Mixed transition metal tungstate

Patent metadata

Field	Value
Publication number	US-10995013-B2
Application number	US-201816189501-A
Country	US
Kind code	B2
Filing date	Nov 13, 2018
Priority date	Dec 20, 2017
Publication date	May 4, 2021
Grant date	May 4, 2021

Abstract

A unique crystalline mixed transition metal tungstate material has been developed material may be sulfided to generate metal sulfides which are used as a catalyst in a conversion process such as hydroprocessing. The hydroprocessing may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

First claim

The invention claimed is:

1. A crystalline mixed transition metal tungstate material having the formula:
Ni x M (1-x) (OH) a W y O z

where ‘M’ is a metal selected from Mn, Fe, Co, V, Cu, Zn and mixtures thereof; ‘x’ varies from 0.001 to 0.9999; ‘a’ varies from 0.001 to 2; ‘y’ varies from 0.3 to 1.2; ‘z’ is a number which satisfies the sum of the valences of Ni, M, W; the material is further characterized by a x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

TABLE A

d(Å)
I/I 0 (%)

7.54
w-m

4.6
s

3.87
s

2.92
s

2.51
vs

1.7
vs

1.63
m.

2. The novel crystalline mixed transition metal tungstate material of claim 1 wherein the material is present in a mixture with at least one binder and wherein the mixture comprises up to 25 wt-% binder.

3. The crystalline mixed transition metal tungstate material of claim 2 wherein the binder is selected from silicas, aluminas, and silica-aluminas.

4. The crystalline mixed transition metal tungstate material of claim 1 wherein M is zinc or cobalt.

5. The crystalline mixed transition metal tungstate material of claim 1 wherein M is zinc.

6. The crystalline mixed transition metal tungstate material of claim 1 wherein the crystalline mixed transition metal tungstate material is sulfided.

7. A method of making a crystalline mixed transition metal tungstate material having the formula:
Ni x M (1-x) (OH) a W y O z

where ‘M’ is a metal selected from Mn, Fe, Co, V, Cu, Zn and mixtures thereof; ‘x’ varies from 0.001 to 0.9999; ‘a’ varies from 0.001 to 2; ‘y’ varies from 0.3 to 1.2; ‘z’ is a number which satisfies the sum of the valences of Ni, M, W; the material is further characterized by a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

TABLE A

d(Å)
I/I 0 (%)

7.54
w-m

4.6
s

3.87
s

2.92
s

2.51
vs

1.7
vs

1.63
m

the method comprising:
a. forming a reaction mixture containing H 2 O, M, W and Ni;
b. adjusting the pH of the reaction mixture to a pH from 6.5 to 10;
c. reacting the mixture at a temperature from 90° C. and 220° C. in an autogenous environment;
d. recovering the crystalline mixed transition metal tungstate material.

8. The method of claim 7 wherein the reacting is conducted for a period of time from 30 minutes to 14 days.

9. The method of claim 7 wherein the recovering is by filtration, centrifugation, or decantation.

10. The method of claim 7 further comprising adding a binder to the recovered crystalline mixed transition metal tungstate material.

11. The method of claim 10 wherein the binder is selected from aluminas, silicas, and alumina-silicas.

12. The method of claim 7 further comprising sulfiding at least a portion of the recovered crystalline mixed transition metal tungstate material to generate metal sulfides.

13. A conversion process comprising contacting a material with a sulfiding agent to convert at least a portion of the material to a metal sulfide and contacting the metal sulfide with a feed at conversion conditions to give at least one product, the material comprising:
a crystalline mixed transition metal tungstate material having the formula:
Ni x M (1-x) (OH) a W y O z

where ‘M’ is a metal selected from Mn, Fe, Co, V, Cu, Zn and mixtures thereof; ‘x’ varies from 0.001 to 0.9999; ‘a’ varies from 0.001 to 2; ‘y’ varies from 0.3 to 1.2; ‘z’ is a number which satisfies the sum of the valences of Ni, M, W; the material is further characterized by a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

TABLE A

d(Å)
I/I 0 (%)

7.54
w-m

4.6
s

3.87
s

2.92
s

2.51
vs

1.7
vs

1.63
m.

14. The process of claim 13 wherein the conversion process is hydroprocessing.

15. The process of claim 13 wherein the conversion process is selected from hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

16. The process of claim 13 wherein the novel crystalline mixed transition metal tungstate material is present in a mixture with at least one binder and wherein the mixture

Assignees

• Uop Llc

Inventors

• Miller Stuart R
• Koster Susan C
• Mowat John P S
• Sinkler Wharton

Classifications

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• C01G53/82 Primary

  Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements · CPC title