Poorly crystalline transition metal tungstate

Patent metadata

Field	Value
Publication number	US-10737246-B2
Application number	US-201916388418-A
Country	US
Kind code	B2
Filing date	Apr 18, 2019
Priority date	Jun 29, 2018
Publication date	Aug 11, 2020
Grant date	Aug 11, 2020

Abstract

A hydroprocessing catalyst has been developed. The catalyst is a poorly crystalline transition metal tungstate material or a metal sulfide decomposition product thereof. 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 poorly crystalline transition metal tungstate material having the formula:
A m M(OH) n (W) y O z .(NH 3 ) h (H 2 O) i
where ‘A’ is selected from NH 4 + , H 3 O + or combinations thereof, m varies from 0.001 to 2; ‘n’ 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 0.4 to 3; ‘z’ is a number which satisfies the sum of the valency of the cationic species present in the material; ‘h’ varies from 0 to m; and ‘i’ varies from 0 to m; 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 (%)

6.3
w

3.6
vs

3.12
vs

2.74
m

2.38
 w.

2. The poorly crystalline transition metal tungstate material of claim 1 wherein the poorly 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 poorly 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 poorly crystalline transition metal tungstate material of claim 1 wherein M is nickel or zinc.

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

6. A method of making a poorly crystalline transition metal tungstate material having the formula:
A m M(OH) n (W) y O z .(NH 3 ) h (H 2 O) i
where ‘A’ is selected from NH 4 + , H 3 O + or combinations thereof, m varies from 0.001 to 2; ‘n’ 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 0.4 to 3; ‘z’ is a number which satisfies the sum of the valency of the cationic species present in the material; ‘h’ varies from 0 to m; and ‘i’ varies from 0 to m; 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 (%)

6.3
w

3.6
vs

3.12
vs

2.74
m

2.38
w

the method comprising:
a. forming a reaction mixture containing NH 4 + , H 3 O + or combinations thereof, and sources of M and W;
b. reacting the mixture at a temperature of from about 90° C. and to about 350° C. in an autogenous environment to form a reaction product;
c. recovering the reaction product; and
d. drying the recovered product at a temperature from about 100° C. to about 350° C. for about 30 minutes to about 48 hours to generate the poorly crystalline transition metal tungstate material.

7. The method of claim 6 further comprising removing at least some of the NH 4 + , H 3 O + or combination thereof to form an intermediate before reacting the mixture at a temperature from about 90° C. to about 350° C. in an autogenous environment.

8. The method of claim 6 wherein the reacting is conducted 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 adding a binder to the poorly crystalline transition metal tungstate 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 6 further comprising decomposing the poorly crystalline transition metal tungstate material by sulfidation to form 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 poorly crystalline transition metal tungstate material having the formula:
A m M(OH) n (W) y O z .(NH 3 ) h (H 2 O) i
where ‘A’ is selected from NH 4 + , H 3 O + or combinations thereof, m varies from 0.001 to 2; ‘n’ 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 0.4 to 3; ‘z’ is a number which satisfies the sum of the valency of the cationic species present in the material; ‘h’ varies from 0 to m; and ‘i’ varies from 0 to m; 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 (%)

6.3
w

3.6
vs

3.12
vs

2.74
m

2.38
 w.

Assignees

• Uop Llc

Inventors

• Miller Stuart R
• Koster Susan C

Classifications

• B01J27/049 Primary

  with iron group metals or platinum group metals · CPC title

• B01J23/888

  Tungsten · CPC title

• B01J37/20

  Sulfiding · CPC title

• B01J37/033

  Using Hydrolysis · 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