the preparation of such catalysts and precursors, and to a process for the production of a mixture of hydrogen and carbon monoxide by carbon dioxide reforming of a hydrocarbon feedstock.
  • Synthesis gas (commonly termed “ syngas” ) is a mixture of carbon monoxide (CO) and hydrogen (H 2 ) which is used in the manufacture of a wide range of commercially valuable chemicals such as methanol, ammonia, higher alcohols and acetic acid.
  • syngas is primarily produced by steam reforming of a hydrocarbon gas, usually natural gas, in the presence of an appropriate catalyst at high temperature (>700°
  • Choice of product to manufacture is dictated by the ratio of hydrogen to carbon monoxide which is termed the stoichiometric number (SN): For example, methanol synthesis is ideally performed with a value for SN of 2.00
  • the carbon dioxide reforming reaction provides a means of reducing emissions when used in conjunction with the utilization of solar energy.
  • the use of solar energy in this context is via a Chemical Energy Transport System (CETS) known as a heat pipe.
  • CETS Chemical Energy Transport System
  • the thermochemical heat pipe concept is illustrated diagrammatically in Figures 1 & 2. Briefly, in the closed loop configuration illustrated in Figure 1, solar energy is used to supply the process heat for the CO 2 reforming reaction. Subsequently, the reaction products (CO and H 2 ) can be stored and/or transported to a separate site and the reverse methanation reaction may be performed subsequently to release the chemically stored 0 solar energy as required. The methanation products are then returned to the reformer reactor to complete the closed loop. Alternatively, an open loop cycle as illustrated in Figure 2 can be employed.
  • the calorific value of the syngas mixture (CO + H 2 ) is 1137 kJ/mol whereas only 890 kJ/mol would be available if only the original methane was combusted.
  • the present inventors have discovered that certain catalysts obtainable from a composition which includes nickel oxide and a second metal oxide or mixed metal oxide having certain specified properties, are capable of use in a process for reforming hydrocarbons with carbon dioxide to produce a mixture of hydrogen and carbon monoxide, the catalysts having an improved lifetime compared to known catalysts for such a reaction, by virtue of being relatively resistant to deactivation by coking.
  • a catalyst precursor for reforming hydrocarbons to produce synthesis gas at an elevated temperature which catalyst precursor includes a solid solution of nickel oxide in an oxide of cubic structural type which is an oxygen ion conductor at the elevated temperature.
  • a process for producing a catalyst precursor including the steps of (i) impregnating a support material with a solution of a nickel compound, the support material being an oxide of cubic structural type which is an oxygen ion conductor at a temperature in the range 300- 1000°C;
  • a process for producing a catalyst precursor including the steps of (i) impregnating a support material with a solution of a nickel compound, the support material being an oxide of cubic structural type which is an oxygen ion conductor at a temperature in the range 300-1000°C;
  • a catalyst precursor produced by the process of the second or third embodiments.
  • a catalyst for reforming hydrocarbons to produce synthesis gas the catalyst being obtainable by reducing a catalyst precursor of the first or fourth embodiments in a reducing atmosphere at an elevated temperature.
  • a process for producing a catalyst for reforming hydrocarbons to produce synthesis gas including the steps of
  • step (iv) contacting the product of step (iii) with a reducing atmosphere for a time and at a temperature sufficient to reduce at least part of the nickel to nickel metal.
  • a process for reforming a hydrocarbon to produce synthesis gas including the step of contacting a reactant mixture of carbon dioxide and the hydrocarbon with a catalyst of the fifth or seventh embodiments at a temperature and pressure, and for a time sufficient to convert at least part of the reactant mixture to synthesis gas.
  • a catalyst precursor for reforming hydrocarbons to produce synthesis gas at an elevated temperature which catalyst precursor includes a mixture of nickel oxide and an oxide of cubic structural type which is an oxygen ion conductor at the elevated temperature.
  • a process for producing a catalyst precursor including the steps of (i) impregnating a support material with a solution of a nickel compound, the support material being an oxide of cubic structural type which is an oxygen ion conductor at a temperature in the range 300-1000°C;
  • a catalyst precursor produced by the process of the tenth embodiment.
