AU759921B2 - Catalysts and process for reforming of hydrocarbons - Google Patents

Description

WO 00/16899 PCT/AU99/00802 Catalysts and process for reforming of hydrocarbons Field of the Invention 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.

Background of the Invention Synthesis gas (commonly termed syngas") is a mixture of carbon monoxide (CO) i 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.

Industrially, syngas is primarily produced by steam reforming of a hydrocarbon gas, usually natural gas, in the presence of an appropriate catalyst at high temperature (>7000 C) and high pressure (1-30 atri). For example, -with methane as the hydrocarbon source the theoretical reaction can be described as follows:

CH

4

H

2 0 CO 3H 2

(AH

298 -206.4 kJ/mole) Choice of product to manufacture is dictated by the ratio of hydrogen to carbon monoxide which is termed the stoichiometric number (SN): SN H2 C02 CO CO2 For example, methanol synthesis is ideally performed with a value for SN of 2.00 CO 2H 2

CH

3

OH

However, SN from steam reforming is usually in the range 2.8-2.6 and thus it must be adjusted by the addition of C 2 3CH4 CO-+-2-H20 4CH 3

OH

There is a growing desire to make syngas with SN values of 1.0 or lower as a number of significant chemicals are more favoured by those latter ratios. For instance, acetic acid is manufactured by the carbonylation of methanol in the presence of a homogeneous catalyst: CO+CH3OH CH 3

COOH

Catalytic reforming of methane with carbon dioxide produces syngas with a low hydrogen to carbon monoxide ratio (SN=1): C02 CH 4 2CO 2H 2 This latter reaction is also of considerable interest in terms of present environmental concerns regarding global warming by the so called greenhouse effect". Carbon dioxide WO 00/16899 PCT/AU99/00802 2 is the main greenhouse gas by volume emitted from anthropogenic sources, and in addition methane is also of concern due to its high global warming potential (21 times that for C0 2 even though significantly less by volume of methane is emitted to the atmosphere compared to carbon dioxide.

The consumption of two greenhouse gases in the CO 2

/CH

4 reforming reaction makes it a potential candidate for achieving substantial reductions in emissions of these gases. Furthermore there exist several large sources of carbon dioxide and methane which are not exploited to their full potential as yet. Such sources iiiclude landfill gas which is a mixture of about 50% methane and 50% carbon dioxide (plus trace impurities), o0 coal bed methane which typically contains from 10 to 70% carbon dioxide, and natural gas fields which may contain from 1 to 70% carbon dioxide.

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.

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 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. In this configuration the product syngas is combusted to produce heat and power (typically in a gas turbine system integrated to an IGCC power plant). The advantage of this process is that the calorific value (relative to the combustion of methane alone) of the fuel is "boosted" by about 28% as can be seen by inspection of the thermodynamics of the reactions involved: Conventional Combustion

CH

4 202 CO, 2H20 -AH =-890kJ/mol Solar boosted reforming followed by combustion 3o CO 2

CH

4 2CO-+ 2H 2 AH +247kJ/mol 2CO 02 2CO 2 AH -566 kJ/mol 2H2 02 2H 2 0 AH 571 kJ/mol Thus, 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.

WO 00/16899 PCT/AU99/00802 3 To date, there is no established industrial technology for carbon dioxide reforming of methane lue primarily to excessive carbon deposition on the catalysts used hitherto.

causing catalyst deactivation. Therefore, there is a need for novel catalysts which are not only active for the carbon dioxide reforming reaction, but also of high resistance to Sdeactivation by coking and thereforeof long lifetime. Desirably, such cataflsts will also be of relatively low cost.

Surprisingly, 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.

Summary of the Invention In accordance with a first embodiment of this invention, there is provided a catalyst i. 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.

In accordance with a second embodiment of the invention, there is provided a process for producing a catalyst precursor including the steps of 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; (ii) if necessary heating the mixture in an atmosphere at a temperature and for a time sufficient to calcine the nickel containing compound to nickel oxide; and 23 (iii) heating the resulting-mixture of nickel oxide and support material for a time and at a temperature sufficient to form a solid solution of at least part of the nickel oxide in the support material.

In accordance with a third embodiment of the invention, there is provided a process for producing a catalyst precursor including the steps of 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 300-1000oC; (ii) if necessary heating the mixture in an atmosphere at a temperature and for a time sufficient to calcine the nickel containing compound to nickel oxide; and WO 00/16899 PCT/AU99/00802 4 (iii) heating the resulting mixture of nickel dxide and support material at a temperature of from 250'C to 15001C for a time sufficient to form the catalyst precursor.

In accordance with a fourth embodiment of the invention, there is provided a catalyst precursor produced by the process of the second or third embodiments.

In accordance with a fifth embodiment of the invention, there is provided 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.

In accordance with asixth embodiment of the invention, there is provided a process ir for producing a catalyst for reforming hydrocarbons to produce synthesis gas including the steps of 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; (ii) if necessary heating the mixture in an atmosphere at a temperature and for a time sufficient to calcine the nickel containing compound to nickel oxide; (iii) heating the resulting mixture of nickel oxide and support material for at least about 15 minutes at a temperatureof from 250'C to 1500C; and (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.

