Process and Materials for Trim Dewaxing of Distillates

Patent metadata

Field	Value
Publication number	US-2023211328-A1
Application number	US-202118000735-A
Country	US
Kind code	A1
Filing date	May 12, 2021
Priority date	Jun 17, 2020
Publication date	Jul 6, 2023
Grant date	—

Abstract

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.

First claim

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 selected from the group consisting of palladium, platinum, mixtures of palladium and platinum, and mixtures of 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 .- 9 . (canceled)

10 . 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.

11 . (canceled)

12 . The process of claim 10 , 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.

13 . The process of claim 1 , wherein the effective dewaxing conditions comprise a temperature of at least about 300° C., such as at least about 325° C., such as at least about 350° C. or at least about 400° C.

14 . 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 selected from the group consisting of palladium, platinum, mixtures of palladium and platinum, and mixtures of 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.

15 . The method of claim 14 , wherein the mixture further comprises water, wherein the solids content of the extrudable paste is from about 45% to 55% by weight.

16 . The method of claim 14 , 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, Methocel™, and mixtures thereof.

17 . The method of any one of claim 14 , wherein
the dewaxing catalyst is sulfided.

18 . The method of claim 14 , wherein the dewaxing catalyst is exchanged with a source of ammonium ions, washed with water, dried and calcined.

19 .- 22 . (canceled)

23 . 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 selected from the group consisting of palladium, platinum, mixtures of palladium and platinum, and mixtures of 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.

24 . The catalyst of claim 23 , 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.

25 . The catalyst of claim 23 , 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.

26 . The catalyst of claim 23 , 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.

27 . The catalyst of claim 23 , 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.

28 . The catalyst of claim 23 , 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.

29 . The catalyst of claim 23 , wherein the metal hydrogenation component is a non-noble metal component which comprises 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.

30 . The catalyst of claim 23 , wherein the first metal is nickel or cobalt, and the second metal is molybdenum.

31 . The catalyst of claim 23 , wherein the metal hydrogenation component is a noble metal selected from the group consisting of palladium, platinum and mixtures thereof.

32 . The catalyst of claim 23 , further comprising a binder, the binder comprising alumina, silica, silica-alumina, zirconia, titania, or mixtures thereof.

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Stalzer Madelyn
• Gatt Joseph
• Bai Chuansheng
• Oliveri Christopher

Classifications

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J29/7869

  MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3 · CPC title

• B01J37/20

  Sulfiding · CPC title

• B01J29/7892

  MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13 · CPC title

• B01J2229/18

  to introduce other elements into or onto the molecular sieve itself · CPC title