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Title:
COMPOUND HAVING A PYROCHLORE-STRUCTURE AND ITS USE ASACATALYST CARRIER IN WATER GAS SHIFT REACTION
Document Type and Number:
WIPO Patent Application WO/2006/030179
Kind Code:
A1
Abstract:
A compound of formula (Na0.33A0.66)2B2O7-&dgr wherein A is one or more metals chosen from the lanthanide metals; B is one or more metals chosen from Ti, Sn, Ge, Ru, Mn, Ir, Os and Pb; and &dgr is a number in the range 0-1 is disclosed. Water gas shift catalysts comprising precious metals such as gold dispersed on the (Na0.33A0.66)2B2O7-&dgr compound are also disclosed.

Inventors:
FISHER JANET MARY (GB)
THOMPSETT DAVID (GB)
WALTON RIRCHARD IAN (GB)
WRIGHT CHRISTOPHER STUART (GB)
Application Number:
PCT/GB2005/003428
Publication Date:
March 23, 2006
Filing Date:
September 07, 2005
Export Citation:
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Assignee:
JOHNSON MATTHEY PLC (GB)
FISHER JANET MARY (GB)
THOMPSETT DAVID (GB)
WALTON RIRCHARD IAN (GB)
WRIGHT CHRISTOPHER STUART (GB)
International Classes:
B01J23/00; B01J23/66; C01B3/16; C01G23/00; B01J23/63; B01J35/00; (IPC1-7): B01J23/00; B01J23/38; B01J23/52; B01J23/04; B01J23/10; B01J23/14; B01J23/34; B01J23/46; B01J21/06; C01B3/16
Domestic Patent References:
WO2002096559A12002-12-05
Foreign References:
US4313925A1982-02-02
US6455182B12002-09-24
US4313925A1982-02-02
Other References:
GARVIE L A J ET AL: "Synthesis of (Ca,Ce<3+>,Ce<4+>)2Ti2O7: a pyrochlore with mixed-valence cerium", JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS, PERGAMON PRESS, LONDON, GB, vol. 66, no. 5, May 2005 (2005-05-01), pages 902 - 905, XP004764962, ISSN: 0022-3697
PATENT ABSTRACTS OF JAPAN vol. 2003, no. 12 5 December 2003 (2003-12-05)
KOUTCHEIKO S ET AL: "Electrical, thermal and catalytic properties of CeO2-Sm0.5Ti0.5O1.75 ceramics", CERAMICS INTERNATIONAL, CERAMURGICA, FAENZA, IT, vol. 31, no. 7, 2005, pages 965 - 971, XP004966747, ISSN: 0272-8842
Attorney, Agent or Firm:
Carney, Maeve Mary (Blounts Court Sonning Common, Reading RG4 9NH, GB)
Download PDF:
Claims:
Claims
1. A compound of formula (Na033A0^e)2B2O75 wherein A is one or more metals chosen from the lanthanide metals; B is one or more metals chosen from Ti, Sn, Ge, Ru, Mn, Ir, Os and Pb; and δ is a number in the range 0 1.
2. A compound according to claim 1, wherein A is preferably one or more metals chosen from Ce, Pr and Tb.
3. A compound according to claim 1, wherein A is more than one metal chosen from the lanthanide metals, and at least 70 atomic percent of A is Ce.
4. A compound according to claim 1, wherein A is Ce.
5. A compound according to any preceding claim, wherein B is Ti or Ti and Sn or Ti and Ge.
6. A compound according to any preceding claim, wherein B is Ti.
7. A compound according to any preceding claim, wherein δ is 0.
8. A compound of formula (Nao.33Ceo.66)2Ti207.
9. A catalyst comprising a metal dispersed on a support material, wherein the support material is compound according to any preceding claim.
10. A catalyst according to claim 9, wherein the metal dispersed on the support material comprises a precious metal.
11. A catalyst according to claim 10, wherein the metal dispersed on the support material is gold or an alloy of gold.
12. A water gas shift process wherein water and carbon monoxide are passed over a catalyst according to any one of claims 9 to 11.
Description:
COMPOUND HAVING A PYROCHLORE-STRUCTURE AND ITS USE AS A CATALYST CARRIER IN

WATER GAS SHIFT REACTION

The present invention relates to a novel compound and its use as a catalyst support material in a water gas shift catalyst.

The water gas shift (WGS) reaction converts carbon monoxide and water to carbon dioxide and hydrogen: CO + H2O → CO2 + H2 So-called "low temperature" WGS catalysts catalyse the WGS reaction at temperatures of 200-4000C. WGS catalysts are commonly used in reformer systems to reduce CO concentration.