In accordance with a seventh embodiment of the invention, -there is provided a catalyst produced by the process of the sixth embodiment.

In accordance with an eighth embodiment of the invention, there is provided 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.

In accordance with a ninth embodiment 6f~this invention, -there is provided 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.

In accordance with a tenth embodiment of the-invention, there is provided a process for producing a catalyst precursor including the steps of WO 00/16899 PCT/AU99/00802 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; (ii) if necessary heating the-mixture in an atmosphere at a temperature and for a time sufficient to calcine the nickel containing compound to nickel oxide; and (iii) heating the resulting mixture of nickel oxide and support material for a time and at a temperature sufficient to form the catalyst precursor.

In accordance with an eleventh embodiment of the invention, there is provided a catalyst precursor produced by the process of the tenth embodiment.

.In accordance with a twelfth embodiment of the invention, there is provided 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.

In accordance with a thirteenth embodiment of the invention, there is provided a is 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.

Brief Description of the Drawings 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 wt% 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 5 wt% nickel oxide/gadolinium oxide, 5 wt% nickel oxide/praseodymium oxide and 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 wt% nickel/yttrium oxide catalyst.

WO 00/16899 PCT/AU99/00802 6 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 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 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 wt% nickel/ytterbium oxide catalyst.

1o 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 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 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 wt% nickel/lanthanum-strontium-gallium-magnesium oxide catalyst.

Fig. 15 is a transmission electron microscopy (TEM) image of a 5 wt% nickel/yttrium oxide catalyst after calcination.

Fig. 16 is a transmission electron microscopy (TEM) image of a 5 wt% nickel/yttrium oxide catalyst after reaction at 750 0 C for 50 hours.

Fig. 17 shows transmission electron microscopy (TEM) images of 1 wt%, wt%, 10 wt% and 30wt nickel/silica catalyst after calcination, 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 0 C for 50 h.

Fig. 20 shows XRD traces for yttrium oxide, 5 wt% nickel/yttrium oxide 3. after calcination and 5 wt% nickel/yttrium oxide after reaction with C0 2

/CH

4 at 750° C for Fig. 21 shows XRD traces for magnesium oxide, 30 wt% nickel/magnesium oxide after calcination and 30 wt% nickel/magnesium oxide after reaction with C0O/CH 4 at 750 C for WO 00/1 6899 -PCT/AU99/00802 7 Detailed Description of the Preferred Embodiments In this invention, a novel family of nickel based catalysts characterised by excellent activity and stability for carbon dioxide reforming -of methane (or other hydrocarbons) to p~roduce syngas is described.

~As used herein, the expression "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, pyrochiore. brownimillerite and spinel structures.

In the catalyst precursors, catalysts and processes of the invention, 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 temfperature in the range of about 300-1 000'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.

ISExamples of suitable oxides include but are not limited to ZrlyxQ2-x/2, Cel- LaCrl- 1 g -x2 LajXSrxGaO.

8 MgO.

0 5 SrFeCoo.

5 0x, Lai 1 xSrxCoij Y~Fe)Y0 3 -z Bi,V I xCuAOS LaCoO 3 SrCoO 0 2 5 Sc-0j_ YO0 3 Nd 2 0 3 SM2,0 3 GdO, Yb 9 0 3 Pr 6

O

1 1' Tb,0 3 CaO-La 9 )0 3 Sc-)0'-Zr0 2 Lao.8Sr 0 2 MnO 3 ±x, LaO.

6 CaO.

4 Co0.

2 FeO.

8

O

3 -x and SmO.

6 CaO.

4 Co0 3 BaCeO 3 BaTb 0 9 l 1 .03& BaZro.

3 1no0 7 0 3 BaTh 0 9 Gd 0 j03,_BaTb 0 9 Iln 0 103, CaCe 09 gEro.103. Ca~e 0 9 GdO. 103, Ba 8 1n 6 0 7, Ba 3 InxZrxO 8 Ba,4in 2 Zr0 8 Ba 3 Y-,Zr0 8 Ba 3 GdCeO 8 Ba-)Gdln 1 -xGax0 5 BaBi 4 Ti 3 ln0 1 4 5 BaBi 4 Ti 3 ScO 14.5' Sr 2 Gd 2

O

5 Sr,Dy 2 0 5 Sr 6 Nb 2 )O 1 SrBa 6 Ta 9 0O 1 Sr 3 Ti 2 -0 7 Sr 3 Zr 2

O

7 Ba 3 TiO 7 NdAl0 3 Nd 0 9 qCa 0 1 jA10 3 Ba 3 SC-,Zr0 8 Srln 2 )HfQ, Ba~ lnmTiO 8 Ba 3

Y

4 0 9 Ba 8 1n 6 0 17 BaCe 1 -xd03x Sr 3 Ti 1 9 M9 0 10.9 BaCe0 3 (Gd,Yb,Nd), Cai 3 SrZrO 3 BiV 2

