Poorly crystalline transition metal molybdotungstate

Patent metadata

Field	Value
Publication number	US-2020001282-A1
Application number	US-201916388357-A
Country	US
Kind code	A1
Filing date	Apr 18, 2019
Priority date	Jun 29, 2018
Publication date	Jan 2, 2020
Grant date	—

Abstract

A hydroprocessing catalyst or catalyst precursor has been developed. The catalyst is a poorly crystalline transition metal molybdotungstate material or a metal sulfide decomposition product thereof. The hydroprocessing using the crystalline ammonia transition metal molybdotungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

First claim

1 . A poorly crystalline transition metal molybdotungstate material having the formula:
A m M(OH) n (Mo) x (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; ‘x’ varies from 0.001 to 2; ‘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 (%)

6.5
w

3.75
vs

3.3
vs

2.73
m

2.45
w

1.91
w

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

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

6 . A method of making a poorly crystalline transition metal molybdotungstate material having the formula:
A m M(OH) n (Mo) x (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; ‘x’ varies from 0.001 to 2; ‘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 (%)

6.5
w

3.75
vs

3.3
vs

2.73
m

2.45
w

1.91
w

the method comprising:
b. forming a reaction mixture containing NH 4 + , H 3 O + or combinations thereof, and sources of M, W, and Mo;
c. reacting the mixture from about 90° C. to about 350° C. in an autogenous environment to form a reaction product;
d. recovering the reaction product; and
e. 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 molybdotungstate material.

7 . The method of claim 6 further comprising removing at least some of the NH 4 + , H 3 O + , or a 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 for a period 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 molybdotungstate 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 transition metal molybdotungstate 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 molybdotungstate material having the formula:
A m M(OH) n (Mo) x (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; ‘x’ varies from 0.001 to 2; ‘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 (%)

Assignees

• Uop Llc

Inventors

• Miller Stuart R
• Koster Susan C

Classifications

• C10G45/08 Primary

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

• B01J23/8885

  containing also molybdenum · CPC title

• B01J37/031

  Precipitation · CPC title

• B01J23/007

  Mixed salts · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title