# US 2021/0277318 A1 · Systems and processes for direct crude oil upgrading to hydrogen and chemicals

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- Number: US 2021/0277318 A1
- Document ID: US20210277318A1
- Status: Published application
- Kind: A1
- Application number: 16/810,596
- Filed: 2020-03-05
- Published: 2021-09-09
- Earliest claimed: 2020-03-05
- Assignees: Saudi Arabian Oil Company
- Applicants: Saudi Arabian Oil Company
- Inventors: Aadesh HARALE; Ibrahim ABBA; Ahmad KHOWAITER; Abdennour BOURANE; Aqil JAMAL; Mourad YOUNES
- Web page: https://patentgrep.com/patent/US20210277318A1

## CPC

- C10G 69/00: Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process (C10G67/00 takes precedence)
- C10J 3/00: Production of combustible gases containing carbon monoxide from solid carbonaceous fuels (destructive distillation processes C10B)
- B01D 3/06: Flash distillation
- B01D 19/0057: {the centrifugal movement being caused by a vortex, e.g. using a cyclone, or by a tangential inlet}
- B01J 8/1827: {the fluidising gas being a reactant}
- B01J 8/24: according to "fluidised-bed" technique (B01J8/20 takes precedence)
- B01J 19/2445: {placed in parallel}
- B01J 19/245: {placed in series}
- C01B 3/34: by reaction of hydrocarbons with gasifying agents
- C01B 3/36: using oxygen; using mixtures containing oxygen as gasifying agents
- C01B 3/48: followed by reaction of water vapour with carbon monoxide
- C01B 32/50: Carbon dioxide
- C07C 6/123: {of only one hydrocarbon}
- C07C 6/126: {of more than one hydrocarbon}
- C07C 7/04: by distillation
- C07C 51/14: on a carbon-to-carbon unsaturated bond in organic compounds
- C10G 2/32: {with the use of catalysts}
- C10G 2/344: {according to the "fluidised-bed" technique}
- C10G 11/18: according to the "fluidised-bed" technique
- C10G 11/182: {Regeneration}
- C10G 45/44: Hydrogenation of the aromatic hydrocarbons
- C10G 47/00: Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions (C10G15/00 takes precedence; destructive hydrogenation of non-melting solid carbonaceous or similar materials C10G1/06)
- C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10K 3/04: reducing the carbon monoxide content {, e.g. water-gas shift [WGS]}
- B01J 2208/00893: Feeding means for the reactants
- B01J 2219/00038: Processes in parallel
- B01J 2219/0004: Processes in series
- C01B 2203/0233: the reforming step being a steam reforming step
- C01B 2203/0238: the reforming step being a carbon dioxide reforming step
- C01B 2203/0244: the reforming step being an autothermal reforming step, e.g. secondary reforming processes
- C01B 2203/025: containing a partial oxidation step
- C01B 2203/0255: containing a non-catalytic partial oxidation step
- C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step
- C01B 2203/043: Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
- C01B 2203/0475: the impurity being carbon dioxide
- C01B 2203/06: Integration with other chemical processes
- C01B 2203/1241: Natural gas or methane
- C01B 2203/148: involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
- C01B 2203/86: Carbon dioxide sequestration
- C10G 2300/1044: Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
- C10G 2300/1055: Diesel having a boiling range of about 230 - 330 °C
- C10G 2300/4043: Limiting CO2 emissions
- C10G 2400/20: C2-C4 olefins
- C10G 2400/30: Aromatics
- Y02P 30/00: Technologies relating to oil refining and petrochemical industry
- Y02P 30/40: Ethylene production
- 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
- C10J: PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES (synthesis gas from liquid or gaseous hydrocarbons C01B; underground gasification of minerals E21B43/295); CARBURETTING AIR OR OTHER GASES
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C10K: PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Systems and methods for direct crude oil upgrading to hydrogen and chemicals including separating an inlet hydrocarbon stream into a light fraction and a heavy fraction comprising diesel boiling point temperature range material; producing from the light fraction syngas comprising H2 and CO; reacting the CO produced; producing from the heavy fraction and separating CO2, polymer grade ethylene, polymer grade propylene, C4 compounds, cracking products, light cycle oils, and heavy cycle oils; collecting and purifying the CO2 produced from the heavy fraction; processing the C4 compounds to produce olefinic oligomerate and paraffinic raffinate; separating the cracking products; oligomerizing a light cut naphtha stream; hydrotreating an aromatic stream; hydrocracking the light cycle oils to produce a monoaromatics product stream; gasifying the heavy cycle oils; reacting the CO produced from gasifying the heavy cycle oils; collecting and purifying the CO2; and processing and separating produced aromatic compounds into benzene and para-xylene.

