Crystalline transition metal oxy-hydroxide molybdotungstate

Patent metadata

Field	Value
Publication number	US-2017165648-A1
Application number	US-201615373432-A
Country	US
Kind code	A1
Filing date	Dec 8, 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 crystalline transition metal oxy-hydroxide molybdotungstate material. The hydroprocessing using the crystalline ammonia transition metal oxy-hydroxide molybdotungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

First claim

1 . A crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
(NH 4 ) A M(OH) B MO X W Y O Z
where “a” varies from 0.1 to 10, ‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5; ‘y’ varies from 0.01 to 0.4; where the sum of (x+y) must be ≦1.501; ‘z’ is a number which satisfies the sum of the valency of a, M, b, 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)
I/I 0 %

10.0-9.53
m

7.72-7.76
s

7.49-7.25
m

5.27-5.12
m

 5.1-5.04
m

4.92-4.87
w

3.97-3.91
m

3.69-3.64
s

3.52-3.48
m

3.35-3.32
m

3.31-3.29
m

3.12-3.09
w

  3-2.97
m

2.76-2.73
m

2 . The crystalline transition metal oxy-hydroxide molybdotungstate material of claim 1 wherein the crystalline transition metal oxy-hydroxide 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 oxy-hydroxide 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 oxy-hydroxide molybdotungstate material of claim 1 wherein the crystalline transition metal oxy-hydroxide molybdotungstate material is sulfided.

5 . A method of making a crystalline transition metal oxy-hydroxide molybdotungstate material having the formula:
(NH 4 ) A M(OH) B MO X W Y O Z
where “a” varies from 0.1 to 10, ‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5; ‘y’ varies from 0.01 to 0.4; where the sum of (x+y) must be ≦1.501; ‘z’ is a number which satisfies the sum of the valency of a, M, b, 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)
I/I 0 %

10.0-9.53
m

7.72-7.76
s

7.49-7.25
m

5.27-5.12
m

 5.1-5.04
m

4.92-4.87
w

3.97-3.91
m

3.69-3.64
s

3.52-3.48
m

3.35-3.32
m

3.31-3.29
m

3.12-3.09
w

  3-2.97
m

2.76-2.73
m

the method comprising:
(a) forming a reaction mixture containing NH 3 , H 2 O, and sources of M, W, and Mo;
(b) adjusting the pH of the reaction mixture to a pH of from about 8.5 to about 10;
(c) reacting the reaction mixture between about 100° C. and about 220° C. in an autogenous environment; and
(d) recovering the crystalline transition metal oxy-hydroxide molybdotungstate material.

6 . The method of claim 5 wherein the reacting is conducted at a temperature of from 10° C. to about 200° C. for a period of time from about 30 minutes to 14 days.

7 . The method of claim 5 wherein the recovering is by filtration or centrifugation.

8 . The method of claim 5 further comprising adding a binder to the recovered crystalline transition metal oxy-hydroxide molybdotungstate material.

9 . The method of claim 8 wherein the binder is selected from the group consisting of aluminas, silicas, and alumina-silicas.

10 . The method of claim 5 further comprising sulfiding the recovered crystalline transition metal oxy-hydroxide molybdotungstate material.

11 . 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 oxy-hydroxide molybdotungstate material having the formula:
(NH 4 ) A M(OH) B MO X W Y O Z
where “a” varies from 0.1 to 10, ‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5; ‘y’ varies from 0.01 to 0.4; where the sum of (x+y) must be ≦1.501; ‘z’ is a number which satisfies the sum of the valency of a

Assignees

• Uop Llc

Inventors

• Miller Stuart
• Koster Susan C

Classifications

• B01J23/881

  and iron · CPC title

• B01J23/883

  and nickel · CPC title

• B01J37/10

  in the presence of water, e.g. steam · CPC title

• B01J23/8885

  containing also molybdenum · CPC title

• B01J23/882

  and cobalt · CPC title