HYDROPROCESSING CATALYSTS AND THEIR PRODUCTION

• US 20110294657A1
• Filed: 06/01/2011
• Published: 12/01/2011
• Est. Priority Date: 06/01/2010
• Status: Active Grant

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Venkataraman, Pallassana S., Guzman, Javier, Soled, Stuart L., Miseo, Sabato, Baumgartner, Joseph E., Kennedy, Gordon, Chimenti, Robert J., Levin, Doron, Nistor, Iulian, Kliewer, Chris E.
• Granted Patent: US 8,722,564 B2
• Time in Patent Office: Days
• US Class Current: 502/167
• CPC Class Codes: B01J 2231/60 Reduction reactions, e.g. hydrogenation
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 23/8877 Vanadium, tantalum, niobium or polonium
• CPC Class Codes: B01J 23/888 Tungsten
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/55 Vanadium
• CPC Class Codes: B01J 2523/56 Niobium
• CPC Class Codes: B01J 2523/68 Molybdenum
• CPC Class Codes: B01J 2523/69 Tungsten
• CPC Class Codes: B01J 2523/845 Cobalt
• CPC Class Codes: B01J 2523/847 Nickel
• CPC Class Codes: B01J 2531/64 Molybdenum
• CPC Class Codes: B01J 2531/66 Tungsten
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 2531/847 Nickel
• CPC Class Codes: B01J 31/0237 Amines
• CPC Class Codes: B01J 31/0247 Imides, amides or imidates (R-C=NR(OR))
• CPC Class Codes: B01J 31/04 containing carboxylic acids or their salts B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226
• CPC Class Codes: B01J 35/002 Catalysts characterised by their physical properties
• CPC Class Codes: B01J 35/1014 : 10-100 m2/g
• CPC Class Codes: B01J 35/1019 : 100-500 m2/g
• CPC Class Codes: B01J 35/30 : characterised by their physical properties
• CPC Class Codes: B01J 35/613 : 10-100 m2/g
• CPC Class Codes: B01J 35/615 : 100-500 m2/g
• CPC Class Codes: B01J 37/0203 : the impregnation liquid containing organic compounds
• CPC Class Codes: B01J 37/08 : Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/20 : Sulfiding
• CPC Class Codes: C10G 2300/1074 : Vacuum distillates
• CPC Class Codes: C10G 2300/202 : Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/703 : Activation
• CPC Class Codes: C10G 45/06 : containing nickel or cobalt metal, or compounds thereof
• CPC Class Codes: C10G 45/08 : in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C11B 3/02 : by chemical reaction C11B3/003 takes precedence

Abstract

Described herein is a catalyst precursor composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (i) a first organic compound containing at least one amine group and at least 10 carbon atoms or (ii) a second organic compound containing at least one carboxylic acid group and at least 10 carbon atoms, but not both, wherein the reaction product contains additional unsaturated carbon atoms, relative to the first or second organic compound, wherein the metals of the catalyst precursor composition are arranged in a crystal lattice, and wherein the reaction product is not located within the crystal lattice. A process for preparing the catalyst precursor composition is also described, as is sulfiding the catalyst precursor composition to form a hydroprocessing catalyst.

Claims

1. A catalyst precursor composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, and a reaction product formed from (i) a first organic compound containing at least one amine group and at least 10 carbon atoms or (ii) a second organic compound containing at least one carboxylic acid group and at least 10 carbon atoms, but not both (i) and (ii), wherein the reaction product contains additional unsaturated carbon atoms, relative to (i) the first organic compound or (ii) the second organic compound, wherein the metals of the catalyst precursor composition are arranged in a crystal lattice, and wherein the reaction product is not located within the crystal lattice.

2. The catalyst precursor composition of claim 1, wherein said at least one metal from Group 6 is Mo, W, or a combination thereof, and wherein said at least one metal from Groups 8-10 is Co, Ni, or a combination thereof.

3. The catalyst precursor composition of claim 1, wherein said first organic compound comprises a primary monoamine having from 10 to 30 carbon atoms or said second organic compound comprises only one carboxylic acid group and has from 10 to 30 carbon atoms.

4. A bulk mixed metal catalyst precursor composition produced by heating the composition of claim 1 to a temperature from about 195°

C. to about 250°

C. for a time sufficient for the first or second organic compounds to form a reaction product in situ that contains unsaturated carbon atoms not present in the first or second organic compounds.

5. A bulk mixed metal hydroprocessing catalyst composition produced by sulfiding the catalyst precursor composition of claim 4.

