Mixed metal oxides

Patent metadata

Field	Value
Publication number	US-10286384-B2
Application number	US-201816037746-A
Country	US
Kind code	B2
Filing date	Jul 17, 2018
Priority date	Dec 15, 2015
Publication date	May 14, 2019
Grant date	May 14, 2019

Abstract

A novel mixed metal molybdate useful as a hydroprocessing catalyst or catalyst precursor has been created. The hydroprocessing using the novel mixed metal molybdate material or the decomposition product thereof may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

First claim

The invention claimed is:

1. A conversion process comprising contacting a feed with a catalyst at conversion conditions to give at least one product, the catalyst comprising the decomposition product of the decomposition by sulfidation of a mixed metal oxide having the formula:
MMo x O y

where ‘M’ is a metal selected from Mg, Mn, Fe, Co, Ni, Cu, Zn, and combinations thereof; ‘x’ varies from 0.5 to 1.5; ‘y’ is a number which satisfies the sum of the valences of M and Mo; the mixed metal oxide having a x-ray powder diffraction pattern showing the peaks at the d-spacings listed in Table A:

TABLE A

d (Å)

 4.2-2.89

2.65-2.53

2.17-2.04

1.53-1.45

2. The process of claim 1 wherein the conversion process is hydroprocessing.

3. The process of claim 1 wherein the hydroprocessing process is selected from the group consisting of hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodearomatization, hydroisomerization, hydrodesilication, hydrotreating, hydrofining, and hydrocracking.

4. The process of claim 1 wherein the mixed metal oxide, or the decomposition product, or both are present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt % binder.

5. The process of claim 4 wherein the binder is selected from the group consisting of silicas, aluminas, and silica-aluminas.

6. The process of claim 1 wherein M is nickel or cobalt.

7. The process of claim 1 wherein the feed comprises sulfur and the decomposition by sulfidation comprises contacting mixed metal oxide with the sulfur containing feed.

8. The process of claim 1 wherein the decomposition by sulfidation comprises contacting the mixed metal oxide with a gaseous mixture of H 2 S/H 2 .

9. The process of claim 1 wherein the sulfidation is conducted at a temperature ranging from about 50° C. to about 600° C.

10. The process of claim 1 wherein the sulfidation is conducted at a temperature ranging from about 150° C. to about 500° C.

11. The process of claim 1 wherein the sulfidation is conducted at a temperature ranging from about 250° C. to about 450° C.

12. A method of making a mixed metal oxide having the formula:
MMo x O y

where ‘M’ is a metal selected from Mg, Mn, Fe, Co, Ni, Cu, Zn, and combinations thereof; ‘x’ varies from 0.5 to 1.5; ‘y’ is a number which satisfies the sum of the valences of M and Mo; the mixed metal oxide having a x-ray powder diffraction pattern showing the peaks at the d-spacings listed in Table A:

TABLE A

d (Å)

 4.2-2.89

2.65-2.53

2.17-2.04

1.53-1.45

the method comprising:
(a) forming a reaction mixture containing NH 4 OH, H 2 O, and sources of M and Mo;
(b) adjusting the pH of the reaction mixture to a pH of from about 8.5 to about 10;
(c) heating the reaction mixture to a temperature of about 85° C. to about 100° C. until the resultant pH is from about 8.5 to about 9.5;
(d) recovering a crystalline bis-ammonia metal molybdate pre-cursor having the formula:
(NH 3 ) 2-N M(OH 2 ) n Mo x O y

 where ‘n’ varies from 0.1 to 2.0; ‘M’ is a metal selected from Mg, Mn, Fe, Co, Ni, Cu, Zn, and combinations thereof, ‘x’ varies from 0.5 to 1.5; ‘y’ is a number which satisfies the sum of the valences of M and Mo, the mixed metal oxide having a x-ray powder diffraction pattern showing the crystalline peaks in Table B:

TABLE B

d (Å)
I/I 0 %

7.49-7.28
vs

 5.1-5.05
s

 4.4-4.257
w

3.966-3.915
m

 3.69-3.645
s

3.52-3.48
m

3.35-3.32
m

3.31-3.29
m

 3.12-3.097
w

  3-2.97
m

2.76-2.73
m

(e) heating the crystalline bis-ammonia metal molybdate precursor at a temperature of from about 275° C. to about 350° C. for about 1 to about 24 hours; and
(f) recovering the mixed metal oxide.

13. The method of claim 12 wherein the recovering is by filtration or centrifugation.

14. The method of claim 12 further comprising adding a binder to the crystalline bis-ammonia metal molybdate precursor, or to the mixed metal oxide, or both.

15. The method of claim 14 wherein the binder is selected from the group consisting of aluminas, silicas, and alumina-silicas.

16. The method of claim 12 further comprising decomposing by sulfidation the crystalline bis-ammonia metal molybdate precursor, or the mixed metal oxide, or both.

17. The method of claim 12 wherein M is nickel or cobalt.

Assignees

• Uop Llc

Inventors

• Miller Stuart
• Koster Susan C

Classifications

• B01J37/031

  Precipitation · CPC title

• B01J23/8892

  Manganese · CPC title

• C10G47/04

  Oxides · CPC title

• C10G45/50

  in combination with chromium, molybdenum or tungsten metal, or compounds thereof · CPC title

• B01J37/088

  Decomposition of a metal salt · CPC title