WGS catalysts typically comprise a metal dispersed on the surface of a high surface area support material. Commonly used support materials for WGS catalysts include alumina, titania, ceria and iron oxide. The support material must be durable and the nature of the support material can affect the activity of the WGS catalyst. The present inventors have sought to develop a catalyst support material that is durable and that can be used to provide WGS catalysts with high activity, particularly at low temperatures.

Accordingly the present invention provides a compound of formula

wherein A is one or more metals chosen from the lanthanide metals; B is one or more metals chosen from Ti, Sn, Ge, Ru, Mn, Ir, Os and Pb; and δ is a number in the range 0- 1.

The compound has the pyrochlore structure and has been used to prepare catalysts with excellent low temperature water gas shift activity.

A is suitably one or more metals chosen from the lanthanide metals, including at least Ce. A is preferably one or more metals chosen from Ce, Pr and Tb. If A is more than one metal chosen from the lanthanide metals, then preferably at least 70 atomic percent of A is Ce. Ce is in the 4+ oxidation state, but the other lanthanides may be in the 3+ oxidation state. If any of the A ions are in the 3+ oxidation state, then δ will be greater than 0 to balance the charges. In one embodiment of the invention, A is only one metal chosen from Ce, Pr or Tb. However, in an alternative embodiment of the invention, A is two or more metals chosen from Ce, Pr and Tb, e.g. A is an 80:20 mixture of Ce and Pr. Most preferably, A is Ce.

B is in the 4+ oxidation state and is suitably one or more metals chosen from Ti, Sn, Ge, Ru, Mn, Ir, Os and Pb, including at least Ti. IfB is more than one metal chosen from Ti, Sn, Ge, Ru, Mn, Ir, Os and Pb, then preferably at least 50 atomic percent of B is Ti. Preferably B is Ti or Ti and Sn or Ti and Ge. Most preferably B is Ti.

The compound suitably has the formula (Nao.33A0.66)2B2θ7 (i.e. δ is 0) but can also be oxygen deficient (i.e. δ is greater than 0).

A preferred compound according to the invention is (Nao.33Ceo.66)2Ti207. Further preferred compounds are (Nao.33Ce0.66)2Ti2-xSnx07, wherein x is from 0 to 0.9, (Nao.33Ceo.66)2Ti2-yGey07, wherein y is from 0 to 1 and (Na0133CeC66-2PrZ)2Ti2O7, wherein

The compound can be made by hydrothermal synthesis. A salt of A in the 3+ oxidation state (e.g. CeCl3) is mixed with more than two equivalents of a salt of B in the 3+ oxidation state (e.g. TiF3) in the presence of a base (e.g. NaOH) and an oxidant (e.g. H2O2 or NaBrO3) in an aqueous system. The reactants are heated to about 2400C for a period of about 5 hours in a sealed container.

The invention further provides a catalyst comprising metal dispersed on a support material, wherein the support material is a compound of formula (Nao.33Ao.66)2B207-δ as described above. The metal dispersed on the support material suitably comprises one or more precious metals (Au, Ag, Pt, Pd, Rh, Ir, Ru and Os) and is preferably gold or an alloy of gold. The loading of the catalytic metal is preferably between 0.1-20wt%, based on the weight of the support material. Metal can be dispersed on the surface of the (Nao.33A0.66)2B207-δ compound using techniques that are well known to those skilled in the art. One suitable method is incipient wetness impregnation wherein metal salts are made up into a solution such that the volume of solution is sufficient to fill the entire pore volume of the support material. The solution is added to the support material, the material is mixed thoroughly and then dried and calcined. Another suitable method is co-deposition wherein the support material is dispersed in a slurry containing metal salts. A base is added to deposit the metal onto the support material, and the catalyst is dried and calcined.

The catalysts according to the invention are active for the water gas shift reaction. Therefore in a further aspect the present invention provides a water gas shift process wherein water and carbon monoxide are passed over a catalyst of the invention, thereby providing hydrogen and carbon dioxide. The process is suitably carried out at a temperature of less than 4000C, preferably less than 25O0C.

The invention will now be described by reference to examples which are intended to be illustrative and not limiting of the invention.

CeCl3JH2O (0.3707g, lmmol) and TiF3 (0.2622g, 2.5mmol) were weighed into a PTFE liner and H2O2 (35wt%, 5cm3) was added. NaOH (4M5 5cm3) was added dropwise with stirring. The mixture was then stirred at room temperature for 30 minutes. The liner was then put into a stainless steel autoclave (23ml capacity acid digestion bomb) and placed in an oven. The oven was heated at 160CnUn"1 until 24O0C, and the temperature was then held constant for 5 hours, before cooling to room temperature at a rate of 2.50CnIm"1. The product was then washed in distilled water (~200ml) at 800C for 30 minutes to remove any trace of NaF in the product. The product was filtered, washed with acetone and dried at 5O0C.

