Crystalline oxy-hydroxide transition metal molybdotungstate

Patent metadata

Field	Value
Publication number	US-10875013-B2
Application number	US-201816189057-A
Country	US
Kind code	B2
Filing date	Nov 13, 2018
Priority date	Dec 20, 2017
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

Abstract

A unique crystalline transition metal molybdotungstate material has been developed. The 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 transition metal molybdotungstate material having the formula:
M(OH) a Mo x W y O z

where ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn and mixtures thereof; ‘a’ varies from 0.001 to 2; ‘x’ varies from 0.001 to 1.2; ‘y’ varies from 0.4 to 1.2; the sum of (x+y) varies from 0.4 to 1.4; ‘z’ is a number which satisfies the sum of the valency of M, x and y; the material is further characterized by an 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 crystalline transition metal molybdotungstate 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 transition metal molybdotungstate material of claim 2 wherein the binder is selected from the group consisting of silicas, aluminas, and silica-aluminas.

4. The crystalline transition metal molybdotungstate material of claim 1 wherein M is nickel or cobalt.

5. The crystalline transition metal molybdotungstate material of claim 1 wherein M is nickel.

6. The crystalline transition metal molybdotungstate material of claim 1 wherein the crystalline transition metal molybdotungstate material is sulfided to convert at least a portion of the material to a metal sulfide, wherein the metal sulfide is used as a catalyst.

7. A method of making a crystalline transition metal molybdotungstate material having the formula:
M(OH) a Mo x W y O z

where ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn and mixtures thereof; ‘a’ varies from 0.001 to 2; ‘x’ varies from 0.001 to 1.2; ‘y’ varies from 0.4 to 1.2; the sum of (x+y) varies from 0.4 to 1.4; ‘z’ is a number which satisfies the sum of the valency of M, x and y; the material is further characterized by an 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 Mo;
b. adjusting the pH of the reaction mixture to a pH of about 6.5 to about 10;
c. reacting the reaction mixture at a temperature from about 90° C. to about 250° C. in an autogenous environment; and
d. recovering the crystalline transition metal molybdotungstate material.

8. The method of claim 7 wherein the reacting is conducted for a period of time from about 30 minutes to about 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 transition metal molybdotungstate material.

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

12. The method of claim 7 further comprising sulfiding at least a portion of the recovered crystalline transition metal molybdotungstate material to generate metal sulfides, wherein the metal sulfides are used as catalysts.

13. A hydroprocessing 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 selected from diesel, gasoline, naphtha, kerosene, gas oils, distillates, and reformate at conversion conditions for hydroprocessing the feed, the material comprising: a crystalline transition metal molybdotungstate material having the formula:
M(OH) a Mo x W y O z

where ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn and mixtures thereof; ‘a’ varies from 0.001 to 2; ‘x’ varies from 0.001 to 1.2; ‘y’ varies from 0.4 to 1.2; the sum of (x+y) varies from 0.4 to 1.4; ‘z’ is a number which satisfies the sum of the valency of M, x and y; the material is further characterized by an 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

wherein, the conversion conditions include a reaction pressure from about 2.5 MPa to about 17.2 MPa, and a reacti

Assignees

• Uop Llc

Inventors

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

Classifications

• C10G45/46 Primary

  characterised by the catalyst used · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J27/051

  Molybdenum · CPC title

• B01J27/0515 Primary

  with iron group metals or platinum group metals · CPC title

• B01J23/8885

  containing also molybdenum · CPC title