Hydrotreating catalyst, production and use thereof

Patent metadata

Field	Value
Publication number	US-9713806-B2
Application number	US-201314441806-A
Country	US
Kind code	B2
Filing date	Oct 31, 2013
Priority date	Nov 8, 2012
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

This invention relates to a hydrotreating catalyst suitable for heavy distillate oil hydrodesulfurization, production and use thereof. The present hydrotreating catalyst exhibits significantly improved heavy distillate oil (deep) hydrodesulfurization activity.

First claim

The invention claimed is:

1. A hydrotreating catalyst comprising:
a porous refractory carrier;
one or more compounds selected from the group consisting oxides of elements in Group II, Group III, and Group IV in the periodic table;
an active metal component A, an active metal component B, and an active metal component C; and
optionally an auxiliary component,
wherein the active metal component A is Ni, the active metal component B is one or more metals selected from the group consisting of Group VIII metals other than Ni, the active metal component C is one or more metals selected from the group consisting of Group VIB metals, the auxiliary component is one or more selected from the group consisting of fluorine, silicon, phosphorus, titanium, zirconium, and boron,
wherein the hydrotreating catalyst is in a form of catalyst particles,
wherein C M out presents a ratio of an amount of an active metal component M at an arbitrary point P A on an outmost edge of a cross-section of the catalyst particle to an amount the active metal component M at a central point P o on the cross-section of the catalyst particle, and
when a length of a line segment connecting P o and P A on the cross-section of the catalyst particle is L A ,
C M 1/2 represents a ratio of the amount of M at a point on the line segment (½)L A away from P A to the amount of M at P o ,
C M 1/4 presents a ratio of the amount of M at a point on the line segment (¼)L A away from P A to the amount of M at P o ,
C M 3/4 presents a ratio of the amount of M at a point on the line segment (¾)L A away from P A to the amount of M at P o ,
C M opt , C M opt-1 , C M opt-2 respectively represent ratios of the amount of M at arbitrary points P opt , P opt-1 , and P opt-2 (excluding P a or P o ) on the line segment to the amount of M at P o ,
wherein M stands for the active metal component A, the active metal component B, or the active metal component C,
wherein a distribution of the active metal component A satisfies Conditions (I) or (II),
Condition (I): the active metal component A is substantially uniformly distributed throughout the catalyst particle,
Condition (II): the distribution of the active metal component A simultaneously satisfies Formulas (1) and (2):
C A out >C A 1/4 >C A 1/2 >C A 3/4 >1,  Formula (1):

C A out ≧1.5,  Formula (2):

wherein a distribution of the active metal component B satisfies Conditions (III) or (IV),
Condition (III): the active metal component B is substantially uniformly distributed throughout the catalyst particle,
Condition (IV): the distribution of the active metal component B simultaneously satisfies Formulas (3) and (4):
C B out <C B 1/4 <C B 1/2 <C B 3/4 <1,  Formula 3):

C B out ≦0.80,  Formula (4):

with the proviso that Conditions (I) and (III) are not simultaneously satisfied.

2. The hydrotreating catalyst according to claim 1 , having a specific surface area (by the BET method) of 100-260 m 2 /g, and a pore volume (by the BET method) of 0.20-0.60 ml/g.

3. The hydrotreating catalyst according to claim 1 , based on a total weight of the catalyst, wherein a weight percentage of the porous refractory carrier is 45-89 wt %; a weight percentage of the active metal component A (as NiO) is 1-8 wt %; a weight percentage of the active metal component B (as the corresponding oxide) is at least 0.5 wt %, at most 8 wt %; a weight percentage of the active metal component C (as the corresponding oxide) is 6-60 wt % and a weight percentage of the auxiliary component (as the corresponding element) is 30 wt % or less.