O

1 I (Cu,Ni), Ba-)ln 2 0 5 Ba 3 ln 2 )Ce0 8 -Ba~lnHf08, LaGaO 3 Nd- 2 Zr 2 Nd- 2 Ce 9 O0 7 Nd-)CeZrO,- 7 Gd,,Ti 2 0 7 Gd- 9 Zr 9 O0 7 Gd 2 (Zr,Ti) 2 0 7 Sim>Zr,,0 7

Y

2 (Zr,,Ti 9 y)20 7 Gd,)Zr-,0 7 Nd-)Zr 2

O

7 Sm 2 Zr 2

O

7 Gd-)Zr 2 0 7 Gd- 9 ZrgQ, 7

L

9 Zr-Q 7 -ErT30 7

Y

9

T-,

7 -)dZr 2 0 7 Sm 2 )Ti,0 7 (Sr,Ca,Mg), PbWO 4 PbLa 2

WO

4 1, BiVO 4 Bi(Ca)VQ 4 Bi(Ca,Ce.)V0 4 PbMoO 4 Ca 12 A1 14 0 33 Sr 6 Nb-,0 1 1 Sr 6 Ta-)0 11 Ba 6 Nb 2

,O

1 Ba 6 Ta-,0 1 j, Y 3 A1 5 0 1 2, cx-Ta,0 5

Y

0 7 5 Nb 0 15 Ce) I01.7. 6-Bi,0 3 Bi,,0 3 SrO, Bi-,0 3 -BaO, Bi 9 Bi 2 10 3 -PrA0 1 Bi-,0 3 PbO, Sb 2 BiCuV0O, Bi 9 0 3 Y20(0.25). SrCe0 3 SrCe(Yb)0 3 SrZrO 3 (Y,Sc,Yb), Sr 2 (ScNb)0 6 Ba 3 (CdNb)0 9 d, H-Ln-)Ti 3 0lO (Ln La, Nd, Sm, Gd) and HCa-)Nb 3 0O.

WO 00/16899 SPCT/AU99/00802 8 Typically, 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.

Typically, the amount of nickel in the catalysts and catalyst precursors of the S invention is in the range of from about 1% to 50% by weight, more typically from about 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 to catalyst or catalyst precursor.

Modifiers to enhance the activity of the catalyst and catalyst precursor formulations described above may be added. In general, these can be included in the catalyst by any convenient method, the precise choice may depend on the identity of the additive. For example, 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.

In particular, 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, Rh, Ru, Os, Pd and Re; oxides selected from the group consisting of TiO 2 MoO 3

WO

3 ZrOz, Nb 2 Os, Sc 2 05 and Ta2Os; oxides of elements selected from the group consisting of boron, aluminium, gallium and indium; elements selected from the group consisting of Ag, Cu, Au and Zn; and elements selected from the group consisting of P, Sb, As. Sn and Ge.

Where an additive is included in the catalyst precursor or the catalyst, the amounts included are typically in the range of: for noble metals selected from the group consisting of Pt, Ir, Rh,-Ru, Os, Pd and Re. from 0.01% to 3o for oxides selected from the group consisting of TiO 2 MoO 3 W0 3 ZrO2, 5 Nb 2 Sc 2 0 5 and Ta 2 O0, from 0.01% to for oxides of elements selected from the group consisting of .boron, aluminium, gallium and indium, from 0.01% to WO 00/16899 PCT/AU99/00802 9 for elements selected from the group consisting of Ag, Cu; Au and Zn, from 0.01% to 20%; and for elements selected from the group consisting of P, Sb, As, Sn and Ge, from 0.01% to s wherein the percentages are expressed as percentages-by weight based on the total weight of the catalyst.

If desired the active catalyst components can be dispersed on the surface of a conventional oxide carrier of which_ silica, alumina, zirconia, th6iia, silica-alumina, zeolites, clay minerals and derivatives of clay minerals are common examples. There is i no specific limitation onf the support material employed although it is desirable that the catalyst display good attrition resistance and high crush strengfh 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.

i~ In a process of the second, third, sixth or tenth embodiments, step 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. Naturally, 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.

If desired, 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.

In the process of the second, third, sixth or tenth embodiments, the heating temperature in step (ii) is typically carried out in an oxygen containing atmosphere. More typically the atmosphere is air or oxygen gas.

In the process of the second, third, sixth or tenth embodiments, the heating temperature in step (ii) is-typically in the range of from 250°C to 1500C, more typically in the range selected from the group consisting of 250 0 C to 1400 0 C, 250 0 C to 1300 0

C,

250 0 C to 1200 0 C, 250 0 C to 1100 0 C, 250°C to 1000°C, 250 0 C to 950 0 C, 250 0 C to 900 0

C,

250 0 C to 850 0 C, 250 0 C to 800 0 C, 300 0 C to 800 0 C, more- typically 350 0 C to 600 0

C.

