# US 10,767,120 B2 · Method of operating an ebullated bed process to reduce sediment yield

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- Number: US 10,767,120 B2
- Document ID: US10767120B2
- Status: Granted
- Kind: B2
- Application number: 15/495,082
- Filed: 2017-04-24
- Published: 2017-10-26
- Granted: 2020-09-08
- Earliest claimed: 2016-04-25
- Assignees: Shell Oil Company
- Applicants: Shell Oil Company
- Inventors: Josiane Marie-Rose Ginestra
- Web page: https://patentgrep.com/patent/US10767120B2

## CPC

- C10G 47/26: suspended in the oil, e.g. slurries
- B01J 23/883: and nickel
- B01J 27/19: Molybdenum
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/66: Pore distribution
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C10G 47/24: with moving solid particles
- C10G 65/00: Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- B01J 35/50: characterised by their shape or configuration
- B01J 35/55: Cylinders or rings
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/208: Sediments, e.g. bottom sediment and water or BSW
- C10G 2300/70: Catalyst aspects
- 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
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

An improved method of operating a conventional ebullated bed process for the hydroconversion of heavy hydrocarbon feedstocks so as to provide for low or reduced sediment content in the conversion product without the loss of hydrodesulfurization function.

## Claims

### Claim 1

A method of operating an ebullated bed process for the hydroconversion of a heavy hydrocarbon feedstock, wherein said method comprises:
providing an ebullated bed reactor system, comprising an ebullated bed reactor vessel that defines a reactor volume within which is an ebullated bed reaction zone defined by a catalyst bed comprising first shaped hydroprocessing catalyst particles having a first geometry providing for a first ratio of the cross section perimeter-to-cross sectional area that is less than 5 mm−1, and wherein said reactor volume further includes an upper zone above said ebullated bed reaction zone and a lower zone below said ebullated bed reaction zone;
introducing said heavy hydrocarbon feedstock into said ebullated bed reaction zone, which is operated under hydroconversion reaction conditions;
removing a portion of said first shaped hydroprocessing catalyst particles from said catalyst bed at a removal rate in the range upwardly to 5% of the total weight of catalyst inventory within said reactor volume per day of operation;
replacing said first shaped hydroprocessing catalyst particles removed from said catalyst bed by adding to said catalyst bed an incremental amount of a second shaped hydroprocessing catalyst particles at an addition rate in the range upwardly to 5% of the total weight of catalyst inventory within said reactor volume per day of operation, wherein said second shaped hydroprocessing catalyst particles have a second geometry that is polylobal and provides for a second ratio of the cross section perimeter-to-cross sectional area that is at least 5 mm−1 and less than 8 mm−1 and a cross sectional area-to-particle volume in the range of from 5 mm−1 to 15 mm−1; and
yielding from said reactor volume a heavy hydrocarbon conversion product having a reduced sediment content.

### Claim 2 (depends on 1)

The method of claim 1, wherein said first shaped hydroprocessing catalyst particles comprise an inorganic oxide powder in an amount in the range of from about 75 wt. % to 96 wt. %, a molybdenum compound in an amount in the range of from 3 wt. % to 15 wt. %, and a nickel compound in an amount in the range of from 0.5 wt. % to 6 wt. %, wherein each wt. % is based on the total weight of said first shaped hydroprocessing catalyst particle and the metal as an oxide regardless of its actual form, wherein said second shaped hydroprocessing catalyst particles comprise an inorganic oxide powder in an amount in the range of from about 75 wt. % to 96 wt. %, a molybdenum compound in an amount in the range of from 3 wt. % to 15 wt. %, and a nickel compound in an amount in the range of from 0.5 wt. % to 6 wt. %, wherein each wt. % is based on the total weight of said second shaped hydroprocessing catalyst particle and the metal as an oxide regardless of its actual form.

### Claim 3 (depends on 2)

The method of claim 2, wherein said second ratio is at least 5.5 mm−1 and less than 8 mm−1.

