Fcc catalyst with enhanced mesoporosity, its preparation and use

Patent metadata

Field	Value
Publication number	US-2020338536-A1
Application number	US-201916960930-A
Country	US
Kind code	A1
Filing date	Jan 11, 2019
Priority date	Jan 12, 2018
Publication date	Oct 29, 2020
Grant date	—

Abstract

Process for the preparation of a catalyst and a catalyst comprising enhanced mesoporosity is provided herein. Thus, in one embodiment, provided is a particulate FCC catalyst comprising 2 to 50 wt % of one or more ultra stabilized high Si02/A1203 ratio large pore faujasite zeolite or a rare earth containing USY, 0 to 50 wt % of one or more rare-earth exchanged large pore faujasite zeolite, 0 to 30 wt % of small to medium pore size zeolites, 5 to 45 wt % quasi-crystalline boehmite 0 to 35 wt % microcrystalline boehmite, 0 to 25 wt % of a first silica, 2 to 30 wt % of a second silica, 0.1 to 10 wt % one or more rare earth components showiomg enhanced mesoporosity in the range of 6-40 nm, the numbering of the silica corresponding to their orders of introduction in the preparation process.

First claim

1 . An FCC catalyst composition comprising a first zeolite of about 2 to about 50 wt % selected from the group of one or more ultra stabilized or rare earth exchanged ultra stabilized high SiO2/Al2O3 ratio Y, optionally a second zeolite of 0 to about 50 wt % of one or more rare-earth exchanged Y zeolite, optionally 0 to 30 wt % of small to medium pore zeolite, about 5 to about 45 wt % quasicrystalline boehmite, about 0 to about 35 wt % microcrystalline boehmite, a first silica of about 0 to about 20 wt %, a second silica of about 2 to about 30 wt %, about 0.1 to about 10 wt % one or more rare earth components as oxide and the balance clay.

2 . The FCC Catalyst of claim 1 wherein the catalyst has increased mesopores in the range of 6-40 nm compared to standard base catalysts.

3 . The FCC Catalyst of claim 1 further comprising a pore diameter distribution having a peak at a pore diameter of about 2.0 to about 6 nm.

4 . The FCC Catalyst of claim 1 has about 20 to about 30% of the total pore volume contributed by pores at a diameter of about 2.0 to about 6 nm and about 55 to about 70% of the pore volume of pores at a diameter of about 6 to 40 nm.

5 . The FCC Catalyst of claim 1 wherein the first zeolite is one or more ultra stabilized high SiO2/Al2O3 ratio Y zeolite.

6 . The FCC Catalyst of claim 1 wherein the first zeolite is one or more rare earth exchanged ultra stabilized high SiO2/Al2O3 ratio Y.

7 . The FCC Catalyst of claim 1 wherein the one or more rare earth components comprise lanthanum, yttrium, cerium or mixtures thereof.

8 . The FCC Catalyst of claim 1 wherein the one or more rare earth components comprise lanthanum.

9 . The FCC Catalyst of claim 1 wherein the one or more rare earth components are added to the catalyst as hydroxide, chloride, oxide, nitrate, sulfate, oxychlorides, acetates, or carbonates.

10 . The FCC Catalyst of claim 8 wherein the one or more rare earth components comprise lanthanum nitrate.

11 . The FCC Catalyst of claim 1 wherein the medium pore zeolites comprises ZSM-5, ZSM-11, ZSM-22, Beta, Ferrierite, or mixtures thereof.

12 . The FCC Catalyst of claim 1 wherein the first silica comprises sodium stabilized colloidal silica.

