Crystalline transition metal molybdotungstate

Patent metadata

Field	Value
Publication number	US-10046315-B2
Application number	US-201615377734-A
Country	US
Kind code	B2
Filing date	Dec 13, 2016
Priority date	Dec 15, 2015
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

A hydroprocessing catalyst has been developed. The catalyst is a unique transition metal tungstate material. The hydroprocessing using the crystalline transition metal molybdotungstate material 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:
(NH 4 ) a MMo x W y O z
where ‘a’ varies from 0.1 to 3; ‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn, and mixtures thereof; ‘x’ ranges from 0.1 to 5; ‘y’ ranges from 1 to 10; the sum of (x+y) must be ≤10.1 and z is a number which satisfies the sum of the valences of a, M, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

TABLE A

d(Å)
I0/I %

9.67-9.49
vs

9.09-8.94
m

8.18-8.13
m

8.22-10.91
w

5.05-5.0
m

4.96-4.91
m

4.80-4.76
m

4.51-4.47
w

4.09-4.05
w

3.84-3.81
w

3.74-3.68
m

3.60-3.55
w.

2. The crystalline transition metal molybdotungstate material of claim 1 wherein the crystalline 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 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.

7. A method of making a crystalline transition metal molybdotungstate material having the formula:
(NH 4 ) a MMo x W y O z
where ‘a’ varies from 0.1 to 3; ‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn, and mixtures thereof; ‘x’ ranges from 0.1 to 5; ‘y’ ranges from 1 to 10; the sum of (x+y) must be ≤10.1 and z is a number which satisfies the sum of the valences of a, M, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

TABLE A

d(Å)
I0/I %

9.67-9.49
vs

9.09-8.94
m

8.18-8.13
m

8.22-10.91
w

5.05-5.0
m

4.96-4.91
m

4.80-4.76
m

4.51-4.47
w

4.09-4.05
w

3.84-3.81
w

3.74-3.68
m

3.60-3.55
w

the method comprising:
(a) forming a reaction mixture containing NH 3 , H 2 O, and sources of M, Mo and W;
(b) adjusting the pH of the reaction mixture to a pH of from around 8.5 to about 10;
(c) heating the reaction mixture at temperatures between about 30° C. to about 100° C. until the resultant pH is between about 8 and about 9; and
(d) recovering the crystalline transition metal molybdotungstate material.

8. The method of claim 7 wherein the reacting is conducted at a temperature of from 30° C. to about 130° C. for a period of time from about 30 minutes to 14 days.

9. The method of claim 7 wherein the recovering is by filtration, centrifugation or drying.

10. The method of claim 7 further comprising adding a binder to the recovered crystalline transition metal molybdotungstate material.

11. The method of claim 7 wherein the binder is selected from the group consisting of aluminas, silicas, and alumina-silicas.

12. The method of claim 7 further comprising sulfiding the recovered crystalline transition metal molybdotungstate material.

13. A conversion process comprising contacting a feed with a catalyst at conversion conditions to give at least one product, the catalyst comprising a crystalline transition metal molybdotungstate material having the formula:
(NH 4 ) a MMo x W y O z
where ‘a’ varies from 0.1 to 3; ‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn, and mixtures thereof; ‘x’ ranges from 0.1 to 5; ‘y’ ranges from 1 to 10; the sum of (x+y) must be ≤10.1 and z is a number which satisfies the sum of the valences of a, M, x and y; the material having a unique x-ray powder diffraction pattern showing peaks at the d-spacings listed in Table A:

TABLE A

d(Å)
I0/I %

9.67-9.49
vs

9.09-8.94
m

Assignees

• Uop Llc

Inventors

• Miller Stuart
• Collins Laura

Classifications

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title

• B01J37/0009

  Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst · CPC title

• B01J37/20

  Sulfiding · CPC title

• C10G45/08

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• C10G47/04 Primary

  Oxides · CPC title