Method for making a hydroprocessing catalyst

Patent metadata

Field	Value
Publication number	US-9512372-B2
Application number	US-201314100779-A
Country	US
Kind code	B2
Filing date	Dec 9, 2013
Priority date	Dec 6, 2009
Publication date	Dec 6, 2016
Grant date	Dec 6, 2016

Abstract

The present invention is directed to a method for making a catalyst for hydroprocessing a carbonaceous feedstock under hydroprocessing conditions, and the use of that catalyst. More particularly, the present invention is directed to methods for inhibiting rapid decomposition of ammonium nitrate during calcination of the catalyst following metal impregnation, wherein ammonium nitrate is formed when a nitrate-containing composition and an ammonium-containing component is used in the deposition of metal onto the catalyst.

First claim

What is claimed is:

1. A method for hydroprocessing a carbonaceous feedstock, comprising contacting the carbonaceous feedstock with a sulfided hydroprocessing catalyst and hydrogen under hydroprocesssing conditions, the hydroprocessing catalyst comprising at least one metal deposited on a catalyst support, wherein the hydroprocessing catalyst is made by a method comprising the steps of:
(a) forming an extrudable mass containing the catalyst support,
(b) extruding the mass to form a shaped extrudate,
(c) calcining the mass to form a calcined extrudate,
(d) preparing an impregnation solution containing at least one metal nitrate, a modifying agent and an ammonium containing component, and adjusting the pH of the impregnation solution with a hydroxide to between 1 and 5.5, inclusive,
(e) contacting the shaped extrudate with the impregnation solution, and
(f) drying the impregnated extrudate at a temperature sufficient to remove the impregnation solution solvent, to form a dried impregnated extrudate.

2. The method of claim 1 , wherein the sulfided hydroprocessing catalyst further comprises at least one molecular sieve.

3. The method of claim 2 , wherein the molecular sieve is a Y zeolite with a unit cell size of between 24.15 Å and 24.55 Å.

4. The method of claim 2 , wherein the at least one molecular sieve is a Y zeolite having a silica-to-alumina ratio of greater than 5, a micropore volume of from 0.15 mL/g to 0.27 mL/g, a BET surface area of from 700 m 2 /g to 825 m 2 /g, and a unit cell size of from 24.15 Å to 24.55 Å.

5. The method of claim 1 , wherein the sulfided hydroprocessing catalyst further comprises a Y zeolite having a silica-to-alumina ratio of greater than 10, a micropore volume of from 0.15 mL/g to 0.27 mL/g, a BET surface area of from 700 m 2 /g to 825 m 2 /g, and a unit cell size of from 24.15 Å to 24.35 Å, and a low-acidity, highly dealuminated ultrastable Y zeolite having an Alpha value of less than about 5 and Brønsted acidity of from 1 to 40 micro-mole/g.

6. The method of claim 1 , wherein the modifying agent is selected from the groups consisting of compounds represented by structures (1) through (4), and condensated forms thereof:

wherein:
(1) R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen; hydroxyl; methyl; amine; and linear or branched, substituted or unsubstituted C 1 -C 3 alkyl groups, C 1 -C 3 alkenyl groups, C 1 -C 3 hydroxyalkyl groups, C 1 -C 3 alkoxyalkyl groups, C 1 -C 3 aminoalkyl groups, C 1 -C 3 oxoalkyl groups, C 1 -C 3 carboxyalkyl groups, C 1 -C 3 aminocarboxyalkyl groups and C 1 -C 3 hydroxycarboxyalkyl groups;
(2) R 4 through R 10 are independently selected from the group consisting of hydrogen; hydroxyl; and linear or branched, substituted or unsubstituted C 2 -C 3 carboxyalkyl groups; and
(3) R 11 is selected from the group consisting of linear or branched, saturated and unsaturated, substituted or unsubstituted C 1 -C 3 alkyl groups, C 1 -C 3 hydroxyalkyl groups, and C 1 -C 3 oxoalkyl groups.

7. The method of claim 1 , wherein the modifying agent is selected from the group consisting of N,N′-bis(2-aminoethyl)-1,2-ethane-diamine, 2-amino-3-(1H-indol-3-yl)-propanoic acid, benzaldehyde, [[(carboxymethyl)imino]bis(ethylenenitrilo)]-tetra-acetic acid, 1,2-cyclohexanediamine, 2-hydroxybenzoic acid, thiocyanate, thiosulfate, thiourea, pyridine, and quinoline.

8. The method of claim 1 , wherein the at least one metal nitrate comprises a metal selected from the group consisting of elements from Group 6 and Groups 8 through 10 of the Periodic Table.

9. The method of claim 8 , wherein the at least one metal is selected from the group consisting of nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iron (Fe), chromium (Cr), molybdenum (Mo), tungsten (W), and mixtures thereof.

10. The method of claim 1 , wherein the hydroprocessing conditions comprise a temperature in the range of 175-485° C., hydrogen pressures in the range of 5 to 300 bar, and LHSV in the range of 0.1-30 h −1 .

11. The method of claim 1 , wherein the hydroprocessing conditions comprise a reaction temperature between 204-482° C., a feed rate (LHSV) of 0.5 hr −1 to 20 hr −1 (v/v), and an overall hydrogen consumption of 53.4 to 356 m 3 H 2 per m 3 of liquid hydrocarbon feed.

12. The method of claim 1 , wherein the hydroxide comprises ammonium hydroxide.

Assignees

• Zhan Bi-Zeng
• Chevron Usa Inc

Inventors

• Zhan Bi-Zeng

Classifications

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/50

  characterised by their shape or configuration · CPC title

• C10G45/64

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title

• B01J29/166

  Y-type faujasite · CPC title