Calcination temperatures for nickel salts; that is, temperatures at which nickel salts may WO 00/16899 PCT/AU99/00802 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 0 C to 1500 0 C, more typically in the range selected from the group consisting of 250 0 C to 1400 0 C, 2506C to 1300 0

C,

250 0 C to 1200 0 C, 250 0 C to 1100 0 C, 250 0 C to 1000 0 C, 250 0 C to 950 0 C, 250 0 C to 900 0

C,

250 0 C to 850 0 C, 250 0 C to 800 0 C, 300 0 C to 800 0 C, more typically 350 0 C to 600 0 C. The temperature for step (ii) may be the same or different to the temperature for step (iii): Usually, the time required in step (iii) of the process of the second, third or tenth o 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 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 minutes, about 80 minutes to about 90 minutes. It is also usual that the time required in ii 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 isshown 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.

Significantly, the XRD pattern becomes less intense and the lines become broader in character as the nickel is added. Indeed 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 nanocrystalline oxide material. In harmony, with this observation is the presence of very wide reflections attributable to nickel oxide which again not only indicates the presence of amorphous or nanocrystalline nickel oxide but also the weak intensity of these latter features can be WO 00/16899 PCT/AU99/00802 11 interpreted as meaning that there may exist a fraction of the nickel species in a solid solution with the yttrium oxide.

Inspection of comparative XRD profiles for known nickel/silica catalysts provides a clear indication of the novel and surprising behaviour of the catalysts disclosed in this invention. Figure 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 .whereas sharp, intense peaks are apparent for nickel oxide at 37, 43 and 63 degrees 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.

to 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. Consequently, the nickel particles are neither as well dispersed as in those catalysts described in this invention or as small and amorphous or nanocrystalline in structure. Further illustration of the behaviour of the novel catalysts of the present invention can be seen by inspection of Figures 5 and 6 which display XRD patterns for a nickel Soxide/terbium oxide and-nickel oxide/praseodymium catalysts, respectively. As in the case of the nickel oxide-yttrium oxide catalyst the features for the terbium oxide component diminish in intensity as the nickel loading is increased, again indicative of a more amorphous or nanocrystalline material. Furthermore, the reflections characteristic for nickel oxide are extremely weak in intensity. Therefore, without-wishing to be bound by theory, it appears that 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. Similarly, for the nickel oxide/praseodymium oxide system (Figure the XRD trace clearly illustrates that thereflections assigned to praseodymium oxide become very broad and weak in intensity as the nickel loading increases. Furthermore, there is very little evidence for the presence of nickel crystallites, thus again indicating that either a solid solution has formed or that the praseodymium has a surprising ability to disperse nickel oxide particles extremely well, that-is to an extent where the nickel oxide particles become amorphous or nanocrystalline. Other examples are provided in Fig. 7 which show similar behaviour for nickel/gadolinium oxide and nickel/ytterbium oxide catalysts.

Another feature of the catalysts of the present invention is the general observation that the catalyst surface area increases as the nickel loading increases. For example, Table WO 00/16899 PCT/AU99/00802 12 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, such as in step (iv) of the process of the sixth embodiment, 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. For some catalyst compositions, it is sufficient to reduce the sample at a temperature as low as 3000 io C. although a temperature in excess of 500'C is more typical. Other catalyst precursor compositions may require reduction at still higher temperatures, such as up to about 9000

C.

Without wishing to be bound by theory, it appears that it is necessary to partially reducea fraction of the nickel ions present in the solid solution or amorphous or nanocrystalline form to produce small metal crystallites which participate in the catalytic reaction. Therefore, the reduction procedure employed should preferably be at a temperature which will facilitate reduction of a fraction of the nickel -ions to nickel metal.

Given the teaching _herein, it is a matter of no more than routine experimentation toestablish appropriate reduction conditions to achieve this-objective for any given catalyst precursor of the invention.

Alternatively, where a catalyst precursor is to be used to generate a catalyst to be used directly in a reforming process of the invention, 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 Sthe art for carbon dioxide reforming reactions. That is, 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 0 C to 850 0 C, at a pressure of from about 10kPa to about 10,000kPa, more typically from about 100kPa to about 5,000kPa, still more typically from about 100kPa to about 3,000kPa, at an apparent space velocity in the range of from about 1000 to 1000000h-., more typically from about 10000 to 500000h WO 00/16899 PCT/AU99/00802 13 The hydrocarbion 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.

Generally, the proportion of hydrocarbon relative to carbon dioxide will be in the 0t range of from 20:1 to 1:20, more typically 9:1 to 1:9, even more typically 4:1 to 1:4.

EXAMPLES

Example 1 Commercially available yttrium oxide (Pi-KEM, UK) was impregnated with an aqueous solution of Ni(N0 3 2 .6H 2 0 (Aldrich, 99.999 and the resulting slurry dried at 100 0 C for several hours. The impregnated, catalyst consisting of 1 wt% nickel was then calcined in flowing air at 500 0 C for 2 h to decompose the nitrate species. Example 2 Commercially available yttrium oxide (Pi-KEM, UK) was impregnated with an aqueous solution of Ni(N0 3 )2.6H 2 0 (Aldrich, 99.999 and the resulting slurry dried at 100 0 C for several hours. The impregnated catalyst consisting of 5 wt% nickel was then calcined in flowing air at 500 0 C for 2 h to decompose the nitrate species. The catalyst was subsequently reduced in hydrogen at 500 0 C for 2 hours and then cooled to ambient temperature. Catalyst activity for the CO 2 reforming reaction was demonstrated by heating the catalyst at a rate of 20K/min in the presence of a 1:1 mixture of CO 2 and CH 4 to a temperature-of 1073K, with all gas products continuously monitored by on-line mass spectrometry. This technique is known to those of average skill in the art as temperature programmed reaction (TPRxn). The resultant TPRxn profile is shown in Figure 8.