  • a catalyst for reforming hydrocarbons to produce synthesis gas the catalyst being obtainable by reducing a catalyst precursor of the ninth or eleventh embodiments in a reducing atmosphere at an elevated temperature.
  • a process for reforming a hydrocarbon to produce synthesis gas including the step of contacting a reactant mixture of carbon dioxide and the hydrocarbon with a catalyst of the twelfth embodiment at a temperature and pressure, and for a time sufficient to convert at least part of the reactant mixture to synthesis gas.
  • Fig. 1 is a schematic of the concept of a closed loop thermochemical heat pipe
  • Fig. 2 is a schematic of the concept of an open loop thermochemical heat pipe
  • Figs. 3(a) to 3(c) are XRD traces for nickel oxide/yttrium oxide catalyst precursors including respectively 0, 5 and 30 wt% nickel.
  • Fig. 4 includes XRD traces for nickel oxide/silica catalyst precursors, not in accordance with the present invention, having three different weight loadings of nickel.
  • Figs. 5(a) to 5(c) are XRD traces for nickel oxide/terbium oxide catalyst precursors including respectively 0, 5 and 30 wf% nickel.
  • Figs. 6(a) to 6(c) are XRD traces for nickel oxide/praseodymium oxide catalyst precursors including respectively 0, 5 and 30 wt% nickel.
  • Fig. 7 includes XRD traces for (a) 5 wt% nickel oxide/gadolinium oxide, (b) 5 wt% nickel oxide/praseodymium oxide and (c) 5 wt% nickel oxide/ytterbium oxide
  • Fig. 8 is a temperature programmed reaction profile of the interaction between carbon dioxide and methane (1 :1 ratio) as a function of temperature in the presence of a 5 wt% nickel/yttrium oxide catalyst.
  • Fig. 9 is a temperature programmed reaction profile of the interaction between carbon dioxide and methane (1 :1 ratio) as a function of temperature in the presence of a 5 wt% nickel/gadolinium oxide catalyst.
  • Fig. 10 is a temperature programmed reaction profile of the interaction between carbon dioxide and methane (1 : 1 ratio) as a function of temperature in the presence of a 5 wt% nickel/praseodymium oxide catalyst.
  • Fig. 11 is a temperature programmed reaction profile of the interaction between carbon dioxide and methane (1 :1 ratio) as a function of temperature in the presence of a 5 wt% nickel/ytterbium oxide catalyst.
  • Fig. 12 is a temperature programmed reaction profile of the interaction between carbon dioxide and methane (1 : 1 ratio) as a function of temperature in the presence of a 5 wt% nickel/terbium oxide catalyst.
  • Fig. 13 is a temperature programmed reaction profile of the interaction between carbon dioxide and methane (1 :1 ratio) as a function of temperature in the presence of a 5 5 wt% nickel/samarium oxide catalyst.
  • Fig. 14 is a temperature programmed reaction profile of the interaction between carbon dioxide and methane (1 : 1 ratio) as a function of temperature in the presence of a 5 wt% nickel/lanthanum-strontium-gallium-magnesium oxide catalyst.
  • Fig. 15 is a transmission electron microscopy (TEM) image of a 5 wt% o nickel/yttrium oxide catalyst after calcination.
  • TEM transmission electron microscopy
  • Fig. 16 is a transmission electron microscopy (TEM) image of a 5 wt% nickel/yttrium oxide catalyst after reaction at 750°C for 50 hours.
  • TEM transmission electron microscopy
  • Fig. 17 shows transmission electron microscopy (TEM) images of (a) 1 wt%, (b) 5 wt , (c) 10 wt% and (d) 30wt % nickel/silica catalyst after calcination.
  • 5 Fig. 18 is a transmission electron microscopy (TEM) image of a 30 wt% nickel/MgO catalyst after calcination.
  • Fig. 19 is a transmission electron microscopy (TEM) image of a 30 wt% nickel/MgO catalyst after reaction at 750°C for 50 h.
