# US 10,118,158 B2 · Process and catalyst for the hydrotreatment of a heavy hydrocarbon feedstock

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- Number: US 10,118,158 B2
- Document ID: US10118158B2
- Status: Granted
- Kind: B2
- Application number: 14/254,130
- Filed: 2014-04-16
- Published: 2014-10-23
- Granted: 2018-11-06
- Earliest claimed: 2013-04-17
- Assignees: Shell Oil Company
- Applicants: Shell Oil Company
- Inventors: John Anthony Smegal
- Web page: https://patentgrep.com/patent/US10118158B2

## CPC

- B01J 23/883: and nickel
- B01J 21/04: Alumina
- B01J 23/85: Chromium, molybdenum or tungsten
- B01J 27/199: with chromium, molybdenum, tungsten or polonium
- B01J 35/615: {100-500 m2/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
- B01J 35/30: characterised by their physical properties
- B01J 35/50: characterised by their shape or configuration
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## Abstract

A method of hydrotreating a heavy hydrocarbon feedstock using a hydrotreating catalyst having specific properties that make it effective in removing nitrogen and sulfur from the feedstock is disclosed. The catalyst is composed of an alumina support particle having a specific pore diameter distribution which is achieved in part, by the use of pseudo-boehmite as the alumina source and specific calcining temperatures. The hydrotreatment catalyst also comprises a Group 6 metal component (e.g., molybdenum) and a Group 10 metal component (e.g., nickel), and optionally, a phosphorus metal component, which are supported by the alumina support particle.

## Claims

### Claim 1

A method of making a catalyst composition useful in the hydrotreatment of a heavy hydrocarbon feedstock, said method comprising the steps of:
providing an alumina support particle comprising gamma alumina, said support having a median pore diameter in the range of from 100 Å to 120 Å, a surface area in the range of from 280 m2/g to 240 m2/g, greater than 70% of the total pore diameter distribution between 90 Å and 130 Å, less than 5 percent of the total pore size distribution is greater than 350 Å, and a total mercury pore volume of less than 0.85 cc/g by mixing a composition comprising high purity pseudo-boehmite powder and water at a weight ratio of pseudo-boehmite-to-water in the range of from 0.1:1 to 10:1, and an acid to form an extrudable paste and extruding said paste to thereby provide a shaped support particle; and heat treating said shaped support particle at a temperature between 676° C. and 788° C.;
contacting said alumina support particle with a catalytic solution, said solution comprising a Group 6 metal component and a Group 10 metal component to thereby provide an impregnated alumina support; and
heat treating said impregnated alumina support to provide said catalyst composition having a median pore diameter in the range of from 120 Å to 150 Å, and wherein said catalyst composition has a total mercury pore volume between 0.3 and 0.6 cc/g.

### Claim 2 (depends on 1)

A method according to claims 1 wherein said catalyst composition exhibits an increase in relative volumetric activity of at least 10% with respect to the kinetic rate constant for a reduction in nitrogen content to 10 ppm as compared to a catalyst comprising and alumina support particle having a surface area of at least 300 m2/g.

### Claim 3 (depends on 2)

A method according to claims 2 wherein the total mercury pore volume of said alumina support particle is less than 0.8 cc/g.

### Claim 4 (depends on 3)

A method according to claim 3, wherein said catalyst composition contains an amount of Group 6 metal in the range of from about 3 to about 30 weight percent, calculated as a trioxide and based on the weight of said catalyst composition.

### Claim 5 (depends on 4)

A method according to claim 4, wherein said catalyst composition contains an amount of Group 10 metal in the range of from about 0.01 to about 10 weight percent, calculated as a monoxide and based on the weight of said catalyst composition.

### Claim 6 (depends on 5)

A method according to claim 5, wherein said catalyst composition further contains a phosphorous component at a concentration in the range of from about 0.01 to about 5 weight percent calculated as phosphorous.

### Claim 7 (depends on 6)

A method according to claim 6, wherein said catalyst composition has a surface area between 120 and 200 m2/g.

### Claim 8

A method of making a catalyst composition useful in the hydrotreatment of a heavy hydrocarbon feedstock, said method comprising the steps of:
forming a shaped support particle comprising high purity pseudo-boehmite powder;
heat treating said shaped support particle at a temperature between 676° C. and 788° C. to achieve a heat treated support particle having a median pore diameter in the range of from 100 Å to 120 Å, a surface area in the range of from 280 m2/g to 240 m2/g, greater than 70% of the total pore diameter distribution between 90 Å and 130 Å, less than 5 percent of the total pore size distribution is greater than 350 Å, and a total mercury pore volume less than 0.85 cc/g; and
contacting said heat treated support particle with a catalytic solution, said solution comprising a Group 6 metal component and a Group 10 metal component to thereby provide an impregnated alumina support having a median pore diameter in the range of from 120 Å to 150 Å and a total mercury pore volume of less than 0.85 cc/g; and
heat treating said impregnated alumina support to provide said catalyst composition having a median pore diameter in the range of from 120 Å to 150 Å, and wherein said catalyst composition has a total mercury pore volume between 0.3 and 0.6 cc/g.

### Claim 9 (depends on 8)

A method according to claims 8 wherein said catalyst composition exhibits an increase in relative volumetric activity of at least 10% with respect to the kinetic rate constant for a reduction in nitrogen content to 10 ppm as compared to a catalyst comprising and alumina support particle having a surface area of at least 300 m2/g.

### Claim 10 (depends on 9)

A method according to claim 9 wherein the total mercury pore volume of the support particle is less than 0.8 cc/g.

### Claim 11

A catalyst composition useful in the hydrotreatment of a heavy hydrocarbon feedstock, wherein said catalyst composition comprises:
an alumina support particle comprising gamma-alumina, wherein said alumina support particle has a median pore diameter in the range of from 100 Å to 120 Å, a surface area in the range of from 280 m2/g to 240 m2/g, greater than 70% of the total pore diameter distribution between 90 Å and 130 Å, less than 5 percent of the total pore size distribution is greater than 350 Å, and a total mercury pore volume less than 0.85 cc/g; and
wherein said alumina support particle is impregnated with a Group 6 metal component and a Group 10 metal component to provide an impregnated alumina support particle having a median pore diameter in the range of from 120 Å to 150 Å; and wherein said catalyst composition exhibits an increase in relative volumetric activity of at least 10% with respect to the kinetic rate constant for a reduction in nitrogen content to 10 ppm as compared to a catalyst comprising an alumina support particle having a surface area of at least 300 m2/g , and wherein said catalyst composition has a total mercury pore volume between 0.3 and 0.6 cc/g.

### Claim 12 (depends on 11)

A catalyst composition according to claim 11 wherein the total mercury pore volume of said support particle is less than 0.8 cc/g.