### Claim 4 (depends on 2)

The method of claim 2, wherein said second ratio is at least 6 mm−1 and less than 8 mm−1.

### Claim 5 (depends on 4)

The method of claim 4, wherein said hydroconversion reaction conditions include a contacting temperature in the range of from 316° C. (600° F.) to 538° C. (1000° F.), a contacting pressure in the range of from 500 psia to 6,000 psia, a hydrogen-to-oil ratio in the range of from 500 scf/bbl to 10,000 scf/bbl, and liquid hourly space velocity (LHSV) in the range of from 0.1 hr−1 to 5 hr−1.

### Claim 6

A method of operating an ebullated bed process for the hydroconversion of a heavy hydrocarbon feedstock, wherein said method comprises:
providing an ebullated bed reactor system designed for the use of first shaped hydroprocessing catalyst particles having a first geometry providing for a first ratio of the cross section perimeter-to-cross sectional area that is less than 5 mm−1 in a catalyst bed defining an ebullated bed reaction zone contained within a reactor volume defined by an ebullated bed reactor vessel, wherein said reactor volume includes an upper zone above said ebullated bed reaction zone and a lower zone below said ebullated bed reaction zone;
introducing said heavy hydrocarbon feedstock into said ebullated bed reaction zone, which is operated under hydroconversion reaction conditions;
adding said first shaped hydroprocessing catalyst particles to said catalyst bed at a first incremental addition rate;
introducing into said catalyst bed of said reactor volume at a second incremental addition rate second shaped hydroprocessing catalyst particles having a second geometry that is polylobal and provides for a second ratio of the cross section perimeter-to-cross sectional area that is at least 5 mm−1 and less than 8 mm−1 and a cross sectional area-to-particle volume in the range of from 5 mm−1 to 15 mm−1 to thereby form said ebullated bed reaction zone;
operating said ebullated bed reactor system with a desired ratio of said first shaped hydroprocessing catalyst particles and said second shaped hydroprocessing catalyst particles within said ebullated bed reaction zone by:
adjusting said first incremental addition rate and said second incremental addition rate to maintain the desired ratio while removing a portion of said catalyst bed at a rate to maintain the desired ratio; and
yielding from said reactor volume a heavy hydrocarbon conversion product having a low sediment content.

### Claim 7 (depends on 6)

The method of claim 6, wherein said first shaped hydroprocessing catalyst particles comprise an inorganic oxide powder in an amount in the range of from about 75 wt. % to 96 wt. %, a molybdenum compound in an amount in the range of from 3 wt. % to 15 wt. %, and a nickel compound in an amount in the range of from 0.5 wt. % to 6 wt. %, wherein each wt. % is based on the total weight of said first shaped hydroprocessing catalyst particle and the metal as an oxide regardless of its actual form, wherein said second shaped hydroprocessing catalyst particles comprise an inorganic oxide powder in an amount in the range of from about 75 wt. % to 96 wt. %, a molybdenum compound in an amount in the range of from 3 wt. % to 15 wt. %, and a nickel compound in an amount in the range of from 0.5 wt. % to 6 wt. %, wherein each wt. % is based on the total weight of said second shaped hydroprocessing catalyst particle and the metal as an oxide regardless of its actual form.

### Claim 8 (depends on 7)

The method of claim 7, wherein said second ratio is at least 5.5 mm−1 and less than 8 mm−1.

### Claim 9 (depends on 7)

The method of claim 7, wherein said second ratio is at least 6 mm−1 and less than 8 mm−1.

### Claim 10 (depends on 9)

The method of claim 9, wherein said hydroconversion reaction conditions include a contacting temperature in the range of from 316° C. (600° F.) to 538° C. (1000° F.), a contacting pressure in the range of from 500 psia to 6,000 psia, a hydrogen-to-oil ratio in the range of from 500 scf/bbl to 10,000 scf/bbl, and liquid hourly space velocity (LHSV) in the range of from 0.1 hr−1 to 5 hr−1.