US 2024/0189801 A1 · TETRAMETALLIC BULK HYDROPROCESSING CATALYSTS

Abstract

Bulk catalysts comprised of nickel, molybdenum, tungsten and titanium and methods for synthesizing bulk catalysts are provided. The catalysts are useful for hydroprocessing, particularly hydrodesulfurization and hydrodenitrogenation, of hydrocarbon feedstocks.

Claims41

Dependent claims

-28. (canceled)

A method for preparing a bulk catalyst precursor having a formula of

Av[Ni(OH)x(L)py]z[MomW1-mO4][Ti(OH)nO2-n/2]w
wherein:
(i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, phosphonium cation, or a combination thereof;
(ii) L is an organic compound-based component;
and
(iii) 0≤y≤−2/p;
0≤x<2;
0≤v<2;
0<z;
0<m<1;
0<<4;
0.1<w/(z+1)<10;
the method comprising:
(a) combining in a reaction mixture;
(i) a Ni-containing precursor;
(ii) a Mo-containing precursor;
(iii) a W-containing precursor;
(iv) a Ti-containing precursor;
(v) an organic compound-based component;
and
(vi) a protic liquid;
and
(b) reacting the mixture under conditions sufficient to cause precipitation of the bulk catalyst precursor;
with the steps to prepare the bulk catalyst precursor carried out at a temperature of no more than 200° C.;
and
recovering a bulk catalyst precursor defined by a region of a quaternary phase diagram wherein the region is defined by ten points ABCDEFGHIJ and wherein the ten points, on a metal oxide basis (wt. %), are:
A (Ni=39, Mo=1, W=41, Ti=20), B (Ni=39, Mo=1, W=72, Ti=20), C (Ni=9, Mo=17, W=54, Ti=20), D (Ni=31, Mo=25, W=24, Ti=20), E (Ni=40, Mo=14, W=26, Ti=20), F (Ni=34, Mo=1, W=36, Ti=30), G (Ni=7, Mo=1, W=63, Ti=30), H (Ni=8, Mo=15, W=48, Ti=30), I (Ni=27, Mo=22, W=21, Ti=30), and J (Ni=35, Mo=12, W=23, Ti=30).

24 more elements

A method for preparing a bulk catalyst precursor having a formula of

Av[Ni(OH)x(L)py]z[MomW1-mO4][Ti(OH)nO2-n/2]w
wherein:
(i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, phosphonium cation, or a combination thereof;
(ii) L is an organic compound-based component;
and
(iii) 0≤y≤−2/p;
0≤x<2;
0≤v<2;
0<z;
0<m<1;
0<<4;
0.1<w/(z+1)<10;
the method comprising:
(a) combining in a reaction mixture;
(i) a Ni-containing precursor;
(ii) a Mo-containing precursor;
(iii) a W-containing precursor;
(iv) an organic compound-based component;
and
(v) a protic liquid;
and
(b) reacting the mixture under conditions sufficient to cause precipitation of an intermediate bulk catalyst precursor;
and
(c) compositing the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor;
wherein the steps to prepare the bulk catalyst precursor are carried out at a temperature of no more than 200° C.;
and
recovering a bulk catalyst precursor defined by a region of a quaternary phase diagram wherein the region is defined by ten points ABCDEFGHIJ and wherein the ten points, on a metal oxide basis (wt. %), are:
A (Ni=39, Mo=1, W=41, Ti=20), B (Ni=39, Mo=1, W=72, Ti=20), C (Ni=9, Mo=17, W=54, Ti=20), D (Ni=31, Mo=25, W=24, Ti=20), E (Ni=40, Mo=14, W=26, Ti=20), F (Ni=34, Mo=1, W=36, Ti=30), G (Ni=7, Mo=1, W=63, Ti=30), H (Ni=8, Mo=15, W=48, Ti=30), I (Ni=27, Mo=22, W=21, Ti=30), and J (Ni=35, Mo=12, W=23, Ti=30).