16. The catalyst precursor composition of claim 1, wherein one or more of the following are satisfied:

the catalyst precursor composition exhibits a content of unsaturated carbon atoms, as measured according to peak area comparisons using ¹³C NMR techniques, of at least 29%;

the catalyst precursor composition exhibits an increase in content of unsaturated carbon atoms, as measured according to peak area comparisons using ¹³C NMR techniques, of at least about 17%, compared to a collective content of unsaturated carbon atoms present in the first or second organic compound;

the catalyst precursor composition exhibits a ratio of unsaturated carbon atoms to aromatic carbon atoms, as measured according to peak area ratios using infrared spectroscopic techniques of a deconvoluted peak centered from about 1700 cm<sup>−

1</sup> to about 1730 cm<sup>−

1</sup>, compared to a deconvoluted peak centered from about 1380 cm<sup>−

1</sup> to about 1450 cm<sup>−

1</sup>, of at least 0.9; and

the catalyst precursor composition exhibits a ratio of unsaturated carbon atoms to aromatic carbon atoms, as measured according to peak area ratios using infrared spectroscopic techniques of a deconvoluted peak centered from about 1700 cm<sup>−

1</sup> to about 1730 cm<sup>−

1</sup>, compared to a deconvoluted peak centered from about 1380 cm<sup>−

1</sup> to about 1450 cm<sup>−

1</sup>, of up to 15.

17. The bulk mixed metal catalyst precursor of claim 5, wherein one or more of the following are satisfied:

the sulfided bulk mixed metal catalyst precursor exhibits a layered structure comprising a plurality of stacked layers of sulfided Group 6 metal(s), such that the average number of stacked layers is from about 1.5 to about 3.5;

the sulfided bulk mixed metal catalyst precursor exhibits a layered structure comprising a plurality of stacked layers of sulfided Group 6 metal(s), such that the average number of stacked layers is at least about 0.8 stacked layers less than an identical sulfided bulk mixed metal catalyst precursor that has not been treated using first or second organic compounds;

upon exposure of the sulfided bulk mixed metal catalyst precursor to a vacuum gasoil feedstock under hydroprocessing conditions, the sulfided bulk mixed metal catalyst precursor exhibits a hydrodenitrogenation RMA of at least 57% greater than a sulfided catalyst composition that has not been treated using first or second organic compounds;

upon exposure of the sulfided bulk mixed metal catalyst precursor to a vacuum gasoil feedstock under hydroprocessing conditions, the sulfided bulk mixed metal catalyst precursor exhibits a hydrodenitrogenation RMA of up to 500% greater than a sulfided catalyst composition that has not been treated using first or second organic compounds;

upon exposure of the sulfided bulk mixed metal catalyst precursor to a vacuum gasoil feedstock under hydroprocessing conditions, the sulfided bulk mixed metal catalyst precursor exhibits a hydrodenitrogenation RMA at least 30% greater than a sulfided catalyst composition that has been treated with only a single organic compound having less than 10 carbon atoms; and

upon exposure of the sulfided bulk mixed metal catalyst precursor to a vacuum gasoil feedstock under hydroprocessing conditions, the sulfided bulk mixed metal catalyst precursor exhibits a hydrodenitrogenation RMA up to 500% greater than a sulfided catalyst composition that has been treated with only a single organic compound having less than 10 carbon atoms.

6. A process for producing a catalyst precursor composition containing in situ formed unsaturated carbon atoms, the process comprising:

(a) treating a catalyst precursor composition comprising at least one metal from Group 6 of the Periodic Table of the Elements, at least one metal from Groups 8-10 of the Periodic Table of the Elements, with a first organic compound containing at least one amine group and at least 10 carbons or a second organic compound containing at least one carboxylic acid group and at least 10 carbons, to form an organically treated precursor catalyst composition; and

(b) heating said organically treated precursor catalyst composition at a temperature from about 195°

C. to about 250°

C. for a time sufficient for the first or second organic compounds to react to form additional in situ unsaturated carbon atoms not present in the first or second organic compounds, but not for so long that more than 50% by weight of the first or second organic compound is volatilized,

thereby forming a catalyst precursor composition containing in situ formed unsaturated carbon atoms.

7. The process of claim 6, wherein said at least one metal from Group 6 is Mo, W, or a combination thereof, and wherein said at least one metal from Groups 8-10 is Co, Ni, or a combination thereof.

8. The process of claim 6, wherein said first organic compound comprises a primary monoamine having from 10 to 30 carbon atoms or said second organic compound comprises only one carboxylic acid group and has from 10 to 30 carbon atoms.