13 . The FCC Catalyst of claim 1 wherein the second silica comprises acidic colloidal silica or ammonia stabilized colloidal silica or low-sodium stabilized colloidal silica or polysilicic acid, or mixtures thereof

14 . A process for the manufacturing of a catalyst composition of the present invention prepared by:
a. Adding, clay, boehmite, a first silica to form a slurry; b. Digesting the slurry with a monoprotic acid to a pH of less than 4; c. Adding one or more zeolites from the group of ultra stabilized high SiO2/Al2O3 Y zeolite, rare earth exchanged USY, rare earth exchanged Y zeolites, zeolites with pentasil and beta structures to the slurry and mixtutres thereof; d. Adding a rare earth component to the slurry either after step (a) or after step (c) and mixing; e. Adjust the slurry pH to below 4 with monoprotic acid; f Adding a second silica anywhere in the above steps a-e; g. Destabilizing the slurry by raising the pH to above 4.0; h. Shaping and collecting the resulting catalyst. i. Optionally followed by a calcination and post washing step to remove excess sodium as necessary.

15 . The process of claim 14 wherein the first silica comprises sodium stabilized colloidal silica.

16 . The process of claim 14 wherein the second silica comprises acidic colloidal silica or ammonia stabilized colloidal silica or low-sodium stabilized colloidal silica or polysilicic acid, or mixtures thereof

17 . The process of claim 14 wherein the one or more rare earth components are added to the catalyst as hydroxide, chloride, oxide, nitrate, sulfate, oxychlorides, acetates, or carbonates.

18 . The process of claim 17 wherein the one or more rare earth components comprise lanthanum nitrate.

19 . The process of claim 14 wherein the resulting catalyst has increased mesopores in the range of 6-40 nm compared to standard base catalysts.

20 . The process of claim 14 wherein the resulting catalyst further comprises a pore diameter distribution having a peak at a pore diameter of about 2.0 to about 6 nm.

21 . The process of claim 14 wherein the resulting catalyst further comprises about 20 to about 30% of total pore volume contributed by pores at diameter about 2.0 to about 6 nm and 55 to about 70% of total pore volume at about 6 to 40 nm.

22 . An FCC catalyst composition comprising a first zeolite of about 2 to about 50 wt % selected from the group of one or more ultra stabilized or rare earth exchanged ultra stabilized high SiO2/Al2O3 ratio Y, optionally a second zeolite of 0 to about 50 wt % of one or more rare-earth exchanged Y zeolite, optionally 0 to 30 wt % of small to medium pore zeolite, about 5 to about 45 wt % quasicrystalline boehmite, about 0 to about 35 wt % microcrystalline boehmite, a first silica of about 0 to about 20 wt %, a second silica of about 2 to about 30 wt %, about 0.1 to about 10 wt % one or more rare earth components as oxide and the balance clay manufactured by the process of claim 14 .

23 . A process for cracking a petroleum fraction feedstock said process comprising the steps of:
a) a first zeolite of about 2 to about 50 wt % selected from the group of one or more ultra stabilized or rare earth exchanged ultra stabilized high SiO2/Al2O3 ratio Y, optionally a second zeolite of 0 to about 50 wt % of one or more rare-earth exchanged Y zeolite, optionally 0 to 30 wt % of small to medium pore zeolite, about 5 to about 45 wt % quasicrystalline boehmite, about 0 to about 35 wt % microcrystalline boehmite, a first silica of about 0 to about 20 wt %, a second silica of about 2 to about 30 wt %, about 0.1 to about 10 wt % one or more rare earth components as oxide and the balance clay; b) contacting the FCC catalyst with said petroleum fraction feedstock at a temperature in the range of from 400 to 650° C., with a dwell time in the range of from 0.5 to 12 seconds.

Assignees

• Albemarle Corp

Inventors

• Sabahi Amir
• Iyyamperumal Eswaramoorthi
• Vargas Nataly Garcia
• Knowles William
• Loebl Andrew
• Francis Julie

Classifications

• C07C2529/06

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title

• C07C2527/167

  Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)- · CPC title

• C07C2529/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 · CPC title

• C07C2529/70

  of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 · CPC title

• C07C2527/14

  Phosphorus; Compounds thereof · CPC title