Spheroidal resid hydrodemetallation catalyst
Spheroidal catalyst support, supported catalyst, and method of preparing and using the catalyst for hydrodemetallation of metal-containing heavy oil feedstocks are disclosed. The catalyst supports comprise titania alumina having 5 wt % or less titania and have greater than 30% percent of their pore volume in pores having a diameter of between 200 and 500 Å. Catalysts prepared from the supports contain Group 6, 9 and 10 metals or metal compounds supported on the titania alumina supports. Catalysts in accordance with the invention exhibit improved catalytic activity and stability to remove metals from heavy feedstocks during a hydrotreating process. The catalysts also provide increased sulfur and MCR conversion during a hydrotreating process.
1. A calcined spheroidal catalyst support comprising co-precipitated titania alumina having less than 5 wt % titania based on the total titania alumina, said support having a total pore volume in the range of about 0.7 to about 1.2 cc/g, and a pore volume distribution such that greater than 40% of the total pore volume have pores in a diameter larger than 200 Å, about 30% or greater of the total pore volume have pores in the range of about 200 Å to about 500 Å and, greater than 10% of the total pore volume have pores with a diameter above 1000 Å; wherein:
(a) the co-precipitated titania alumina results from simultaneous co-precipitation of aqueous solutions of aluminum sulfate, sodium aluminate and titanium sulfate; and
(b) the calcined support has been calcined at a temperature of about 960° C. to about 1100° C.
2. The support of claim 1 having a total pore volume in the range of about 0.8 to about 1.1 cc/g.
3. The support of claim 1 wherein titania is present in the co-precipitated titania alumina in an amount ranging from about 2.5 to about 4.0 wt % titania, based on the total weight of the titania alumina.
4. The support of claim 1 wherein the support comprises at least 90wt % titania alumina having an alumina R value of from about 0.4 to about 1.7, wherein R is the ratio between the integrated intensity of the X-ray diffraction peak at 2Θ=32° and the integrated intensity of the X-ray diffraction peak at 2Θ=46°.
5. The support of claim 1 wherein from about 50% to about 90% of the total pore volume is in pores having a diameter larger than 200 Å; from about 30% to about 80% of the total pore volume is in pores having a diameter from about 200 to about 500 Å; and greater than 15% of the total pore volume of the support have pores in a diameter above 1000 Å.
6. The support of claim 1 wherein from about 30% to about 80% of the total pore volume is in pores having a diameter from about 200 to about 500 Å.
7. The support of claim 1 wherein greater than 15% of the total pore volume of the support is in pores having a diameter above 1000 Å.
8. A calcined spheroidal catalyst support comprising co-precipitated titania alumina having less than 5 wt % titania based on the total titania alumina, said support having a total pore volume in the range of about 0.7 to about 1.2 cc/g, and a pore volume distribution such that greater than 40% of the total pore volume have pores in a diameter larger than 200 Å, about 30% or greater of the total pore volume have pores in the range of about 200 Å to about 500 Å and, greater than 30% of the total pore volume have pores with a diameter above 1000 Å.
9. The support of claim 8 having a total pore volume in the range of about 0.8 to about 1.1 cc/g.
10. The support of claim 8 wherein titania is present in the co-precipitated titania alumina in an amount ranging from about 2.5 to about 4.0 wt % titania, based on the total weight of the titania alumina.
11. The support of claim 8 wherein the support comprises at least 90 wt % titania alumina having an alumina R value of from about 0.4 to about 1.7, wherein R is the ratio between the integrated intensity of the X-ray diffraction peak at 2Θ=32° and the integrated intensity of the X-ray diffraction peak at 2Θ=46°.
12. The support of claim 8 wherein from about 50% to about 90% of the total pore volume is in pores having a diameter larger than 200 Å; from about 30% to about 80% of the total pore volume is in pores having a diameter from about 200 to about 500 Å; and greater than 15% of the total pore volume of the support have pores in a diameter above 1000 Å.
13. The support of claim 8 wherein from about 30% to about 80% of the total pore volume is in pores having a diameter from about 200 to about 500 Å.
14. The support of claim 8 wherein greater than 15% of the total pore volume of the support is in pores having a diameter above 1000 Å.
15. The support of claim 8 wherein the support has been calcined at a temperature of about 960° C. to about 1100° C.