Crystalline transition metal molybdotungstate

Patent metadata

Field	Value
Publication number	US-2017165652-A1
Application number	US-201615377734-A
Country	US
Kind code	A1
Filing date	Dec 13, 2016
Priority date	Dec 15, 2015
Publication date	Jun 15, 2017
Grant date	—

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

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

Assignees

• Uop Llc

Inventors

• Miller Stuart
• Collins Laura

Classifications

• B01J27/19

  Molybdenum · CPC title

• B01J21/04

  Alumina · CPC title

• C10G47/04 Primary

  Oxides · CPC title

• C10G2300/202

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

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title