Example 3 Commercially available gadolinium oxide (Pi-KEM, UK) was impregnated with an aqueous solution of Ni(N0 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 0 C for 2 h to decompose the -nitrate species. The catalyst was subsequently reduced in hydrogen at 500 0 C for 2 hours and then cooled to ambient temperature. Catalyst activity for the CO 2 reforming reaction was demonstrated by WO 00/16899 PCT/AU99/00802 14 heating the catalyst at a rate-of 20K/min in the presence of a 1:1 mixture of CO 2 and CH 4 to a temperature of 1073K, with all gas products continuously monitored by on-line mass spectrometry. The resultant TPRxn profile is shown in Figure 9.

Example 4 Commercially available praseodymium oxide (Pi-KEM, UK) was impregnated with an aqueous solution of Ni(N0 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 0 C for.2 h to decompose the nitrate species. The catalyst was subsequently reduced in hydrogen at 500 0 C for 2 hours and then cooled to ambient 1o temperature. Catalyst-activity for the CO 2 reforming reaction was demonstrated by heating the catalyst at a rate of 20K/min in the presence of a 1:1 mixture of CO_ and CH 4 to a temperature of 1073K, with all gas products continuously monitored by on-line mass spectrometry. The resultant TPRxn profile is shown in Figure Example Is Commercially available samarium oxide (Pi-KEM, UK) was impregnated with an aqueous solution-of Ni(N0 3 2 .6H20 (Aldrich, 99.999 and the resulting slurry dried at 100 0 C for several hours. The impregnated catalyst consisting of 5 wt% nickel was then calcined in flowing air at 500 0 C for 2 h to decompose the nitrate species. The catalyst was subsequently reduced in hydrogen at 500 0 C for 2 hours and then cooled to amibient temperature. Catalyst activity for the CO 2 reforming reaction was demonstrated by heating the catalyst at a rate of-20K/min in the presence of a 1:1 mixture of CO 2 and CH 4 to a temperature of 1073K, with all gas products continuously monitored by on-line mass spectrometry. The resultant TPRxn profile is shown in Figure 13.

Example 6 Commercially available ytterbium 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 0 C for 2 h to decompose the nitrate species. The catalyst was subsequently reduced in hydrogen at 500 0 C for 2 hours and then cooled to ambient temperature. Catalyst activity for the CO 2 reforming reaction was demonstrated by heating the catalyst at a rate of 20K/min in the presence of a 1:1 mixture of CO 2 and CH 4 to a temperature of 1073 K, with all gas products continuously monitored by on-line mass spectrometry. The resultant TPRxn profile is shown in Figure 11.

Example 7 WO 00/16899 PCT/AU99/00802 Commercially available terbium oxide (Pi-KEM, UK) was impregnated with an aqueous solution of Ni(NO 3 2 .6H20 (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 0 C for 2 hours and then cooled to ambient temperature. Catalyst activity for the CO 2 reforming reaction was demonstrated by heating the catalyst at a rate of 20K/min in the presence of a 1:1 mixture of CO2 and CH 4 to a temperature of 1073K, with all gas products continuously monitored by on-line mass spectrometry. The resultant TPRxn profile is shown in Figure 12.

Example 8 A portion of the oxygen ion conductor lanthanum-strontium-gallium-magnesium oxide (Lao.,Sro.iGa 0 .8Mg 0 was impregnated with an aqueous solution of Ni(N0 3 )2.6H 2 0 (Aldrich, 99.999%) and the resulting slurry dried at 100 0 C for several hours. The impregnated catalyst consisting of-5-wt nickel was then calcined in flowing 1i air at 500°C for 2 h-to -decompose the nitrate species. The catalyst was subsequently reduced in hydrogen at 500 0 C for 2 hours and -then cooled to ambient temperature.

Catalyst activity for the CO 2 reforming reaction was demonstrated by heating the catalyst at a rate of 20K/min in the presence of a 1:1 mixture of CO 2 and CH 4 to a temperature of 1073K. with all gas products continuously monitored by on-line mass spectrometry. The -resultant TPRxn profile is shown in Figure 14.

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- 07 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 0 C. Samples were pre-reduced in a 20% hydrogen/helium mixture at 500 0 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- The catalyst activity and selectivity was then monitored as a function of reaction time for a period of 50h at 750 0 C. The conversion of carbon dioxide was stable over this period at a value of 98.5%. Notably, the testing conditions employed were such that coking of the catalyst surface was thermodynamically favoured, but no coking was observed.

WO 00/16899 PCT/AU99/00802 16 Comparative Example 1 The activity of a 5wt%- nickel on silica catalyst was evaluated using the conditions outlined in example 8. This catalyst exhibited deactivation over the 50 h testing period the conversion of carbon dioxide falling from an initial value of 96% to 93% and according-to'the criteria described above this catalyst is not part of the current invention.