  • TEM transmission electron microscopy
  • Fig. 20 shows XRD traces for (a) yttrium oxide, (b) 5 wt% nickel/yttrium oxide o after calcination and (c) 5 wt% nickel/yttrium oxide after reaction with CO 2 /CH 4 at 750° C for 5 Oh.
  • Fig. 21 shows XRD traces for (a) magnesium oxide, (b) 30 wt% nickel/magnesium oxide after calcination and (c) 30 wt% nickel/magnesium oxide after reaction with C0 2 /CH 4 at 750°C for 50h.
  • oxide of cubic structural type means an oxide of a metal or a mixed metal oxide which has an ideal cubic or distorted cubic structure. Examples of such structures includes fluorite, perovskite, pyrochlore, brownmillerite and spinel structures.
  • the oxide of cubic structural type may be any such metal oxide, including an oxide of a single metal or a mixed metal oxide, provided it is also an oxygen ion conductor at a temperature in the range of about 300-1000°C; that is, a temperature range which includes the typical temperatures for the hydrocarbon reforming reaction for which the catalysts of the invention, obtainable from the catalyst precursors of the invention, may be used.
  • suitable oxides include but are not limited to Z ⁇ - ] _ x Y x O 2 _ x/2 , Ce ⁇ _ ⁇ Gd x° 2 -x /2> La Ci"i- ⁇ Mg x O 3 . x/2 , La 1 .
  • the oxide of cubic structural type is an oxide of an element selected from the group consisting of yttrium, gadolinium, praseodymium, samarium, ytterbium and terbium.
  • the amount of nickel in the catalysts and catalyst precursors of the invention is in the range of from about 1% to 50% by weight, more typically from about 5%> to about 40% by weight, or from about 6% to about 40%> by weight, or from about 7% to about 40%) by weight, or from about 8% to about 40% by weight, or from about 9% to about 40%) by weight, still more typically from about 10% to about 40% by weight, even more typically from about 10% to about 30% by weight, based on the total weight of the catalyst or catalyst precursor.
  • Modifiers to enhance the activity of the catalyst and catalyst precursor formulations described above may be added.
  • these can be included in the catalyst by any convenient method, the precise choice may depend on the identity of the additive.
  • promoting species may simply be added to the initial impregnating solution of nickel precursor, or they be incorporated as part of a co-precipitation procedure.
  • a catalyst of the invention may further include one or more additives selected from the group consisting of:
  • noble metals selected from the group consisting of Pt, Ir, Rl , Ru, Os, Pd and Re
  • oxides selected from the group consisting of TiO 2 , Mo0 3 . WO 3 , ZrO 2 , V 2 O 5 ,
  • elements selected from the group consisting of Ag, Cu, Au and Zn elements selected from the group consisting of P, Sb, As, Sn and Ge.
  • the amounts included are typically in the range of:
  • V 2 0 , Nb 2 0 5 , Sc 2 O 5 and Ta 2 O 5 from 0.01% to 20%;
  • the active catalyst components can be dispersed on the surface of a conventional oxide carrier of which silica, alumina, zirconia, thoria, silica-alumina, zeolites, clay minerals and derivatives of clay minerals are common examples.
  • a conventional oxide carrier of which silica, alumina, zirconia, thoria, silica-alumina, zeolites, clay minerals and derivatives of clay minerals are common examples.
  • the support material employed although it is desirable that the catalyst display good attrition resistance and high crush strength for industrial usage. Formation of a supported catalyst of this kind may readily be achieved by impregnation of soluble precursors of the nickel oxide and the oxide of cubic structural type on the support of choice, followed by drying and calcination.
  • step (i) is a step of wet impregnation of the oxide of cubic structural type by an aqueous solution of a soluble nickel compound.
  • a suitable soluble nickel compound is nickel nitrate.
  • any other metal salt which is soluble in an aqueous solution can alternatively be used, such as nickel bromide, nickel chloride, nickel iodide and nickel sulfate.
  • use may also be made of an organic solvent and a nickel compound which is soluble in the organic solvent.
  • Catalyst precursors of the invention may be prepared using methods other than wet impregnation techniques, however.