XPS, XRD and chemical analysis confirmed that the product was (Nao.33Ceo.6δ)Ti207 having the pyrochlore structure. Example 2: (Na^Cen^WTM)?

CeCl3JH2O (0.3707g, lmmol) and TiF3 (0.2622g, 2.5mmol) were weighed into a PTFE liner and NaBrO3 (0.5M, 5cm3) was added gradually with stirring. After complete addition of the bromate, the mixture was stirred for 5 minutes. NaOH (4M, 5cm3) was then added gradually and the mixture was then stirred for 30 minutes. The liner was then put into an autoclave and heated at 24O0C for 5 hours. The product was filtered and washed until the conductivity of the filtrate was less than lOOμS and then dried at 50°C overnight.

This compound was prepared according to example 2 except that Sn(CH3COO)4 (0.5 mrαol) and TiF3 (2.0mmol) were used instead of 2.5mmol OfTiF3.

This compound was prepared according to example 2 except that GeCl4 (0.5 mmol) and TiF3 (2.0mmol) were used instead of 2.5mmol OfTiF3.

This compound was preparing according to example 2 except that Pr(NO3)3.6H2θ was added to the reaction mixture with the CeCl3-VH2O.

Pyrochlore produced according to example 1 (9.4g) was slurried in water (400ml) and wanned to 6O0C with stirring. The pH of the slurry was adjusted to 8.7 with addition of sodium carbonate solution (0.05M). HAuCl4 (0.39g, 49.24%Au) was dissolved in water (75ml) and pumped into the slurry at about lOml/rnin. The pH of the slurry was allowed to fall to 8.0 and then maintained at this value by the addition of sodium carbonate solution (0.05M). When the gold addition was complete the slurry was stirred for 1 hour at 600C. The catalyst sample was recovered by filtration, washed free of chloride ions on the filter bed and dried at 1050C.

Comparative Example 1; Au on ceria WGS catalyst

Ceria (from Rhodia, 19.6g) was slurried in water (800ml) and the pH of the slurry was adjusted to 8.0 with the dropwise addition of lithium carbonate solution (0.1M). HAuCl4 (0.81g, 49.24%Au) was dissolved in water (150ml). This solution was pumped into the slurry at about lOml/min. The pH was maintained at 8.0 by the simultaneous addition of lithium carbonate solution (0.1M). When the gold addition was complete the slurry was stirred for one hour. The catalyst was recovered by filtration, washed free of chloride ions on the filter bed and dried at 1050C.

Comparative Example 2: Au on ceria-zirconia WGS catalyst

CeZrO4 from Rhodia was fired at 5000C for 2 hours. 19.6g of the fired support material was slurried in water (800ml). The pH of the slurry was adjusted from approximately 4.0 to 8.0 by the careful addition of Li2CO3 solution (0.1M). HAuCl4 (0.8 Ig, 49.24%Au) was dissolved in demineralised water and the volume made up to 200ml. This solution was added dropwise over 25mins to the stirred slurry of CeZrO4. Throughout the gold addition the pH was maintained at 8.0 with the addition of further Li2CO3 (0.1M). After the addition was complete the slurry was stirred for a further 1 hour and then filtered. The catalyst was washed to remove chloride ions and then dried at 1050C overnight.

Example 7: WGS activity

The catalysts of Example 6 and Comparative Examples 1 and 2 were tested for WGS activity across a range of temperatures. Catalyst samples were pelletised, crushed and sieved to give a fraction in the particle size range 250-355μm. 0.45g of catalyst was placed in a sample holder sitting inside a ceramic tube inside a three-zone furnace. Gases were introduced using mass flow controllers and water was fed to an evaporator via peristaltic pumps. The space velocity was 40,00Oh"1 and the gases were 5% CO, 30% H2O and N2 balance. Inlet and outlet gas streams were dried and then passed to analysers to determine conversions. Hydrogen was analysed using gas chromatography and CO and CO2 using infra-red spectroscopy.

The activity of the catalysts (expressed as a % conversion of CO) versus temperature is shown in Figure 1. The catalyst of the invention has better activity than the gold on ceria catalyst (comparative example 1) and has activity that is almost as good as the state-of-the-art gold on ceria-zirconia catalyst (comparative example 2).