Example The unique behaviour of the catalysts described in this invention is also revealed by Sinspection of transmission electron microscopy (TEM) obtained before-after 50 hours if

CO,/CH

4 reaction at 750 0

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 nm) detected. Even after reaction at 750 0 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. In contrast to the catalysts of the present invention, 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. Comparative Example 3 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 (as evidenced by XRD analysis). However, after C0 2

/CH

4 reaction at 750°C for 50h the TEM images revealed (Fig. F9) the growth of large (>10nm) nickel crystallites (dark, angular features in image) which suggests that MgO was-not as efficient at minimising the growth -of nickel grains relative to those catalysts disclosed in this invention.

Consequently, the reduced nickel dispersion will lead to poorer industrial performance compared to the catalysts of this invention.

Example 11 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 WO 00/16899 PCT/AU99/00802 17 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 wt nickel/yttrium oxide after reaction. Significantly, no evidence for nickel crystallite growth is detected.

Comparative Example 4 The XRD pattern for 30 wt nickel/magnesium oxide catalyst after the carbon dioxide reforming reaction (Figure 21) shows dramatic changes in the catalyst structure. In particular, a reflection at 43 degrees 2 characteristic of large nickel crystallites appears after reaction which is in harmiony with the observation of crystallite growth by to TEM. Thus, this known catalyst system is less effective than those described in this invention.

WO 00/16899 PCT/AU99/00802 Catalyst composition BET surface area (M 2 gyttrium oxide 2.46 Ni on yttrium oxide 15.71 Ni on yttrium oxide 49.36 terbium oxide 0.76 Ni on terbium oxide 5.82 Ni on terbium oxide 14.51 praseodymium oxide 3.58 Ni on praseodymium oxide 8.47 Ni on praseodymium oxide 11.69 silica 206.28 Ni on silica 171.80 Ni on silica 123.40 Table 1, BET surface areas of a representative sample of catalysts for this invention.

Claims (21)