## Claims

### Claim 1

A method for hydrocarbon separation and upgrading, the method comprising the steps of:
separating an inlet hydrocarbon stream into a light fraction comprising naphtha boiling point temperature range material and a heavy fraction comprising diesel boiling point temperature range material;
producing from the light fraction syngas comprising H2 and CO;
reacting the CO produced from the light fraction via at least one reaction selected from the group consisting of: carbonylation, polymerization, and water-gas shift;
producing from the heavy fraction and separating CO2, polymer grade ethylene, polymer grade propylene, C4 compounds, cracking products comprising naphtha boiling point temperature range products with olefins and aromatics, light cycle oils, and heavy cycle oils;
collecting and purifying the CO2 produced from the heavy fraction;
processing the C4 compounds to produce olefinic oligomerate and paraffinic raffinate, the paraffinic raffinate being used to produce hydrogen;
separating the cracking products comprising naphtha boiling point temperature range products with olefins and aromatics into a light cut naphtha stream including C5 and C6 olefins and an aromatic stream comprising aromatic compounds;
oligomerizing the light cut naphtha stream;
hydrotreating the aromatic stream;
hydrocracking the light cycle oils to produce a monoaromatics product stream;
gasifying the heavy cycle oils to produce hydrogen, CO, and CO2;
reacting the CO produced from gasifying the heavy cycle oils via at least one reaction selected from the group consisting of: carbonylation, polymerization, and water-gas shift;
collecting and purifying the CO2 produced from gasifying the heavy cycle oils; and
processing and separating produced aromatic compounds into benzene and para-xylene.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the inlet hydrocarbon stream comprises at least one component selected from the group consisting of: crude oil and gas condensates.

### Claim 3 (depends on 1)

The method according to claim 1, wherein gasoline and diesel are not final products of the method.

### Claim 4 (depends on 1)

The method according to claim 1, wherein greater than about 90 wt. % by mass of the CO2 and greater than about 90 wt. % by mass of the CO produced in the method are captured and further processed to other compounds.

### Claim 5 (depends on 1)

The method according to claim 1, further comprising the step of collecting and purifying CO2 produced during the step of producing from the light fraction syngas comprising H2 and CO.

### Claim 6 (depends on 1)

The method according to claim 1, further comprising the step of processing at least a portion of the produced CO2 in at least one process selected from the group consisting of: dry reforming; steam reforming, and hydrogenation.

### Claim 7 (depends on 1)

The method according to claim 1, further comprising the step of processing at least a portion of the produced CO2 to produce at least one product selected from the group consisting of: a synthetic fuel; syngas comprising H2 and CO; and olefins.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the step of separating the inlet hydrocarbon stream comprises the use of at least one unit selected from the group consisting of: a flash drum, a distillation-based separation unit, and a cyclonic vapor-liquid separation unit.

### Claim 9 (depends on 1)

The method according to claim 1, where the steps of reacting the CO produced from the light fraction and reacting the CO produced from gasifying the heavy cycle oils include the step of producing adipic acid via carbonylation of butadiene.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the step of producing from the light fraction syngas comprising H2 and CO comprises the use of at least one unit selected from the group consisting of: a steam reforming unit, a partial oxidation unit, and an auto-thermal reforming unit.

### Claim 11 (depends on 1)

The method according to claim 1, wherein the step of producing from the heavy fraction is carried out using a high-severity fluidized catalytic cracking system comprising a downflow reactor.

### Claim 12 (depends on 1)

The method according to claim 1, wherein a portion of H2 produced in the method is used internally for hydrotreating.

### Claim 13 (depends on 1)

The method according to claim 1, wherein the step of hydrocracking the light cycle oils includes hydrocracking and reforming reactions.

### Claim 14 (depends on 1)

The method according to claim 1, further comprising the step of processing the monoaromatics product stream via trans-alkylation to convert toluene and C9-C11 aromatics into benzene and mixed xylenes.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the CO2 produced from the heavy fraction includes CO2 produced from coke burned in a regenerator of a catalytic cracking system.

### Claim 16 (depends on 1)

The method according to claim 1, wherein at least a portion of the heavy cycle oils produced from the heavy fraction is utilized to provide energy to the method.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the step of producing from the light fraction syngas comprising H2 and CO further comprises producing hydrogen from at least one stream comprising saturated C1 to C4 compounds.

### Claim 18 (depends on 1)

The method according to claim 1, wherein the step of processing and separating produced aromatic compounds into benzene and para-xylene further produces heavy aromatics which are recycled to the step of hydrocracking the light cycle oils or gasifying the heavy cycle oils.

