Phosphorus-Modified FCC Catalysts
Described are fluid catalytic cracking (FCC) compositions, methods of manufacture and use. FCC catalyst compositions comprise catalytic microspheres containing a zeolite, a non-zeolitic component, and a rare earth component. The microspheres are modified with phosphorus. The FCC catalyst composition can be used to crack hydrocarbon feeds, particularly resid feeds containing high V and Ni, resulting in lower hydrogen and coke yields.
1 . A fluid catalytic cracking (FCC) catalyst composition for processing resid feeds comprising:
catalytic microspheres containing a non-zeolitic component, 5 to 25% by weight of a transition alumina, 20% to 65% by weight of a zeolite component intergrown with the non-zeolitic component, a rare earth component and 1% to 5% by weight of a phosphorus component on an oxide basis,
wherein the catalytic microspheres are obtained by forming rare earth-containing microspheres containing the non-zeolitic component, the transition alumina, the zeolite component intergrown within the non-zeolitic component, and yttria or a rare earth component, and further adding the phosphorus component to the rare earth-containing microspheres to provide the catalytic microspheres, and wherein the FCC catalyst composition is effective in preventing at least one of nickel and vanadium from increasing coke and hydrogen yields during cracking of a hydrocarbon.
2 . The FCC catalyst composition of claim 1 , wherein the non-zeolitic component is selected from the group consisting of kaolinite, halloysite, montmorillonite, bentonite, attapulgite, kaolin, amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay, gibbsite (alumina trihydrate), boehmite, titania, alumina, silica, silica-alumina, silica-magnesia, magnesia and sepiolite.
3 . The FCC catalyst composition of claim 2 , wherein the phosphorus component is in the range of 2 wt. % to about 4.0 wt. % P 2 O 5 on an oxide basis.
4 . The FCC catalyst composition of claim 3 , wherein the rare-earth component is selected from one or more of ceria, lanthana, praseodymia, and neodymia.
5 . The FCC catalyst composition of claim 4 , wherein the rare earth component is lanthana, and the lanthana is present in a range of 1 wt. % to about 5.0 wt. % on an oxide basis.
6 . The FCC catalyst composition of claim 5 , wherein the phosphorus component is present in a range of 2 wt. % and about 3.5 wt. % P 2 O 5 on an oxide basis.
7 . The FCC catalyst composition of claim 6 , wherein the microsphere has a phosphorus level of about 2.5-3.5 wt. % P 2 O 5 on an oxide basis and the rare earth metal component is present in an amount of about 2-3 wt. % on an oxide basis.
8 . A method of cracking a hydrocarbon feed under fluid catalytic cracking conditions, the method comprising contacting the hydrocarbon feed with the catalyst of claim 1 .
9 . The method of claim 8 , wherein the non-zeolitic matrix component is selected from the group consisting of kaolinite, halloysite, montmorillonite, bentonite, attapulgite, kaolin, amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay, gibbsite (alumina trihydrate), boehmite, titania, alumina, silica, silica-alumina, silica-magnesia, magnesia and sepiolite.
10 . The method of claim 9 , wherein the phosphorus component is in the range of 1 wt. % to about 5.0 wt. % P 2 O 5 on an oxide basis.
11 . The method of claim 10 , wherein the rare-earth component is selected from one or more of ceria, lanthana, praseodymia, and neodymia.
12 . The method of claim 11 , wherein the rare earth component is lanthana, and the lanthana is present in a range of 1 wt. % to about 5.0 wt. % on an oxide basis.
13 . The method of claim 12 , wherein the microsphere has a phosphorus level of about 2.5 to 3.5 wt. % P 2 O 5 on an oxide basis, and the rare-earth metal component is present in an amount of about 2-3 wt. %, based on the weight of the catalyst.
14 . A method of manufacturing an FCC catalyst comprising:
pre-forming a precursor microsphere comprising a non-zeolitic material and alumina;
in situ crystallizing a zeolite on the pre-formed microsphere to provide a zeolite-containing microsphere;
adding a rare earth component to the zeolite-containing microsphere to provide a rare-earth-containing microsphere; and
adding a phosphorus component to the rare earth-containing precursor microsphere to provide a catalytic microsphere.
15 . The method of claim 14 , wherein the phosphorus component is added by contact with diammonium phosphate.
16 . The method of claim 15 , wherein the rare earth component comprises lanthana, wherein the lanthana is added by ion exchange.
17 . The method of claim 16 , further comprising adding a phosphorus component to the zeolite-containing microsphere.
18 . The method of claim 16 , wherein the rare earth component and the phosphorus component are added sequentially in separate steps.
19 . The method of claim 28 , wherein the method comprises adding a portion of the phosphorus component, then ion exchanging the rare earth component and then adding an additional phosphorus component.