Transition metal tungstate material

Patent metadata

Field	Value
Publication number	US-10682632-B2
Application number	US-201916388481-A
Country	US
Kind code	B2
Filing date	Apr 18, 2019
Priority date	Jun 26, 2018
Publication date	Jun 16, 2020
Grant date	Jun 16, 2020

Abstract

A hydroprocessing catalyst or catalyst precursor has been developed. The catalyst is a 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 transition metal tungstate material having the formula:
A m M(OH) n (W) y O z
where ‘A’ is 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; ‘y’ varies from 0.5 to 2; ‘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.

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

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

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

6. A method of making a transition metal tungstate material having the formula:
A m M(OH) n (W) y O z
where ‘A’ is 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; ‘y’ varies from 0.5 to 2; ‘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 and W;
b. reacting the reaction mixture at a temperature of from about 50° C. to about and 250° C. in an autogenous environment; and
c. recovering the transition metal tungstate material.

7. The method of claim 6 further comprising removing at least some of the NH 3 , the H 2 O, or the combination thereof 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 at a temperature of from 50° C. to about 250° C. 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 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 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. The method of claim 6 further comprising decomposing the recovered transition metal tungstate material by sulfidation to form metal sulfides.

14. 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 transition metal tungstate material having the formula:
A m M(OH) n (W) y O z
where ‘A’ is 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; ‘y’ varies from 0.5 to 2; ‘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:

Assignees

• Uop Llc

Inventors

• Miller Stuart R
• Koster Susan C

Classifications

• B01J2235/15

  X-ray diffraction · CPC title

• C10G2300/202

  Heteroatoms content, i.e. S, N, O, P · CPC title

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• B01J21/04

  Alumina · CPC title

• C10G2300/70

  Catalyst aspects · CPC title