### Claim 19

A system for hydrocarbon separation and upgrading, the system comprising:
an inlet hydrocarbon stream;
a feed inlet splitter operable to separate the inlet hydrocarbon stream into a light fraction comprising naphtha boiling point temperature range material and a heavy fraction comprising diesel boiling point temperature range material;
a hydrogen production unit operable to produce from the light fraction syngas comprising H2 and CO;
a carbon reaction unit operable to react the CO produced from the light fraction via at least one reaction selected from the group consisting of: carbonylation, polymerization, and water-gas shift;
a high-severity fluidized catalytic cracking (HS-FCC) unit operable to produce from the heavy fraction CO2, polymer grade ethylene, polymer grade propylene, C4 compounds, cracking products comprising naphtha boiling point temperature range products with olefins and aromatics, light cycle oils, and heavy cycle oils;
a CO2 collection and processing unit operable to collect and purifying the CO2 produced from the heavy fraction;
an oligomerization unit operable to process the C4 compounds to produce olefinic oligomerate and paraffinic raffinate, the paraffinic raffinate being used to produce hydrogen in the hydrogen production unit;
a cracked naphtha splitter operable to separate the cracking products comprising naphtha boiling point temperature range products with olefins and aromatics into a light cut naphtha stream including C5 and C6 olefins and an aromatic stream comprising aromatic compounds, wherein the oligomerization unit is operable to oligomerize the light cut naphtha stream;
a heavy naphtha selective hydrotreating unit operable to hydrotreat the aromatic stream;
a cycle oils hydrocracker unit operable to hydrocrack the light cycle oils to produce a monoaromatics product stream;
a gasifier unit operable to gasify the heavy cycle oils to produce hydrogen, CO, and CO2, wherein the carbon reaction unit is operable to react the CO produced from gasifying the heavy cycle oils via at least one reaction selected from the group consisting of: carbonylation, polymerization, and water-gas shift, wherein the CO2 collection and processing unit is operable to collect and purifying the CO2 produced from gasifying the heavy cycle oils; and
an aromatic extraction unit operable to process and separate produced aromatic compounds into benzene and para-xylene.

### Claim 20 (depends on 19)

The system according to claim 19, wherein the inlet hydrocarbon stream comprises at least one component selected from the group consisting of: crude oil and gas condensates.

### Claim 21 (depends on 19)

The system according to claim 19, wherein gasoline and diesel are not final products of the system.

### Claim 22 (depends on 19)

The system according to claim 19, wherein greater than about 90 wt. % by mass of the CO2 and greater than about 90 wt. % by mass of the CO produced in the system are captured and further processed to other compounds.

### Claim 23 (depends on 19)

The system according to claim 19, wherein the CO2 collection and processing unit is operable to collect and purify CO2 produced from the hydrogen production unit.

### Claim 24 (depends on 19)

The system according to claim 19, further comprising a CO2 conversion unit operable to react CO2 in at least one process selected from the group consisting of: dry reforming; steam reforming; and hydrogenation.

### Claim 25 (depends on 19)

The system according to claim 19, further comprising a CO2 conversion unit operable to process at least a portion of the produced CO2 to produce at least one product selected from the group consisting of: a synthetic fuel; syngas comprising H2 and CO; and olefins.

### Claim 26 (depends on 19)

The system according to claim 19, where the feed inlet splitter comprises at least one unit selected from the group consisting of: a flash drum, a distillation-based separation unit, and a cyclonic vapor-liquid separation unit.

### Claim 27 (depends on 19)

The system according to claim 19, where the carbon reaction unit is operable to react CO to produce adipic acid via carbonylation of butadiene.

### Claim 28 (depends on 19)

The system according to claim 19, wherein the hydrogen production unit includes at least one unit selected from the group consisting of: a steam reforming unit, a partial oxidation unit, and an auto-thermal reforming unit.

### Claim 29 (depends on 19)

The system according to claim 19, wherein the HS-FCC unit includes a downflow reactor.

### Claim 30 (depends on 19)

The system according to claim 19, wherein a portion of H2 produced in the system is used internally for hydrotreating.

### Claim 31 (depends on 19)

The system according to claim 19, wherein the cycle oils hydrocracker unit includes hydrocracking and reforming reactions.

### Claim 32 (depends on 19)

The system according to claim 19, where the aromatic extraction unit includes at least one unit selected from the group consisting of: a benzene extraction unit, a toluene plus C9-C11 trans-alkylation unit, a xylenes isomerization unit, and a para-xylene extraction unit.

### Claim 33 (depends on 19)

The system according to claim 19, further comprising a catalyst regenerator to remove coke from catalyst.

### Claim 34 (depends on 19)

The system according to claim 19, wherein at least a portion of the heavy cycle oils produced from the heavy fraction is utilized to provide energy to the system.

### Claim 35 (depends on 19)

The system according to claim 19, wherein the hydrogen production unit includes a feed including saturated C1 to C4 compounds.

### Claim 36 (depends on 19)

The system according to claim 19, wherein heavy aromatics produced in the aromatic extraction unit are recycled to the cycle oils hydrocracker unit or the gasifier unit.