4. The hydrotreating catalyst according to claim 1 , wherein the active metal component C is Mo, and the distribution of Mo meets Conditions (V) or (VI),
Condition (V): Mo is substantially uniformly distributed throughout the catalyst particle,
Condition (VI): the distribution of Mo simultaneously satisfies Formulas (5) and (6):
C Mo out <C Mo 1/4 <C Mo 1/2 <C Mo 3/4 <1,  Formula (5):

0.08≦ C Mo out ≦0.70,  Formula (6):

or,
the active metal component C is a combination of Mo and W, the distribution of Mo meets Conditions (V) or (VI), while the distribution of W meets Conditions (VII) or (VIII),
Condition (V): Mo is substantially uniformly distributed throughout the catalyst particle,
Condition (VI): the distribution of Mo simultaneously satisfies Formulas (5) and (6):
C Mo out <C Mo 1/4 <C Mo 1/2 <C Mo 3/4 <1,  Formula (5):

0.08≦ C Mo out ≦0.70,  Formula (6):

Condition (VII): W is substantially uniformly distributed throughout the catalyst particle,
Condition (VIII): the distribution of Mo simultaneously satisfies Formulas (5) and (6):
C W out >C W 1/4 >C W 1/2 >C W 3/4 >1,  Formula (7):

7.0≧ C W out ≧1.2.  Formula (8):

5. The hydrotreating catalyst according to claim 1 , wherein in Formula (5): C Mo out <C Mo opt <1; and in Formula (7): C W out >C W opt >1.

6. The hydrotreating catalyst according to claim 1 , wherein on the outmost surface of the catalyst particle, the ratio of the amount of the active metal component A to the amount of the active metal component C is 0.22-0.80, and/or,
at P o , the ratio of the amount of the active metal component B to the amount of the active metal component C is 0.20-0.78.

7. The hydrotreating catalyst according to claim 6 , wherein the value of (d2 A −d1 A )/L A is 0.5% or less.

8. The hydrotreating catalyst according to claim 6 , wherein C A opt-1 >98% C A opt-2 is true.

9. The hydrotreating catalyst according to claim 6 , wherein the Formula (1) is C A out >C A opt-1 >C A opt-2 >1.

10. The hydrotreating catalyst according to claim 6 , wherein the value of (d2 B −d1 B )/L B is 0.5% or less.

11. The hydrotreating catalyst according to claim 6 , wherein C B opt-1 <102% C B opt-2 is true.

12. The hydrotreating catalyst according to claim 6 , wherein the Formula (3) is C B out <C B opt-1 <C B opt-2 <1.

13. The hydrotreating catalyst according to claim 1 , wherein, when the active metal component A is distributed according to Formula (1), the amount of the active metal component A along the line segment from P A to P o substantially gradually decreases, with the proviso that (d2 A −d1 A )/L A is 5% or less, C A opt-1 >90% C A opt-2 is true, and
wherein d1 A is the linear distance between P A and P opt-1 , d2 A is the linear distance between P A and P opt-2 , and d1 A /d2 A <1,
or,
when the active metal component B is distributed according to Formula (3), the amount of the active metal component B along the line segment from a point P B to P o substantially gradually increases, with the proviso that when (d2 B −d1 B )/L B is 5% or less, C B opt-1 <110% C B opt-2 is true,
wherein d1 B is the linear distance between P B and P opt-1 , d2 B is the linear distance between P B and P opt-2 , and d1 B /d2 B <1.

14. A method of using a hydrotreating catalyst, comprising:
providing the hydrotreating catalyst according to claim 1 ;
contacting a heavy distillate oil with the hydrotreating catalyst to remove at least a portion of sulfur in the heavy distillate oil.

15. A process for hydrodesulfurizating heavy distillate oil, comprising a step of contacting a heavy distillate oil feedstock with the hydrotreating catalyst according to claim 1 under hydrodesulfurization conditions.

16. The hydrotreating catalyst according to claim 1 , wherein the carrier is one or more sel

Assignees

• China Petroleum & Chem Corp
• Fushun Res Inst Petroleum & Petrochemicals Sinopec

Inventors

• Yang Zhanlin
• Jiang Hong
• Tang Zhaoji
• Wang Jifeng
• Wen Derong
• Wei Dengling

Classifications

• B01J27/1853

  with iron, cobalt or nickel · CPC title

• B01J23/002

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• B01J37/20

  Sulfiding · CPC title

• B01J27/0515

  with iron group metals or platinum group metals · CPC title

• B01J37/0201

  Impregnation · CPC title