Resid hydrotreating catalyst containing titania
Improved catalyst supports, supported catalyst, and method of preparing and using the catalysts for the hydrodesulfurization of a residuum hydrocarbon feedstock are disclosed. The catalyst supports comprise titania alumina having 5 wt % or less titania and have greater than 70% of their pore volume in pores having a diameter between 70 Å and 130 Å and less than 2% in pores having a diameter above 1000 Å. Catalysts prepared from the supports contain Groups 6, 9 and 10 metals or metal compounds, and optionally phosphorus, supported on the titania alumina supports. Catalysts in accordance with the invention exhibit improved sulfur and MCR conversion in hydrotreating processes.
1. A method for preparing a catalyst for hydrodesulfurization of residuum hydrocarbon feedstocks which method comprises: impregnating a porous extruded support comprising a titania alumina extrudate formed from a peptized co-precipitated titania alumina powder having 5 wt % or less titania based on the total weight of the titania alumina, said support having a total pore volume in the range of from about 0.5 to about 1.0 cubic centimeters per gram, at least 70% of the total pore volume in pores having a diameter between about 70 Å and about 130 Å, less than 5% of the total pore volume have pores in a diameter above 300 Å, as determined by nitrogen porosimetry, and less than 2% of the total pore volume in pores having a diameter above 1000 Å, as determined by mercury penetration porosimetry with an aqueous solution containing at least one catalytic agent or catalytic agent precursor selected from the group consisting of a compound of Group 6 metals of The Periodic Table, Group 9 metals of the Periodic Table, Group 10 metals of The Periodic Table, and combinations thereof, and a phosphorous compound in an amount which provides a phosphorous concentration in the range of about 0.22 to about 3.0 wt % of phosphorous, calculated as elemental phosphorous, based on the weight of the total catalyst composition, said compounds being thermally decomposable to their corresponding metal oxides, and thereafter drying and calcining the resulting impregnated support to provide a supported catalyst.
2. A catalyst produced by the method according to claim 1 .
3. A catalyst suitable for use in hydrodesulfurization of residuum hydrocarbon feedstocks comprising:
a) a support comprising a co-precipitated titania alumina having 5 wt % or less titania based on the total weight of the titania alumina; and
b) at least one catalytic agent comprising a metal selected from the group consisting of a Group 6 metal of The Periodic Table, a Group 9 metal of The Periodic Table, a Group 10 metal of The Periodic Table, phosphorous and combinations thereof, and a phosphorous compound in an amount which provides a phosphorous concentration in the range of 0.22 to about 3.0 wt % of phosphorous, calculated as elemental phosphorous, based on the weight of the total catalyst composition;
wherein the support is characterized as having:
(i) a total pore volume of from about 0.5 to about 1.0 cubic centimeters per gram;
(ii) at least 70% of the total pore volume in pores having a diameter between about 70 Å and about 130 Å;
(iii) less than 5% of the total pore volume in pores having a diameter above 300 Å, as determined by nitrogen porosimetry; and
(iv) less than 2% of the total pore volume in pores having a diameter above 1000 Å, as determined by mercury penetration porosimetry.
4. The catalyst of claim 3 wherein the calcined support comprises at least 90 wt % of the co-precipitated titania alumina.
5. The catalyst of claim 3 wherein the amount of titania present in the co-precipitated titania alumina is an amount less than 5 wt %, based on the total weight of the titania alumina.
6. The catalyst of claim 5 wherein the amount of titania present in the co-precipitated titania alumina is an amount from about 0.3 to about 4.5 wt % titania, based on the total weight of the titania alumina.
7. The catalyst of claim 3 wherein at least 79% of the total pore volume of the support is in pores having a diameter between about 70 Å and about 130 Å; or (b) from about 0.40% to about 1.5% of the total pore volume is in pores having a diameter above 1000 Å; or both (a) and (b).
8. The catalyst of claim 3 wherein said at least one catalystic agent comprises a metal selected from the group consisting of cobalt, nickel, molybdenum, and combinations thereof.
9. The catalyst of claim 3 wherein the phosphorous concentration is in the range of 0.22 to 1.95 wt % of phosphorous, calculated as elemental phosphorous, based on the weight of total catalyst composition.
10. The catalyst of claim 3 wherein the phosphorous concentration is in the range of about 0.26 to 1.95 wt % of phosphorous, calculated as elemental phosphorous, based on the weight of the total catalyst composition.
11. A process for hydrotreating sulfur containing residuum hydrocarbon feedstocks, which process comprises contacting said residuum feedstocks with a catalyst of claim 3 under hydrodesulfurization process conditions and producing a hydrotreated residuum hydrocarbon fraction having a reduced sulfur content compared to the residuum hydrocarbon feedstock.
12. The process of claim 11 wherein the residuum hydrocarbon feedstock is contacted with the catalyst at a reaction temperature from about 300° C. to about 450° C., a hydrogen pressure of about 120 bar to about 200 bar, a H 2 :Oil ratio ranging from about 250 Nl/l to about 1400 N1/1, and a space velocity from about 0.2 hr −1 to about 2.0 hr −1 .