1. 2.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. I 3. A catalyst precursor according to claim I or claim 2 wherein the oxide of cubic structural type is a metal oxide including-a single metal oxide or mixed metal oxide.
2. 4. A catalyst precursor according to claim I or claim 2 wherein the oxide of cubic structural type is an oxide of an element selected from the group consisting of yttriumn, gadolinium, praseodymiumn, samarium, ytterbium and terbium.
3. 5. A catalyst precursor according to claim I or claim 2 wherein the oxide of cubic structural type is selected from the group consisting of Zri-xYxO0)-x 2 Cei~xGdx0 2 ,x 2 LaCr 1 M, 3 a S, Gao. 8 M90 2 O 9 85 SrFeCoO. 5 0x, LaS oje, Bi,?Vl-xCuxO 5 35 LaCOQ 3 SrCoO 0 5 Sc 2 O 3 Y 2 0 3 Nd2O 3 Sm-20 3 Gd 2 0 3 Yb.0, Pr 6 0 1 1. Tb,0 3 Ca0-La2O, 3 ScO 3 -ZrO 2 La 0 8 SrO.2Mn0 3 La 0 6 CaO. 4 Co 0 2 FeO. 0 3, and Srn0. 6 Ca6. 4 COO 3 BaCeO 3 BaTb 09 Iln. 1 03, BaZro. 3 11 0 7 0 3 BaTh 0 9 Gd 0 103, Bab 9 J 0 j0, CaCe 0 9 qEr 0 1 03, CaCe 0 9 qGdO. 103, Ba 8 l1n 6 0 17 Ba 3 In Zr0 8 Ba 3 In)Zr08-, Ba' 3 Y- 2 Zr0 8 Ba 3 Gd-)CeO 8 Ba-)Gdln 1 -xGaxO 5 BaBi 4 Ti 3 InO 1 4 5 lBaBi 4 Ti 3 ScO 14 5 Sr,)Gd 2 O 5 Sr-)Dy2O 5 Sr 6 Nb 9 0l 1 SrBa 6 Ta 2 Ol 1 Sr 3 Ti 9 O 7 Sr 3 Zr 2 O 7 Ba 3 TiO 7 NdAIO 3 Nd 0 9 Ca 0 1 A10 3 Ba 3 Sc?,ZrO 8 SrIn?,Hf0 8 Ba 3 In 9 )TiO 8 Ba 3 Y 4 0 9 2S Ba1n 6 0 7 B~ei~d~0 3 1.Ti 9 M9 01
4. 06.9, BaCeO 3 (Qd,Yb,Nd), CaTiO 3 (Mg), SrZrO 3 BiV 2 O 1 (Cu,Ni), Ba 2 1In, 2 0 5 Ba 3 In2CeO 8 Ba 3 ln 2 HfO 8 LaGaO 3 (Ca), N d-,Zr?0 7 Nd-)Ce 2 0 7 NdCer 7 Gd(rTj0. Gd-)Zr2O 7 Gd-)(Zr,Ti )20 7 Sm-)Zr 2 O 7 Y- 2 (ZrTi- 9 2 0 7 Gd, 9 Zr 9 O0 7 Nd-iZr-,0 7 Sm 2 Zr 2 O0 7 7 Gd 2 ZrO 7 Tb,Zr,0 7 Er-, 2 0 7 Y-,Ti-)0 7 Gd,Zr 2 0 7 (Ru), SmTi-0 7 (Sr,Ca,Mg), PbWO 4 Pb 8 La- 2 WO 4 1 BiVO 4 Bi(Ca)V0 4 Bi(Ca.,Ce)V0 4 PbMoO 4 Ca 1 2 A1 14 0 33 Sr 6 Nb 2 O 1 I. Sr 6 Ta 2 )O 1 Ba 6 Nb 2 )O 1 Ba 6 Ta 2 0 1 1 j, Y 3 A1 5 0 12 ca-Ta2,0 5 YO. 75 Nb 0 15 Ce. 0 1.7, 8-Bi'20 3 Bi 9 0-rBi, 3 BO Bi 2 Bi-,0 3 -Pr 6 O 1 Bi- 2 0 3 PbO, SbO, BiCuVO\, Bi 3 Y 2 0?O WO 00/16899 PCT/AU99/00802 SrCeO 3 SrCe(Yb)O 3 SrZrO 3 (Y,Sc,Yb), Sr 2 (ScNb)O6-d, Ba 3 (CaNb)0 9 -d, H-Ln2Ti 3 0 1 o (Ln La, Nd, Sm, Gd) and HCa 2 Nb 3 Olo. 6. A catalyst precursor according to claim 1 or claim 2 wherein the elevated temperature is a temperature in the range of about 300-1000 0 C.
5. 7. A process for producing a catalystprecursor including the steps of 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 0 C; (ii) if necessary heating the mixture in an atmospheirat a temperature and for a oI time sufficient to calcine the nickel containing compound to nickel oxide; and (iii) heating the resulting mixture of nickel oxide and support material for a time and at a temperature sufficient to form the catalyst precursor.
6. 8. A process for producing a catalyst precursor including the steps of impregnating a support material with a solution of a nickel compound, the I support material being an oxide of cubic structural type which is an oxygen ion conductor at a temperature in the range 300-1000 0 C; (ii) if necessary heating the mixture in an atmosphere at a temperature and for a time sufficient to calcine the nickel containing compound to nickel oxide; and (iii) heating the resulting mixture of nickel oxide and support material for a time and at a temperature sufficient to form a solid solution of at least part of the nickel oxide in the support material.
7. 9. A process according to claim 7 wherein in step (iii) the heating is at a temperature of from 250°C to 1500 0 C. A process according to claim 7 wherein the support material is a metal oxide including a single metal oxide or mixed metal oxide.
8. 11. A process according to claim 7 wherein 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.
9. 12. A process according to claim 7 wherein the oxide of cubic structural type is selected from the group consisting of Zri.xYxO2-x/ 2 CelxGdxO2-x/2. LaCrl-xMgxO 3 -x/2, La i-SrxGao.8Mgo.202. 85 SrFeCoo.50, Lal_,SrxCo _yFeyO0 3 z Bi 2 V -xCuxO5.35, LaCoO 3 SrCoOo. 25 Sc 2 0 3 Y 2 0 3 Nd 2 0 3 Sm120 3 Gd2O 3 Yb20 3 Pr 6 0 11 Tb20 3 CaO-La 2 03, Sc 2 03-ZrO 2 Lao. 8 Sr0. 2 Mn0 3 Lao. 6 Ca 0 4 Coo.2Fe.80 3 .x and Sino.6Cao. 4 Co0 3 BaCeO 3 BaTbo.9lno.103, BaZro 3 Ino. 7 0 3 BaTh 0 .9Gdo.03, WO 00/1 6899 -PCT/AU99/00802 21 BaTbo. 9 ln 0 0 1 03, CaCe 0 9 gEr. 1 03, CaCe 0 9 qGdO. 1 03, Ba 8 l'n 6 0 17 Ba 3 InxZrxO8, Ba 3 ln- 2 ZrO 8 Ba 3 YZrO 8 Ba 3 Gd-,CeO 8 Ba2Gdln I GaX0 5 BaBi 4 Ti 3 InO 14.5' BaBi' 4 Ti 3 ScO 14 5 Sr, 2 Gd 2 0 5 Sr 2 Dy 2 0 5 Sr 6 Nb 2 0 1 1 SrBa 6 Ta 2 O 1 1, Sr 3 Ti 2 O 7 SIr 3 ZIr 9 0 7 Ba 3 Ti 9 O0 7 NdAIO 3 Nd 0 9 Ca 0 1 A10 3 Ba 3 Sc 9 )ZrO 8 Srln,)HfO 8 Ba 3 In-TiO 8 B 3 4 9 Ba 8 1n1 6 0 17 BaCel- 1 d 3x Sr 3 Til. 9 Mg. 106.9, BaCeO 3 (Gd,Yb,Nd), CaTi0 3 (Mg), Sr-ZrO 3 BiV-)O 1 j(Cu,Ni), Ba-)ln 2 0 5 Ba 3 In 2 CeO 8 Ba 3 In 2 )HfO 8 LaGaO 3 (Ca), Nd-,Zr,0 7 Nd-,Ce-,0 7 Nd,)CeZrO 7 Gd- 2 (Zr,Ti\,) 2 0 7 Gd 2 0 7 Gd 2 Zr0 7 Gd-.