  • Alternative synthesis routes known to those skilled in the art can also be employed, examples of which include coprecipitation and solid state reaction.
  • the heating temperature in step (ii) is typically carried out in an oxygen containing atmosphere. More typically the atmosphere is air or oxygen gas.
  • the heating o temperature in step (ii) is typically in the range of from 250°C to 1500°C, more typically in the range selected from the group consisting of 250°C to 1400°C, 250°C to 1300°C, 250°C to 1200°C, 250°C to 1100°C, 250°C to 1000°C, 250°C to 950°C, 250°C to 900°C, 250°C to 850°C, 250°C to 800°C, 300°C to 800°C, more typically 350°C to 600°C.
  • Calcination temperatures for nickel salts that is, temperatures at which nickel salts may be converted to nickel oxide, are generally known to persons of ordinary skill in the art, as are appropriate calcination times.
  • Step (iii) of the process of the second, third, sixth or tenth embodiments may also be carried out a temperature typically in the range of from 250°C to 1500°C, more typically in the range selected from the group consisting of 250°C to 1400°C, 250°C to 1300°C, 250°C to 1200°C, 250°C to 1100°C, 250°C to 1000°C, 250°C to 950°C, 250°C to 900°C, 250°C to 850°C, 250°C to 800°C, 300°C to 800°C, more typically 350°C to 600°C.
  • the temperature for step (ii) may be the same or different to the temperature for step (iii).
  • the time required in step (iii) of the process of the second, third or tenth embodiments to heat the mixture of the nickel oxide and support material to form the catalyst precursor is in the range selected from the group consisting of about 15 to about 30 minutes, about 30 to about 40 minutes, about 40 to about 50 minutes, about 50 to about 60 minutes, about 60 minutes to about 70 minutes, about 70 minutes to about 80 minutes, about 80 minutes to about 90 minutes. It is also usual that the time required in step (iii) of the process may take at least 100 minutes or more, or at least 2 hours or more. It will be appreciated, however, that the time required is dependent on the temperature of process step (iii).
  • Conditions for step (iii) of the process of the second embodiment may be determined readily by monitoring the heated composition for the formation of a solid solution.
  • the identification of the formation of the catalyst precursor which in one embodiment of the invention entails the identification of the formation of a solid solution is readily made by inspection of an X-ray powder diffraction profile for the material, as illustrated in accompanying Figures 3 to 7. There is shown in Figure 3, X-ray diffraction (XRD) patterns for yttrium oxide, 10 wt % nickel oxide-yttrium oxide and 30 wt % nickel oxide-yttrium oxide. Notably, the XRD trace for pure yttrium oxide is very sharp and intense which is indicative, to those of ordinary skill, of a highly crystalline material.
  • the XRD pattern becomes less intense and the lines become broader in character as the nickel is added.
  • the 30 wt % nickel oxide-yttrium oxide catalyst exhibits extremely broad lines due to the yttrium oxide component which is recognised by those skilled in the art to be representative of an amorphous or nanocrystallme oxide material.
  • the presence of very wide reflections attributable to nickel oxide which again not only indicates the presence of amorphous or nanocrystallme nickel oxide but also the weak intensity of these latter features can be interpreted as meaning that there may exist a fraction of the nickel species in a solid solution with the yttrium oxide.
  • FIG. 4 illustrates XRD profiles recorded for a series of calcined nickel/silica catalysts.
  • the silica support is characterized by an amorphous "lump" at low values of 2 ⁇ . whereas sharp, intense peaks are apparent for nickel oxide at 37, 43 and 63 degrees 20. As the loading of nickel becomes higher, the XRD peaks become narrower, thus indicating that the nickel particles were becoming larger and more crystalline in character. o Electron microscopy observations are consistent with this interpretation. Importantly, the silica support of the nickel/silica catalyst does not have the ability to form a solid solution with nickel.
  • Nickel particles are neither as well dispersed as in those catalysts described in this invention or as small and amorphous or nanocrystalline in structure.
  • Figures 5 and 6 which display XRD patterns for a nickel oxide/terbium oxide and nickel oxide/praseodymium catalysts, respectively.
