Catalysts supports
A method for preparing a silica-modified catalyst support is described including: (i) applying an alkyl silicate to the surface of a porous support material in an amount to produce a silica content of the silica-modified catalyst support, expressed as Si, in the range 0.25 to 15% by weight, (ii) optionally drying the resulting silicate-modified support, (iii) treating the support with water, (iv) drying the resulting water-treated support, and (v) calcining the dried material to form the silica-modified catalyst support.
1. A process for the Fischer-Tropsch synthesis of hydrocarbons comprising contacting a gas mixture containing hydrogen and carbon monoxide over a catalyst prepared by steps comprising applying a catalytically active material comprising cobalt to a silica-modified catalyst support, wherein the silica-modified support is prepared by steps comprising:
(i) applying an alkyl silicate of formula Si(OR) 4 , where R is a C1-C4 alkyl group to the surface of a porous support material in an amount to produce a silica content of the silica-modified catalyst support, expressed as Si, in the range 0.25 to 15% by weight,
(ii) drying the silicate-modified support,
(iii) treating the silicate-modified support with water to force the hydrolysis of the alkyl silicate on the support causing cross-linking to form a silicate material having a greater molecular mass and reduced volatility than the alkyl silicate,
(iv) drying the resulting water-treated support, and
(v) calcining the dried material to form the silica-modified catalyst support.
2. A process according to claim 1 , wherein the porous support comprises a transition alumina or hydrated alumina.
3. A process according to claim 1 , wherein the porous support is a spray-dried powder with an average particle size in the range 1 to 200 micrometers.
4. A process according to claim 1 , wherein the porous support is a pellet, extrudate or granule with a particle size in the range 1 to 25 mm.
5. A process according to claim 1 , wherein the alkyl silicate is tetraethyl-orthosilicate (TEOS).
6. A process according to claim 1 , wherein the a silica content of the silica-modified catalyst support, expressed as Si, is in the range 1 to 10% by weight.
7. A process according to claim 1 , wherein the alkyl silicate is applied as a solution in an alcohol.
8. A process according to claim 7 , wherein the volume of the alkyl silicate solution is less than or equal to the pore volume of the porous support material.
9. A process according to claim 1 , wherein the silicate-modified support is dried at a temperature in the range 30-150° C. prior to the treatment with water.
10. A process according to claim 1 , wherein the water treatment comprises immersing or slurrying the silicate-modified support in water.
11. A process according to claim 10 , wherein the water treatment comprises applying a volume of liquid water to the dried silicate-modified support, said volume of water equal to or less than the pore volume of the dried silicate-modified support.
12. A process according to claim 1 , wherein the water-treated support is dried for a period at ambient pressure or under a vacuum of 1-10 mm Hg.
13. A process according to claim 1 , wherein the water treated support is dried at a temperature in the range 30-150° C.
14. A process according to claim 1 , wherein the calcination step is performed by heating the dried support to a temperature in the range 500-950° C. for between 0.5 and 8 hours.
15. A process according to claim 1 , wherein the silica content of the calcined catalyst support is ≥90% wt of that derivable from the amount of alkyl silicate applied to the porous support.
16. A process according to claim 1 , wherein the mixture of carbon monoxide and hydrogen is a synthesis gas having a hydrogen:carbon monoxide ratio in the range 1.6-3.0:1.
17. A process according to claim 1 , wherein the reaction is performed in a continuous or batch process using one or more fixed bed reactors, stirred slurry-phase reactors, jet-loop reactors, bubble-column reactors, or fluidised bed reactors.
18. A process according to claim 1 , wherein the process is operated at pressures in the range 0.1-10 Mpa and temperatures in the range 150-350° C.
19. A process according to claim 1 , wherein the gas-hourly-space velocity (GHSV) for continuous operation is in the range 100-25000 hr −1 .
20. A process according to claim 1 , wherein the catalysts prepared on the supports prepared according to the present invention provide C5+ hydrocarbons at >200 g/kg catalyst per hour at a selectivity of >75% molar carbon.