# US 10,118,161 B2 · Catalyst and process for hydroconversion of a heavy feedstock

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- Number: US 10,118,161 B2
- Document ID: US10118161B2
- Status: Granted
- Kind: B2
- Application number: 15/156,485
- Filed: 2016-05-17
- Published: 2016-09-08
- Granted: 2018-11-06
- Earliest claimed: 2012-05-21
- Assignees: Shell Oil Company
- Applicants: Shell Oil Company
- Inventors: John George Kester; David Andrew Komar; David Edward Sherwood
- Web page: https://patentgrep.com/patent/US10118161B2

## CPC

- B01J 27/19: Molybdenum
- B01J 23/883: and nickel
- B01J 27/199: with chromium, molybdenum, tungsten or polonium
- B01J 35/45: Nanoparticles
- B01J 35/50: characterised by their shape or configuration
- 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 37/0036: {Grinding}
- B01J 37/0201: {Impregnation}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- 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
- C10G 49/04: containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
- C10G 65/00: Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G 65/12: including cracking steps and other hydrotreatment steps
- C10G 2300/1077: Vacuum residues
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- 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 hydroconversion catalyst comprising a Group VIB metal component, a Group VIII metal component and a carrier material is disclosed wherein the catalyst has a total pore volume of 0.5 to 0.9 cc/g; and a pore volume distribution such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å and greater than 5% of the total pore volume is in pores of diameter greater than 210 Å.

## Claims

### Claim 1

A hydroprocessing catalyst for treating heavy hydrocarbon feedstocks, wherein said catalyst comprises: a calcined particle comprising a co-mulled mixture made by co-mulling inorganic oxide powder or powders, solution or solutions containing molybdenum and Group VIII metals and optionally water, acid and flocculating agent, and then forming said co-mulled mixture into a particle that is calcined to thereby provide said calcined particle, said calcined particles having: a total pore volume of 0.5 to 0.9 cc/g; and a pore volume distribution such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å and greater than 5% of the total pore volume in pores of diameter greater than 210 Å.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein said calcined particle has a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall.

### Claim 3 (depends on 1)

The catalyst of claim 1, wherein said inorganic oxide material is selected from the group consisting of alumina, silica and alumina-silica.

### Claim 4 (depends on 1)

The catalyst of claim 1, wherein said calcined mixture has a molybdenum content in the range of from 1 weight percent to 24 weight percent with the weight percent being based upon the molybdenum as MoO3 and the total weight of the calcined mixture, a nickel content in the range of from 0.2 weight percent to 6 weight percent based on the nickel as NiO and the total weight of the calcined mixture, and a phosphorous content in the range from 0 weight percent to 6 weight percent, with the weight percent being based upon the phosphorous as P2O5 and the total weight of the calcined mixture.

### Claim 5 (depends on 2)

The catalyst of claim 2, wherein each calcined particle has an outer circle diameter of DO, an inner circle diameter of DI, and a height of H; the ratio of DO to DI is between about 1.5 to 3.0; the ratio of H to DO is between about 1 to about 4; and the outer circle diameter DO is between about 0.75 and 2 millimeters.

### Claim 6 (depends on 5)

The catalyst of claim 5, wherein the catalyst has a pore volume distribution such that greater than 75% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, and less than 0.10 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å.

### Claim 7 (depends on 1)

The catalyst of claim 1, wherein said calcined mixture has a molybdenum content in the range of from 7.5 weight percent to 11 weight percent with the weight percent being based upon the molybdenum as MoO3 and the total weight of the calcined mixture, a nickel content in the range of from 1.5 weight percent to 3.5 weight percent based on the nickel as NiO and the total weight of the calcined mixture, and a phosphorous content in the range from 0 weight percent to 2 weight percent, with the weight percent being based upon the phosphorous as P2O5 and the total weight of the calcined mixture.

### Claim 8 (depends on 5)

The catalyst of claim 5, wherein said calcined particle has three truncated lobes with rounded intersections of the lobes.

### Claim 9

A method of making a highly stable heavy hydrocarbon hydrodesulfurization, metal removal and pitch conversion catalyst, wherein said method comprises:
a. forming a co-mulled mixture by co-mulling solid inorganic oxide powders, solution or solutions containing molybdenum and Group VIII metals and optionally water, acid and flocculating agent;
b. extruding said co-mulled mixture into particles to form a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall wherein each lobe; and
c. calcining said particles at temperatures such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å greater than 5% of the total pore volume is in pores of diameter greater than 210 Å; and
d. wherein said calcined particle has a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall, wherein each calcined particle has an outer circle diameter of DO, an inner circle diameter of DI, and a height of H; the ratio of DO to DI is between about 1.5 to 3.0; the ratio of H to DO is between about 1 to about 4; and the outer circle diameter DO is between about 0.75 and 2 millimeters.

### Claim 10 (depends on 9)

The method of claim 9, wherein said calcining step is conducted under a controlled temperature condition in which the calcination temperature is in the range of from about 482° C. (900° F.) to about 787.7° C. (1450° F.) for a calcination time period that is effective to provide said calcined mixture having a desired pore structure.

### Claim 11 (depends on 10)

The method of claim 10, wherein said inorganic oxide material is selected from the group consisting of alumina, silica and alumina-silica.

### Claim 12 (depends on 1)

A process comprising: contacting a heavy hydrocarbon feedstock having a nickel content in the range of from 0.1 ppmw to 250 ppmw, a vanadium content in the range of from 0.3 ppmw to 250 ppmw, and a sulfur content in the range of from 0.5 wt% to 8 wt% with the catalyst of claim 1.