  • the features for the terbium oxide component diminish in intensity as the nickel loading is increased, again indicative of a o more amorphous or nanocrystalline material.
  • the reflections characteristic for nickel oxide are extremely weak in intensity.
  • the nickel component may at least in part be forming a solid solution with the rare earth material or at least the rare earth material has the ability to disperse the nickel component to a greater extent, than that for a silica support.
  • the XRD trace clearly illustrates that the reflections assigned to praseodymium oxide become very broad and weak in intensity as the nickel loading increases.
  • Another feature of the catalysts of the present invention is the general observation that the catalyst surface area increases as the nickel loading increases.
  • Table 1 illustrates the surface areas as calculated by the standard BET method for several of the catalysts revealed in this disclosure, and for comparison purposes, surface areas of silica and nickel oxide/silica catalysts are shown.
  • the precursors of catalysts of the invention require reduction to produce the catalysts.
  • Reduction of the catalyst precursor can be achieved by pre-reducing the catalyst at a temperature of 300°C or greater with a gas stream comprising of hydrogen or any other readily available reductant, such as carbon monoxide or a hydrocarbon, such as methane.
  • a gas stream comprising of hydrogen or any other readily available reductant, such as carbon monoxide or a hydrocarbon, such as methane.
  • Other catalyst precursor compositions may require reduction at still higher temperatures, such as up to about 900° C.
  • the reduction procedure employed should preferably be at a temperature which will facilitate reduction of a fraction of the nickel ions to nickel metal.
  • the catalyst precursor may be prereduced in situ by exposure to the reactant mixture itself, and optionally raising the temperature above the desired reaction temperature for the reforming reaction.
  • a process of the eighth or thirteenth embodiments of the invention may be carried out using a catalyst in accordance with the invention under conditions generally known in the art for carbon dioxide reforming reactions.
  • typically conditions for carrying out the process of the fourth embodiment of the present invention include a temperature range of from about 300-1100°C, more typically from about 400°C to 850°C, at a pressure of from about lOkPa to about 10,000kPa, more typically from about lOOkPa to about 5,000kPa, still more typically from about lOOkPa to about 3,000kPa. at an apparent space velocity in the range of from about 1000 to lOOOOOOlr' ., more typically from about 10000 to 500000h- ] .
  • the hydrocarbon in a reactant mixture for the process of the eighth or thirteenth embodiments is typically methane but may also be a mixture of one or more hydrocarbons selected from methane and higher hydrocarbons such as ethane, ethene, ethyne, propane, propene, butane(s), butene(s), butyne(s), etc.
  • Typical reactant mixture compositions in the process of the eighth or thirteenth embodiments may contain, in addition to the hydrocarbon and carbon dioxide, other gases such as hydrogen, carbon monoxide, substantially inert gases such as nitrogen, helium and/or argon, and/or small amounts of oxygen.
  • the proportion of hydrocarbon relative to carbon dioxide will be in the range of from 20:1 to 1 :20, more typically 9: 1 to 1 :9, even more typically 4: 1 to 1 :4.
  • Example 1 Commercially available yttrium oxide (Pi-KEM, UK) was impregnated with an aqueous solution of Ni(N0 3 ) 2 .6H 2 O (Aldrich, 99.999 %) and the resulting slurry dried at 100°C for several hours. The impregnated catalyst consisting of 1 wt% nickel was then calcined in flowing air at 500°C for 2 h to decompose the nitrate species.
  • yttrium oxide Pi-KEM, UK
  • Ni(NO 3 ) 2 .6H 2 O Aldrich, 99.999 %
  • the impregnated catalyst consisting of 5 wt%> nickel was then calcined in flowing air at 500°C for 2 h to decompose the nitrate species.
  • the catalyst was subsequently reduced in hydrogen at 500°C for 2 hours and then cooled to ambient temperature.
  • TPRxn temperature programmed reaction
  • Example 3 Commercially available gadolinium oxide (Pi-KEM, UK) was impregnated with an aqueous solution of Ni(NO 3 ) 2 .6H 2 0 (Aldrich, 99.999 %) and the resulting slurry dried at 100°C for several hours.
