Transition metal molybdotungstate material

Patent metadata

Field	Value
Publication number	US-11033883-B2
Application number	US-201916388495-A
Country	US
Kind code	B2
Filing date	Apr 18, 2019
Priority date	Jun 26, 2018
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

A hydroprocessing catalyst or catalyst precursor has been developed. The catalyst is a transition metal molybdotungstate material or metal sulfides derived therefrom. The hydroprocessing using the transition metal molybdotungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

First claim

The invention claimed is:

1. A transition metal molybdotungstate material having the formula:
A m M(OH) n (Mo) x (W) y O z
where ‘A’ is selected from NH 3 , H 2 O, or combinations thereof; ‘m’ varies from 0.001 to 50; ‘n’ varies from 0.001 to 10; ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn, and combinations thereof; ‘x’ varies from 0.001 to 1; ‘y’ varies from 0.5 to 2; ‘x+y’≤2.25; and ‘z’ is a number which satisfies the sum of the valency of the cationic species present in the material; the material 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 (%)

11.29
s

8.9
vs

5.93
vs

5.65
w

5.26
m

4.84
m

4.44
m

4.27
w

4.1
m

3.77
m

3.66
m.

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

3. The transition metal molybdotungstate material of claim 2 wherein the binder is selected from the group consisting of silicas, aluminas, and silica-aluminas.

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

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

6. A method of making a transition metal molybdotungstate material having the formula:
A m M(OH) n (Mo) x (W) y O z
where ‘A’ is selected from NH 3 , H 2 O, or combinations thereof; m varies from 0.001 to 50; ‘n’ varies from 0.001 to 10; ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn, and combinations thereof; ‘x’ varies from 0.001 to 1; ‘y’ varies from 0.5 to 2; ‘x+y’≤2.25; and ‘z’ is a number which satisfies the sum of the valency of the cationic species present in the material; the material 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 (%)

11.29
s

8.9
vs

5.93
vs

5.65
w

5.26
m

4.84
m

4.44
m

4.27
w

4.1
m

3.77
m

3.66
m

the method comprising:
a. forming a reaction mixture containing NH 3 , H 2 O, or a combination thereof, and sources of M, W, and Mo;
b. reacting the reaction mixture at a temperature from about 50° C. to about 250° C. in an autogenous environment; and
c. recovering the transition metal molybdotungstate material.

7. The method of claim 6 further comprising removing at least some of the NH 3 or H 2 O, or both to form an intermediate before reacting the mixture at a temperature from about 50° C. to about 250° C. in an autogenous environment.

8. The method of claim 6 wherein the reacting is conducted for a period of time from about 30 minutes to 14 days.

9. The method of claim 6 wherein the recovering is by filtration or centrifugation.

10. The method of claim 6 further comprising drying the recovered transition metal molybdotungstate material at a temperature from about 100° C. to about 350° C. for about 30 minutes to about 48 hours.

11. The method of claim 6 further comprising adding a binder to the recovered transition metal molybdotungstate material.

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

13. The method of claim 6 further comprising decomposing the recovered transition metal molybdotungstate material by sulfidation to form metal sulfides.

14. A hydroprocessing process comprising contacting a material with a sulfiding agent to convert at least a portion of the material to metal sulfides and contacting the metal sulfides with a feed at hydroprocessing conditions to generate at least one product, wherein the material comprises a transition metal molybdotungstate material having the formula:
A m M(OH) n (Mo) x (W) y O z
where ‘A’ is selected from NH 3 , H 2 O, or combinations thereof; m varies from 0.001 to 50; ‘n’ varies from 0.001 to 10; ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn, and combinations thereof; ‘x’ varies from 0.001 to 1; ‘y’ varies from 0.5 to 2; ‘x+y’≤2.25; and ‘z’ is a number which satisfies the sum of the valency of the cationic species present in the material; the material f

Assignees

• Uop Llc

Inventors

• Miller Stuart R
• Koster Susan C

Classifications

• B01J35/70

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

• C01G53/82

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

• B01J2235/15

  X-ray diffraction · CPC title

• B01J23/22

  Vanadium · CPC title

• B01J37/088

  Decomposition of a metal salt · CPC title