(Zr.Ti) 2 0 7 Sm-)Zr 2 0 7 Y)(r.i~ 2 7 GdZr 2 O0 7 Nd-)Zr 2 O0 7 Sm-n 9 Zr 2 O 7 Gd- 9 Zr,0 7 Gd-)Zr-,0 7 T6- 2 Zr 2 )0 7 ErT 2 0 7 Y,)Ti 2 0 7 Gd-)Zr 2 O 7 (Ru), I) Snmii-)T0 7 (Sr.Ca,Mg), PbW0 4 Pb 8 La-)W0 4 BiV04, Bi(Ca)V0 4 Bi(Ca,Ce)V0 4 PbMoO 4 Ca 1 2 A1 14 0 33 Sr 6 Nb,0 1 1, Sr 6 Ta-,0 11 Ba 6 Nb 2 )O 1 1 Ba 6 Ta 2 0 11 Y 3 A1 5 0 1 c&Ta 2 )0 5 Y 0 7 5 Nb 0 15 Ceo- 0 1 6-Bi-,0 3 Bi,)0 3 -SrO, Bi 2 )0 3 -BaO, Bi-,V Pb Q, Bi,0 3 -Pr 6 1 Bi 2 0 3 PbO,. Sb 9 O, BiCuV0,, Bi-,0- 2 3 -SrCeO 3 -SrCe(Yb)0 3 9rZrO 3 (Y,Sc,Yb), Sr-2(ScNb)0 6 Ba 3 (CaNb)0 9 .d, ji H)Li-Ti3O0 1 0 (Ln La, Nd, Sm, Gd) and HCa-)Nb 3 0 10
10. 13. A catalyst precursor produced by the process of any one of claims 7-12.
11. 14. A catalyst for reforming hydrocarbons to produce synthesis gas, the catalyst being obtainable by reducing a catalyst precursor according to claim 1 or claim 2 in a reducing atmosphere at an elevated temperature.
12. 15. A catalyst for reforming hydrocarbons to produce synthesis gas, the catalyst being! obtainable by reducing -a catalyst precursor according to claim 13 in a reducing -atmosphere at an elevated temperature.
13. 16. A catalyst according to claim 14, further including one or more additives selected- fromn the group consisting of: noble metals selected from the group consisting of Pt, Ir, Rhi, Ru, Os, Pd and Re; oxides selected from the group consisting of TiO 2 MoO 3 W0 3 ZrO 2 VA0, Nb,O., Sc,,Oi and Ta 2 O 5 oxides of elements selected from the group consisting of boron, aluminium, ,gallium and indium; -elements selected from the group consisting of Ag, Cu, Au and Zn, and elements selected from the group consisting of P, Sb, As, Sn and Ge.
14. 17. A process for producing a catalyst for reforming hydrocarbons to produce synthesis g_(as including the steps of WO 00/16899 PCT/AU99/00802 22 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; (ii) if necessary .heating the mixture in an atmosphere at a temperature and for a time sufficient to calcine the nickel containing compound to nickel oxide; (iii) heating the resulting mixture of nickel oxide and support material for at least about 15 minutes at a temperature of from 250°C to 1500 0 C; and (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.
15. 18. A catalyst produced by the process of claim 17.
16. 19. 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 according to claim 14 at a temperature and pressure, and for a time sufficient to convert at least part of the reactant mixture to .synthesis gas.
17. 20. 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 according to claim 15 at a temperature and pressure, and for a-time sufficient to convert at least part of the reactant mixture to synthesis gas.
18. 21. 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 according to claim 16 at a temperature and pressure, and for a time sufficient to convert at least part of the reactant mixture to synthesis gas.
19. 22. A process for reforming a hydrocarbon to produce synthesisg as,including the step of contacting a reactant mixture of carbon dioxide and the hydrocarbon with a catalyst according to claim 18 at a temperature and pressure, and for-a.time sufficient to convert. at least part of the reactant mixture to synthesis gas. 23
20. 23. A catalyst precursor for reforming hydrocarbons to produce synthesis gas at an elevated temperature, substantially as hereinbefore described with reference to the accompanying drawings and/or to any one of the Examples but excluding the comparative Examples.
21. 24. A process for reforming a hydrocarbon to produce synthesis gas, substantially as hereinbefore described with reference to the Examples but excluding the comparative Examples. A process for producing a catalyst precursor including the steps of 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 0 C; (ii) if necessary heating the mixture in an atmosphere at a temperature and for a time sufficient to calcine the nickel containing compound to nickel oxide; and s (iii) heating the resulting mixture of nickel oxide and support material for a time 15 and at a temperature sufficient to form the catalyst precursor, substantially as hereinbefore described with reference to the Examples but excluding the comparative Examples. Dated 23 January, 2003 The University of Queensland 20 Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON 6 a a a [R:\LIBA]05469.doc:jjp