Process and materials for trim dewaxing of distillates
Described herein are novel and inventive dewaxing processes that employ dewaxing catalysts which are co-extrusions of two different zeolites, particularly two different 10MR zeolites or a co-extrusion of a 10MR zeolite and a 12MR zeolite in combination with a hydrogenation component. The hydrogenation component can be a mixture of non-noble metal components or a mixture of noble metal components. This novel and inventive process demonstrated a significant activity boost (as measured by increased cloud point reduction) and/or selectivity boost (as measured by reduced diesel loss) compared to either single zeolite component.
1. A process for trim dewaxing a distillate boiling range feed, comprising:
contacting at least a portion of a distillate boiling range feed with a dewaxing catalyst under effective dewaxing conditions to form an a diesel boiling range product, the dewaxing catalyst includes
(a) a co-extrusion of two different zeolites selected from two different 10-membered ring zeolites, or a 10-membered ring zeolite and a 12-membered ring zeolite, and
(b) a metal hydrogenation component comprising a first metal selected from the group consisting of nickel, cobalt and mixtures thereof, and a second metal selected from the group consisting of chromium, molybdenum, tungsten and mixtures thereof.
2. The process of claim 1 , further comprising the step of contacting the portion of the distillate boiling range feed to a hydrotreating catalyst under hydrotreating conditions.
3. The process of claim 2 , wherein the hydrotreating catalyst and the dewaxing catalyst are arranged in fluid communication in a stacked bed of catalyst or are comingled in a mixed bed of catalyst, or a combination thereof.
4. The process of claim 1 , wherein the effective dewaxing conditions comprise a temperature of at least about 300° C.
5. A method comprising:
(a) forming a mixture which comprises a first zeolite, a second zeolite and a binder, wherein the first zeolite and the second zeolite are two different zeolites;
(b) mulling the mixture to form an extrudable paste;
(c) extruding the extrudable paste to form an extrudate; and
(c) drying the extrudate at a temperature of about 80° C. to about 200° C. to form a dried extrudate;
(d) impregnating the dried extrudate with a solution comprising a source of a metal hydrogenation component; and
(e) drying the metal-containing extrudate at a temperature of about 80° C. to about 200° C. to form a dewaxing catalyst, wherein the dewaxing catalyst includes
(a) a co-extrusion of the two different zeolites selected from two different 10-membered ring zeolites, or a 10-membered ring zeolite and a 12-membered ring zeolite, and
(b) the metal hydrogenation component comprising a first metal selected from the group consisting of nickel, cobalt and mixtures thereof, and a second metal selected from the group consisting of chromium, molybdenum, tungsten and mixtures thereof.
6. The method of claim 5 , wherein the mixture further comprises water, wherein the solids content of the extrudable paste is from about 45% to 55% by weight.
7. The method of claim 5 , wherein the mixture further comprises an extrusion aid, the extrusion aid selected from the group consisting of tetraethylammonium hydroxide, citric acid, sodium hydroxide, nitric acid, and mixtures thereof.
8. The method of any one of claim 5 , wherein the dewaxing catalyst is sulfided.
9. The method of claim 5 , wherein the dewaxing catalyst is exchanged with a source of ammonium ions, washed with water, dried and calcined.
10. A dewaxing catalyst, comprising:
(a) a co-extrusion of two different zeolites selected from two different 10-membered ring zeolites, or a 10-membered ring zeolite and a 12-membered ring zeolite; and
(b) a metal hydrogenation component comprising a first metal selected from the group consisting of nickel, cobalt and mixtures thereof, and a second metal selected from the group consisting of chromium, molybdenum, tungsten and mixtures thereof.
11. The catalyst of claim 10 , wherein the 10-membered ring zeolite has a framework type selected from the group consisting of EUO, MEL, MFI, MFS, MRE, MTT, MWW, MWW, NES, TON and mixtures thereof.
12. The catalyst of claim 10 , wherein the 10-membered ring zeolite is selected from the group consisting ZSM-50, EU-1, ZSM-11, ZSM-5, ZSM-57, ZSM-48, ZSM-23, EMM-10, EMM-12, EMM-13, MCM-22, MCM-36, MCM-49, MCM-56, NU-87, ZSM-22, Theta-1, and mixtures thereof.
13. The catalyst of claim 10 , wherein the 12-membered ring zeolite has a framework type selected from the group consisting of *BEA, BEC, EMT, FAU, LTL, MEI, MOR, MOZ, MTW, MSE, OFF and mixtures thereof.
14. The catalyst of claim 10 , wherein the 12-membered ring zeolite is selected from the group consisting of beta, ZSM-2, ZSM-3, ZSM-20, Y, US-Y, L, ZSM-18, mordenite, ZSM-10, ZSM-12, MCM-68, offretite, and mixtures thereof.
15. The catalyst of claim 10 , wherein the co-extrusion of two different zeolites is a co-extrusion of ZSM-11 and ZSM-48, or a co-extrusion of ZSM-23 and ZSM-48, or a co-extrusion of ZSM-48 and ZSM-12.
16. The catalyst of claim 10 , wherein the first metal is nickel or cobalt, and the second metal is molybdenum.
17. The catalyst of claim 10 , further comprising a binder, the binder comprising alumina, silica, silica-alumina, zirconia, titania, or mixtures thereof.
18. The catalyst of claim 10 , wherein the two different zeolites comprise a 10-membered ring zeolite and a 12-membered ring zeolite.