Crystalline transition metal tungstate

Patent metadata

Field	Value
Publication number	US-10688479-B2
Application number	US-201916388524-A
Country	US
Kind code	B2
Filing date	Apr 18, 2019
Priority date	Jun 26, 2018
Publication date	Jun 23, 2020
Grant date	Jun 23, 2020

Abstract

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

First claim

The invention claimed is:

1. A crystalline transition metal tungstate material having the formula:
A m M(OH) x W y O z .n H 2 O

where ‘A’ is selected from NH 4 , H 3 O + or combinations thereof; ‘m’ varies from 1 to 12; ‘x’ varies from 0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn and combinations thereof, ‘y’ varies from 0.5 to 6; 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 (%)

11.84
s

10.52
vs

7.79
w

7.59
w

6.81
w

6.48
w

6.18
w

5.93
w

5.70
w

5.59
w

2. The crystalline transition metal tungstate material of claim 1 wherein the crystalline transition metal tungstate 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 tungstate material of claim 2 wherein the binder is selected from the group consisting of silicas, aluminas, and silica-aluminas.

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

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

6. A method of making a crystalline transition metal tungstate material having the formula:
A m M(OH) x W y O z .n H 2 O

where ‘A’ is selected from NH 4 , H 3 O + or combinations thereof, ‘m’ varies from 1 to 12; ‘x’ varies from 0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn and combinations thereof, ‘y’ varies from 0.5 to 6; 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 (%)

11.84
s

10.52
vs

7.79
w

7.59
w

6.81
w

6.48
w

6.18
w

5.93
w

5.70
w

5.59
w

the method comprising:
a. forming a reaction mixture containing sources of A, M, and W;
b. reacting the reaction mixture at a temperature from about 60° C. to about 110° C. in an autogenous environment; and
c. recovering the crystalline transition metal tungstate material.

7. The method of claim 6 further comprising removing at least some of the NH 4 or the H 3 O + or both to form an intermediate before reacting the reaction mixture at a temperature from about 60° C. to about 110° 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 crystalline transition metal tungstate 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 crystalline transition metal tungstate material.

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

13. A conversion 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 conversion conditions to generate at least one product, wherein the material comprises a crystalline transition metal tungstate material having the formula:
A m M(OH) x W y O z .n H 2 O

where ‘A’ is selected from NH 4 , H 3 O + or combinations thereof; ‘m’ varies from 1 to 12; ‘x’ varies from 0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn and combinations thereof, ‘y’ varies from 0.5 to 6; 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

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

• B01J21/04

  Alumina · CPC title

• B01J23/34

  Manganese · CPC title