25 more elements

A method for preparing a bulk catalyst precursor having a formula of

Av[Ni(OH)x(L)py]z[MomW1-mO4][Ti(OH)nO2-n/2]w
wherein:
(i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, phosphonium cation, or a combination thereof;
(ii) L is an organic compound-based component;
and
(iii) 0≤y≤−2/p;
0≤x<2;
0≤v<2;
0<z;
0<m<1;
0<<4;
0.1<w/(z+1)<10;
the method comprising:
(a) combining in a reaction mixture;
(i) a Ni-containing precursor;
(ii) a Mo-containing precursor;
(iii) a W-containing precursor;
(iv) a Ti-containing precursor;
(v) an organic compound-based component;
and
(vi) a protic liquid;
and
(b) reacting the mixture under conditions sufficient to cause precipitation of the bulk catalyst precursor;
with the steps to prepare the bulk catalyst precursor carried out at a temperature of no more than 200° C.;
and
recovering a bulk catalyst precursor is defined by a region of a quaternary phase diagram defined by eight points ABCDEFGH and wherein the eight points, on a metal oxide basis (wt. %), are:
A (Ni=52.5, Mo=3.5, W=14, Ti=30), B (Ni=38.5, Mo=17.5, W=14, Ti=30), C (Ni=21, Mo=17.5, W=31.5, Ti=30), D (Ni=35, Mo=3.5, W=31.5, Ti=30), E (Ni=60, Mo=4, W=16, Ti=20), F (Ni=44, Mo=20, W=16, Ti=20), G (Ni=24, Mo=20, W=36, Ti=20), and H (Ni=40, Mo=4, W=36, Ti=20).

24 more elements

A method for preparing a bulk catalyst precursor having a formula of

Av[Ni(OH)x(L)py]z[MomW1-mO4][Ti(OH)nO2-n/2]w
wherein:
(i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, phosphonium cation, or a combination thereof;
(ii) L is an organic compound-based component;
and
(iii) 0≤y≤−2/p;
0≤x<2;
0≤v<2;
0<z;
0<m<1;
0<<4;
0.1<w/(z+1)<10;
the method comprising:
(a) combining in a reaction mixture;
(i) a Ni-containing precursor;
(ii) a Mo-containing precursor;
(iii) a W-containing precursor;
(iv) an organic compound-based component;
and
(v) a protic liquid;
and
(b) reacting the mixture under conditions sufficient to cause precipitation of an intermediate bulk catalyst precursor;
and
(c) compositing the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor;
wherein the steps to prepare the bulk catalyst precursor are carried out at a temperature of no more than 200° C.;
and
recovering a bulk catalyst precursor defined by a region of a quaternary phase diagram wherein the region is defined by ten points ABCDEFGHIJ and wherein the ten points, on a metal oxide basis (wt. %), are:
A (Ni=39, Mo=1, W=41, Ti=20), B (Ni=39, Mo=1, W=72, Ti=20), C (Ni=9, Mo=17, W=54, Ti=20), D (Ni=31, Mo=25, W=24, Ti=20), E (Ni=40, Mo=14, W=26, Ti=20), F (Ni=34, Mo=1, W=36, Ti=30), G (Ni=7, Mo=1, W=63, Ti=30), H (Ni=8, Mo=15, W=48, Ti=30), I (Ni=27, Mo=22, W=21, Ti=30), and J (Ni=35, Mo=12, W=23, Ti=30).

25 more elements

Dependencies are inferred from the claim text.

Facts

Application

18/344,380Filed 29 Jun 2023

Priority

4 May 2020

Published

13 Jun 2024

Term ends

Not estimatedThe source records don’t support an estimate.

Classification36 codes

B01J 23/8993
Also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36: with chromium, molybdenum or tungsten
B01J 35/613
Surface area: 10-100 m2/g
B01J 21/063
Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof: titanium; Oxides or hydroxides thereof
B01J 23/002
Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00: mixed oxides other than spinels, e.g. perovskite

Family

Application63/019,479Us provisional application · filed 4 May 2020

Application17/190,611Division · filed 3 Mar 2021

Application18/344,380Division

US 11,731,112 B2Related patent

US 12,011,710 B1Related patent

US 2021/0339232 A1Published application

US 2024/0189801 A1This patent

From the US filing history. Foreign family members aren’t listed.

Tetrametallic bulk hydroprocessing catalysts

Life of this patent

Abstract

Claims41

Tetrametallic bulk hydroprocessing catalysts

Life of this patent

Abstract

Claims41