Modified catalyst supports
A modified catalyst support exhibiting attrition resistance and/or deaggregation resistance is provided. A catalyst composition including the modified catalyst support is also provided. A process to produce a modified catalyst support including treatment of a support slurry with a solution of monosilicic acid is provided. A process to use a catalyst including the modified catalyst support in a Fischer-Tropsch synthesis is provided.
1 . A catalyst composition comprising:
support material having between about 0.1 Si/nm 2 support surface area and about 10.6 Si/nm 2 support surface area deposited thereon wherein the Si atoms are bound directly to the support material through an oxygen atom.
2 . The catalyst composition of claim 1 wherein the silicon is deposited on the support material at a concentration of between about 0.55 Si/nm 2 and about 5.0 Si/nm 2 .
3 . The catalyst composition of claim 1 wherein the silicon is deposited on the support material at a concentration of between about 0.7 Si/nm 2 and about 3.5 Si/nm 2 .
4 . The catalyst composition of claim 1 wherein the support material is selected from the group of gamma alumina, eta alumina, theta alumina, delta alumina, rho alumina, anatase titania, rutile titania, magnesia, zirconia, refractory oxides of Groups III, IV, V, VI and VIII elements and mixtures thereof.
5 . The catalyst composition of claim 4 wherein the support material is aggregated gamma alumina.
6 . The catalyst composition of claim 4 wherein the support material is alumina-bound titania.
7 . The catalyst composition of claim 1 wherein the catalyst has been regenerated.
8 . The catalyst composition of claim 1 wherein the support material is preformed.
9 . The catalyst composition of claim 1 further comprising:
between about 12 wt % and about 30 wt % Co;
between about 0.5 wt % and about 2 wt % of a first additive selected from the group of Ca, Sc, Ba, La, and Hf;
between about 0.03 wt % and about 0.3 wt % of a second additive selected from the group of Ru, Rh, Pd, Re, Ir, and Pt.
10 . The catalyst composition of claim 1 further comprising:
between about 12 wt % and about 30 wt % Co;
between about 0.5 wt % and about 2 wt % La; and
between about 0.03 wt % and about 0.3 wt % Ru.
11 . catalyst composition comprising:
a support material having between about 0.1 Si/nm 2 support surface area and about 10.6 Si/nm 2 support surface area deposited thereon wherein less than about 10 wt % of the silicon is in polymeric form.
12 . The catalyst composition of claim 11 wherein the silicon is deposited on the support material at a concentration of between about 0.55 Si/nm 2 and about 5.0 Si/nm 2 .
13 . The catalyst composition of claim 11 wherein the silicon is deposited on the support material at a concentration of between about 0.7 Si/nm 2 and about 3.5 Si/nm 2 .
14 . The catalyst composition of claim 11 wherein the support material is selected from the group of gamma alumina, eta alumina, theta alumina, delta alumina, rho alumina, anatase titania, rutile titania, magnesia, zirconia, refractory oxides of Groups III, IV, V, VI and VIII elements and mixtures thereof.
15 . The catalyst composition of claim 14 wherein the support material is aggregated gamma alumina.
16 . The catalyst composition of claim 14 wherein the support material is alumina-bound titania.
17 . The catalyst composition of claim 11 wherein less than about 5 wt % of the silicon is present in polymeric form.
18 . The catalyst composition of claim 11 wherein less than about 2.5 wt % of the silicon is in polymeric form.
19 . The catalyst composition of claim 11 wherein the catalyst has been regenerated.
20 . The catalyst composition of claim 11 wherein the support material is preformed.
21 . The catalyst composition of claim 11 further comprising:
between about 12 wt % and about 30 wt % Co;
between about 0.5 wt % and about 2 wt % of a first additive selected from the group of Ca, Sc, Ba, La, and Hf;
between about 0.03 wt % and about 0.3 wt % of a second additive selected from the group of Ru, Rh, Pd, Re, Ir, and Pt.
22 . The catalyst composition of claim 11 further comprising:
between about 12 wt % and about 30 wt % Co;
between about 0.5 wt % and about 2 wt % La; and
between about 0.03 wt % and about 0.3 wt % of Ru.
23 . A method of treating a catalyst support, comprising: contacting a support material with an attrition-suppressing composition comprising monosilicic acid thereby to provide a treated catalyst support.
24 . The method according to claim 23 wherein the treated catalyst support has a surface concentration of between about 0.1 and about 10.60 Si atoms/nm 2 .
25 . The method according to claim 23 , wherein the attrition-suppressing composition comprises between about 0.02% and about 6.9% by weight of Si.
26 . The method according to claim 23 wherein the attrition-suppressing composition comprises between about 0.2% and about 6.9% by weight of Si.
27 . The method according to claim 23 wherein the attrition-suppressing composition is prepared by contacting a silicate with water under acidic conditions.
28 . The method according to claim 27 wherein the silicate comprises monosilicic acid.
29 . The method according to claim 28 wherein the monosilicic acid is prepared by contacting tetraethoxysilane with water under acidic conditions.
30 . The method according to claim 27 , wherein the silicate is sodium orthosilicate or sodium metasilicate and the pH ranges from about 1.5 to about 3.5 at a temperature ranging from about 0° C. to about 5° C.
31 . The method according to claim 27 wherein the attrition-suppressing composition is added to the catalyst support at a temperature ranging from about 0° C. to about 95° C.
32 . The method according to claim 27 wherein the temperature ranges from about 0° C. to about 10° C.
33 . The method according to claim 27 , wherein the attrition-suppressing composition comprises a polysilicic acid species wherein concentration of monosilicic acid is greater than the concentration of trisilicic acid and higher polymers of the silicic acid.
34 . The method according to claim 28 wherein the monosilicic acid is the predominant silicic acid species in the attrition-suppressing composition.
35 . The method of claim 23 wherein the support material is preformed.
36 . A catalyst composition suitable for use in a Fischer-Tropsch process, comprising a mixture or reaction product of:
an attrition-resistant support prepared by contacting a support material with an attrition-suppressing composition comprising monosilicic acid;
cobalt;
a modifier selected from the group of Ca, Sc, Ba, La, Hf, and combinations thereof; and
at least one activator selected from the group of Ru, Rh, Pd, Re, Ir, Pt, and combinations thereof.
37 . The catalyst composition according to claim 36 , wherein the composition is substantially free of particles having a diameter of less than about 20 μm under typical Fischer-Tropsch reaction conditions.
38 . The catalyst composition according to claim 36 , wherein the support material is selected from the group of Group III, IV, V, VI, VIII refractory oxides, and mixtures thereof.
39 . The catalyst composition according to claim 36 , wherein the support material comprises aggregated gamma alumina.
40 . The catalyst composition according to claim 36 wherein the first transition metal is cobalt and the second is ruthenium.
41 . The catalyst composition of claim 36 wherein the support material is preformed.
42 . A Fischer-Tropsch product, comprising:
a paraffinic wax; and
less than about 50 ppm of gamma alumina particles having a diameter of less than about 20 μm; wherein the concentration of gamma alumina particles is determined following primary filtration.
43 . The Fischer-Tropsch product of claim 42 wherein the Fischer-Tropsch product is produced using a regenerated Fischer-Tropsch catalyst.