9. The process of claim 6, wherein the catalyst precursor composition containing in situ formed unsaturated carbon atoms is a bulk metal hydroprocessing catalyst precursor composition consisting essentially of the reaction product, an oxide form of the at least one metal from Group 6, an oxide form of the at least one metal from Groups 8-10, and optionally about 20 wt % or less of a binder.

10. A process for producing a sulfided hydroprocessing catalyst composition, comprising sulfiding the catalyst precursor composition containing in situ formed unsaturated carbon atoms made according to the process of claim 6 under conditions sufficient to produce the sulfided hydroprocessing catalyst composition.

11. A process for producing a sulfided hydroprocessing catalyst composition, comprising sulfiding the catalyst precursor composition containing in situ formed unsaturated carbon atoms made according to the process of claim 9 under conditions sufficient to produce the sulfided hydroprocessing catalyst composition.

12. A catalyst precursor composition containing in situ formed unsaturated carbon atoms made according to the process of claim 6.

13. A sulfided hydroprocessing catalyst composition made according to the process of claim 11.

14. The process of claim 6, wherein one or more of the following are satisfied:

the catalyst precursor composition exhibits a content of unsaturated carbon atoms, as measured according to peak area comparisons using ¹³C NMR techniques, of at least 29%;

the catalyst precursor composition exhibits an increase in content of unsaturated carbon atoms, as measured according to peak area comparisons using ¹³C NMR techniques, of at least about 17%, compared to a collective content of unsaturated carbon atoms present in the first or second organic compound;

the catalyst precursor composition exhibits a ratio of unsaturated carbon atoms to aromatic carbon atoms, as measured according to peak area ratios using infrared spectroscopic techniques of a deconvoluted peak centered from about 1700 cm<sup>−

1</sup> to about 1730 cm<sup>−

1</sup>, compared to a deconvoluted peak centered from about 1380 cm<sup>−

1</sup> to about 1450 cm<sup>−

1</sup>, of at least 0.9; and

the catalyst precursor composition exhibits a ratio of unsaturated carbon atoms to aromatic carbon atoms, as measured according to peak area ratios using infrared spectroscopic techniques of a deconvoluted peak centered from about 1700 cm<sup>−

1</sup> to about 1730 cm<sup>−

1</sup>, compared to a deconvoluted peak centered from about 1380 cm<sup>−

1</sup> to about 1450 cm<sup>−

1</sup>, of up to 15.

15. A process for producing a sulfided hydroprocessing catalyst composition, comprising sulfiding the catalyst precursor composition made according to the process of claim 6 under conditions sufficient to produce the sulfided hydroprocessing catalyst composition, wherein one or more of the following are satisfied:

the sulfided hydroprocessing catalyst composition exhibits a layered structure comprising a plurality of stacked layers of sulfided Group 6 metal(s), such that the average number of stacked layers is from about 1.5 to about 3.5;

the sulfided hydroprocessing catalyst composition exhibits a layered structure comprising a plurality of stacked layers of sulfided Group 6 metal(s), such that the average number of stacked layers is at least about 0.8 stacked layers less than an identical sulfided hydroprocessing catalyst composition that has not been treated using first or second organic compounds;

upon exposure of the sulfided hydroprocessing catalyst composition to a vacuum gasoil feedstock under hydroprocessing conditions, the sulfided hydroprocessing catalyst composition exhibits a hydrodenitrogenation RMA of at least 57% greater than a sulfided catalyst composition that has not been treated using first or second organic compounds;

upon exposure of the sulfided hydroprocessing catalyst composition to a vacuum gasoil feedstock under hydroprocessing conditions, the sulfided hydroprocessing catalyst composition exhibits a hydrodenitrogenation RMA of up to 500% greater than a sulfided catalyst composition that has not been treated using first or second organic compounds;

upon exposure of the sulfided hydroprocessing catalyst composition to a vacuum gasoil feedstock under hydroprocessing conditions, the sulfided hydroprocessing catalyst composition exhibits a hydrodenitrogenation RMA at least 30% greater than a sulfided catalyst composition that has been treated with only a single organic compound having less than 10 carbon atoms; and

upon exposure of the sulfided hydroprocessing catalyst composition to a vacuum gasoil feedstock under hydroprocessing conditions, the sulfided hydroprocessing catalyst composition exhibits a hydrodenitrogenation RMA up to 500% greater than a sulfided catalyst composition that has been treated with only a single organic compound having less than 10 carbon atoms.