Crystalline transition metal molybdotungstate

Patent metadata

Field	Value
Publication number	US-2019388877-A1
Application number	US-201916388463-A
Country	US
Kind code	A1
Filing date	Apr 18, 2019
Priority date	Jun 26, 2018
Publication date	Dec 26, 2019
Grant date	—

Abstract

A hydroprocessing catalyst has been developed. The catalyst is a crystalline transition metal molybdotungstate material. 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 crystalline transition metal molybdotungstate material having the formula:
(NH 4 ) m M(OH) n Mo x W y O z where ‘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 0.5; ‘y’ varies from 0.4 to 1.75; and ‘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 (%)

10.45
vs

9.79
m

8.05
w

6.97
w

5.83
m

5.03
m

4.96
m

4.87
m

4.49
m

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 zinc.

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

6 . A method of making a crystalline transition metal molybdotungstate material having the formula:
(NH 4 ) m M(OH) n Mo x W y O z where ‘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 0.5; ‘y’ varies from 0.4 to 1.75; and ‘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 (%)

10.45
vs

9.79
m

8.05
w

6.97
w

5.83
m

5.03
m

4.96
m

4.87
m

4.49
m

the method comprising:
a. forming a reaction mixture containing H 2 O, sources of NH 3 , M, W, and Mo;
b. reacting the reaction mixture at a temperature from about 60° C. to about 120° C.;
c. recovering the crystalline transition metal molybdotungstate material.

7 . The method of claim 6 further comprising removing at least some of the H 2 O, NH 3 , or a combination thereof to form an intermediate before reacting the reaction mixture.

8 . The method of claim 6 wherein the reacting is conducted at a temperature of from 60° C. to about 120° C. for a period of time of 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 crystalline transition metal molybdotungstate 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 crystalline transition metal molybdotungstate 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 crystalline transition metal molybdotungstate 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 crystalline transition metal molybdotungstate material having the formula:
(NH 4 ) m M(OH) n Mo x W y O z where ‘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 0.5; ‘y’ varies from 0.4 to 1.75; and ‘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

Assignees

• Uop Llc

Inventors

• Miller Stuart R
• Koster Susan C

Classifications

• C01P2002/77

  by unit-cell parameters, atom positions or structure diagrams · CPC title

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title

• C01P2002/54

  one element only · CPC title

• C01P2002/52

  containing elements as dopants · CPC title

• C01G53/40

  Complex oxides containing nickel and at least one other metal element · CPC title