# US 11,306,263 B1 · Processes for thermal upgrading of heavy oils utilizing disulfide oil

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- Number: US 11,306,263 B1
- Document ID: US11306263B1
- Status: Granted
- Kind: B1
- Application number: 17/167,412
- Filed: 2021-02-04
- Granted: 2022-04-19
- Earliest claimed: 2021-02-04
- Assignees: Saudi Arabian Oil Company
- Applicants: Saudi Arabian Oil Company
- Inventors: Ki-Hyouk Choi; Mazin M. Fathi; Maddala Venkata Bhanumurthy; Abdullah M. Salma; Faisal M. Almulla; Ali M. Alsomali; Young-Kyoung Ahn
- Web page: https://patentgrep.com/patent/US11306263B1

## CPC

- C10G 55/04: including at least one thermal cracking step
- C10B 55/00: Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material (cracking oils C10G)
- C10B 57/045: {containing mineral oils, bitumen, tar or the like or mixtures thereof}
- C10G 9/005: {Coking (in order to produce liquid products mainly)}
- C10G 9/007: {Visbreaking}
- C10G 75/04: by addition of antifouling agents
- C10G 2300/1011: Biomass
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- C10G 2300/1077: Vacuum residues
- C10G 2300/201: Impurities
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/205: Metal content
- C10G 2300/207: Acid gases, e.g. H2S, COS, SO2, HCN
- C10G 2300/301: Boiling range
- C10G 2300/305: Octane number, e.g. motor octane number [MON], research octane number [RON]
- C10G 2300/307: Cetane number, cetane index
- C10G 2300/308: Gravity, density, e.g. API
- 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
- C10B: DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS (cracking oils C10G; underground gasification of minerals E21B43/295)

## Abstract

A process for upgrading a heavy oil includes passing heavy oil and disulfide oil to a thermal cracking system that includes a thermal cracking unit and a cracker effluent separation system downstream of the thermal cracking unit and thermally cracking at least a portion of the heavy oil in the presence of the disulfide oil in the thermal cracking unit to produce solid coke and a cracking effluent comprising reaction products. The reaction products include one or more liquid reaction products, one or more gaseous reaction products, or both. The presence of the disulfide oil in the thermal cracking unit promotes conversion of hydrocarbons from the heavy oil to the liquid reaction products, the gaseous reaction products, or both relative to the production of the solid coke.

## Claims

### Claim 1

A process for upgrading a heavy oil, the process comprising:
passing heavy oil and disulfide oil to a thermal cracking system comprising a thermal cracking unit and a cracker effluent separation system downstream of the thermal cracking unit, where passing the disulfide oil to the thermal cracking system increases the total sulfur content in the thermal cracking unit by at least 3% compared to operation of the thermal cracking system without the disulfide oil;
thermally cracking at least a portion of the heavy oil in the presence of the disulfide oil in the thermal cracking unit to produce solid coke and a cracking effluent comprising one or more reaction products, where:
the one or more reaction products comprise one or more liquid reaction products, one or more gaseous reaction products, or both; and
the presence of the disulfide oil promotes conversion of hydrocarbons from the heavy oil to the liquid reaction products, the gaseous reaction products, or both over the solid coke.

### Claim 2 (depends on 1)

The process of claim 1, where the heavy oil is an atmospheric residue, a vacuum residue, or a combination of these produced from distillation of a hydrocarbon feed.

### Claim 3 (depends on 2)

The process of claim 2, where the hydrocarbon feed comprises crude oil, distilled crude oil, residue oil, topped crude oil, product streams from oil refineries, product streams from steam cracking processes, liquefied coals, liquids recovered from oil or tar sands, bitumen, shale oil, asphaltene, biomass hydrocarbons, or combinations of these.

### Claim 4 (depends on 1)

The process of claim 1, where the heavy oil has one or more of the following properties:
an API gravity less than or equal to 16;
a 10% boiling point temperature of greater than or equal to 600 degrees Fahrenheit (315° C.); or
a Conradson Carbon Residue of greater than or equal to 5 weight percent.

### Claim 5 (depends on 1)

The process of claim 1, where the disulfide oil comprises less than 20 weight percent water based on the total weight of the disulfide oil.

### Claim 6 (depends on 1)

The process of claim 1, where the disulfide oil comprises greater than or equal to 5 weight percent disulfide compounds based on the total weight of the disulfide oil.

### Claim 7 (depends on 1)

The process of claim 1, where the disulfide oil comprises greater than or equal to 3 weight percent total sulfur based on the total weight of the disulfide oil.

### Claim 8 (depends on 1)

The process of claim 1, where a sulfur content of the disulfide oil is greater than a sulfur content of the heavy oil.

### Claim 9 (depends on 1)

The process of claim 1, where the disulfide oil has an alkali metal content less than or equal to 100 parts per million by weight as determined through inductively coupled plasma mass spectrometry.

### Claim 10 (depends on 1)

The process of claim 1, where the thermal cracking unit comprises a delayed coker, a visbreaker, or combinations of these.

### Claim 11 (depends on 1)

The process of claim 1, further comprising passing the cracker effluent to the cracker effluent separation system that separates the cracker effluent into one or more product effluents and a cracker bottom stream.

### Claim 12 (depends on 11)

The process of claim 11, where a sulfur content of the disulfide oil is greater than a sulfur content of the cracker bottom stream.

### Claim 13 (depends on 11)

The process of claim 11, comprising:
passing the heavy oil to the cracker effluent separation system that separates the heavy oil and the cracker effluent into the one or more product streams and the cracker bottom stream;
combining the disulfide oil with the cracker bottom stream to produce a cracker feed; and
passing the cracker feed to the thermal cracking unit.

### Claim 14 (depends on 13)

The process of claim 13, where the cracker feed comprises from 0.5 weight percent to 30 weight percent disulfide oil based on the total weight of the cracker feed.

### Claim 15 (depends on 13)

The process of claim 13, where combining the disulfide oil with the cracker bottom stream further comprises mixing the disulfide oil and the cracker bottom stream to produce the cracker feed.

### Claim 16 (depends on 15)

The process of claim 15, where mixing comprises passing the disulfide oil and the cracker bottom stream through at least one static mixer upstream of the thermal cracking unit, where the at least one static mixer mixes the disulfide oil with the cracker bottom stream to produce the cracker feed.

### Claim 17 (depends on 1)

The process of claim 1, where the disulfide oil comprises a disulfide oil effluent from a sweetening process.

### Claim 18 (depends on 1)

The process of claim 1, further comprising:
treating a sulfur containing hydrocarbon stream in a sweetening process that removes sulfur and sulfur compounds from the sulfur containing hydrocarbon stream to produce at least a reduced sulfur hydrocarbon stream and a disulfide oil stream; and
passing the disulfide oil stream to the thermal cracking system as the disulfide oil.

### Claim 19 (depends on 1)

The process of claim 1, where the thermal cracking system cracks at least a portion of disulfide compounds in the disulfide oil to increase the yield of the gaseous reaction products, the liquid reaction products, or both.

### Claim 20 (depends on 1)

The process of claim 1, where disulfide oil comprises disulfide compounds having the general formula (I):
R1—S—S—R2 (I)
where R1 and R2 are both hydrocarbyl groups.