  • the impregnated catalyst consisting of 5 wt% nickel was then calcined in flowing air at 500°C for 2 h to decompose the nitrate species. The catalyst was subsequently reduced in hydrogen at 500°C for 2 hours and then cooled to ambient temperature.
  • Example 7 Commercially available terbium oxide (Pi-KEM, UK) was impregnated with an aqueous solution of Ni(NO 3 ) 2 .6H 2 O (Aldrich, 99.999 %) and the resulting slurry dried at
  • a portion of the oxygen ion conductor lanthanum-strontium-gallium-magnesium oxide (La 0.9 Sro .
  • the impregnated catalyst consisting of 5 wt % nickel was then calcined in flowing air at 500°C for 2 h to decompose the nitrate species. The catalyst was subsequently reduced in hydrogen at 500°C for 2 hours and then cooled to ambient temperature.
  • Example 9 The calcined 5% Ni/yttrium oxide precursor, prepared as described in Example 2, after calcining, was pelleted, crushed and sieved to a particle size between 0.7 and 1.0 mm before placement into a microreactor facility for catalyst activity evaluation. Approximately 0.2 g of catalyst was loaded into a 12 mm diameter quartz reactor tube situated in an electrically heated furnace which was capable of operation between 25 and 1000°C. Samples were pre-reduced in a 20% hydrogen/helium mixture at 500°C for lh. Subsequently, an equimolar mixture of carbon dioxide and methane (total flow rate 200 mL/min) was contacted with the catalyst resulting in an apparent space velocity (GHSV) of 35,000h"' .
  • GHSV apparent space velocity
  • Example 10 The unique behaviour of the catalysts described in this invention is also revealed by inspection of transmission electron microscopy (TEM) obtained before after 50 hours of C0 2 /CH 4 reaction at 750°C.
  • Fig. 15 displays TEM images of a 5 wt % Ni/yttrium oxide catalyst following calcination of the sample. Notably, the images reveal the presence of only nanocrystalline yttrium oxide with no evidence for large nickel grain (>5 nm) detected. Even after reaction at 750°C for 50 h (Fig. 16) no nickel crystallites were discerned: indeed the only significant feature was the growth of yttrium oxide tubules. Comparative Example 2
  • Fig. 17 displays TEM images of a range of nickel/silica catalysts following the calcination procedure.
  • nickel particles were readily detected which illustrated that silica was not an effective support for dispersing nickel. Consequently, those skilled in the art would realise that silica supported catalysts would not only deactivate due to significant coking on the large nickel crystallites but also nickel sintering would occur during reaction conditions leading to disastrous loss of surface area.
  • Fig. 18 provides an image of a 30 wt % Ni/MgO catalyst following calcination. The nickel species appeared to be well dispersed due to the formation of a solid solution
  • Example 1 1 The efficiency of the catalysts disclosed in this invention for dispersion and stabilization of nickel species is further shown by inspection of the relevant X-ray diffraction (XRD) patterns for the catalyst before and after reaction at 750°C for 50 hours.
  • Figure 20 shows XRD traces for yttrium oxide, calcined 5 wt % nickel/yttrium oxide and 5 wt % nickel/yttrium oxide after reaction. Significantly, no evidence for nickel crystallite growth is detected.
  • XRD X-ray diffraction
  • Table 1 BET surface areas of a representative sample of catalysts for this invention.

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  • Engineering & Computer Science (AREA)
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EP99948601A 1998-09-21 1999-09-21 Katalysator zur umwandlung von kohlenwasserstoffen Withdrawn EP1124635A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPP6073A AUPP607398A0 (en) 1998-09-21 1998-09-21 Catalysts and process for reforming of hydrocarbons
AUPP607398 1998-09-21
PCT/AU1999/000802 WO2000016899A1 (en) 1998-09-21 1999-09-21 Catalysts and process for reforming of hydrocarbons

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EP1124635A1 true EP1124635A1 (de) 2001-08-22
EP1124635A4 EP1124635A4 (de) 2002-01-30

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