# US 11,078,434 B2 · Process and system for upgrading low-quality oils

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- Number: US 11,078,434 B2
- Document ID: US11078434B2
- Status: Granted
- Kind: B2
- Application number: 16/646,070
- Filed: 2017-09-11
- Published: 2020-09-10
- Granted: 2021-08-03
- Earliest claimed: 2017-09-11
- Assignees: China Petroleum & Chemical Corporation; Research Institute of Petroleum Processing, Sinopec
- Applicants: China Petroleum & Chemical Corporation; Research Institute of Petroleum Processing, Sinopec
- Inventors: Jun Long; Huandi Hou; Zijun Wang; Haiping Shen; Ming Dong; Lishun Dai; Jianhong Gong; Jiguang Li; Shuhong Zhang; Cuihong Wang; Yucheng She; Yuzhang Wang; Mengying Tao
- Web page: https://patentgrep.com/patent/US11078434B2

## CPC

- C10G 21/14: Hydrocarbons
- C10G 67/02: plural serial stages only
- B01D 3/06: Flash distillation
- B01D 11/04: of solutions which are liquid
- B01J 19/0006: {Controlling or regulating processes (controlling or regulating in general G05)}
- B01J 19/0013: {Controlling the temperature of the process}
- B01J 19/245: {placed in series}
- C10G 11/18: according to the "fluidised-bed" technique
- C10G 21/003: {Solvent de-asphalting}
- C10G 45/00: Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- 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 65/12: including cracking steps and other hydrotreatment steps
- C10G 65/14: plural parallel stages only
- C10G 67/04: including solvent extraction as the refining step in the absence of hydrogen
- C10G 69/04: including at least one step of catalytic cracking in the absence of hydrogen
- B01J 2219/0004: Processes in series
- B01J 2219/00051: Controlling the temperature
- B01J 2219/00162: controlling the pressure
- C10G 2300/1044: Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/205: Metal content
- C10G 2300/206: Asphaltenes
- C10G 2300/301: Boiling range
- C10G 2300/304: Pour point, cloud point, cold flow properties
- C10G 2300/307: Cetane number, cetane index
- C10G 2300/308: Gravity, density, e.g. API
- C10G 2300/4006: Temperature
- C10G 2300/4012: Pressure
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- C10G 2300/4081: Recycling aspects
- C10G 2400/02: Gasoline
- C10G 2400/04: Diesel oil
- C10G 2400/08: Jet fuel
- 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
- 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

## Abstract

Disclosed is a process and system for upgrading low-quality oils. The upgrading process comprises: (1) subjecting a low-quality oil to a conversion reaction in the presence of hydrogen and optionally in the presence of a conversion catalyst to obtain a conversion product, (2) processing the conversion product to obtain a first processed product, wherein the first processed product comprises a specific amount of a special component, and (3) subjecting the first processed product to extraction separation to obtain an upgraded oil and a pitch. The upgrading process and the upgrading system have the advantages of stable operation, high upgrading efficiency, environmental friendliness, low coke yield or high yield of upgraded oil.

## Claims

### Claim 1

An upgrading process, comprising:
(1) subjecting a low-quality oil used as an upgrading feedstock to a conversion reaction in the presence of hydrogen to obtain a conversion product,
(2) processing the conversion product to obtain a first processed product, wherein the first processed product comprises from 20 wt % to 60 wt % of a component having a boiling point or boiling range between 350° C. and 524° C., and
(3) subjecting the first processed product to extraction separation to obtain an upgraded oil and a pitch.

### Claim 2 (depends on 1)

The upgrading process according to claim 1, wherein the step (2) further comprises:
(2-1) subjecting the conversion product to a first separation at a first pressure and a first temperature to obtain a gas component and a liquid component, and
(2-2) subjecting the liquid component to a second separation at a second pressure and a second temperature to obtain a second separated product and a first separated product, wherein the first separated product is the first processed product, and the second separated product or any component thereof has a final boiling point of less than or equal to 350° C.,
wherein the first pressure is 4-24 MPa greater than the second pressure.

### Claim 3 (depends on 2)

The upgrading process according to claim 2, wherein the first pressure is in a range from 10.0 MPa to 25.0 Mpa and the first temperature is in a range from 380° C. to 470° C.; or the second pressure is in a range from 0.1 MPa to 5.0 Mpa, and the second temperature is in a range from 150° C. to 390° C.

### Claim 4 (depends on 2)

The upgrading process according to claim 2, wherein the step (2) further comprises:
(2-3) separating the second separated product to obtain naphtha and atmospheric gas oil, and
(2-4) subjecting the gas component to step (1), and
wherein the first pressure is 7-19 MPa greater than the second pressure.

### Claim 5 (depends on 1)

The upgrading process according to claim 1, wherein the step (3) further comprises:
(3-1) contacting the first processed product with a solvent at a third pressure and a third temperature to obtain the upgraded oil and the pitch.

### Claim 6 (depends on 5)

The upgrading process according to claim 5, wherein the solvent is one or more of C3-7 hydrocarbons, and a weight ratio of the solvent to the first processed product is 1-7:1.

### Claim 7 (depends on 5)

The upgrading process according to claim 5, wherein the third pressure is in a range from 3 MPa to 12 Mpa, and the third temperature is in a range from 55° C. to 300° C.

### Claim 8 (depends on 5)

The upgrading process according to claim 5, wherein the step (3) further comprises one or more of the following steps:
(3-2) subjecting the upgraded oil to hydrogenation to obtain a hydrotreated upgraded oil,
(3-3) subjecting the upgraded oil to hydrocracking to obtain a hydrocracked product, and then separating the hydrocracked product into dry gas, liquefied gas, aviation kerosene, diesel oil, and hydrogenated tail oil,
(3-4) subjecting the hydrotreated upgraded oil to catalytic cracking to obtain a first catalytic cracked product, and then separating the first catalytic cracked product into dry gas, liquefied gas, gasoline, cycle oil and slurry oil,
(3-5) catalytically cracking a mixture comprising the hydrotreated upgraded oil and the atmospheric gas oil to obtain a second catalytic cracked product, and then separating the second catalytic cracked product into dry gas, liquefied gas, gasoline, cycle oil and slurry oil,
(3-6) catalytically cracking a mixture comprising the hydrotreated upgraded oil and the second separated product to obtain a third catalytic cracked product, and then separating the third catalytic cracked product into dry gas, liquefied gas, gasoline, cycle oil and slurry oil,
(3-7) subjecting the atmospheric gas oil to a hydrogenation reactor to obtain diesel oil,
(3-8) subjecting the cycle oil obtained in any step of the upgrading process to a hydrogenation reactor alone or together with the upgraded oil to obtain a hydrotreated oil,
(3-9) catalytically cracking a mixture comprising the hydrotreated oil and the second separated product to obtain a fourth catalytic cracked product, and then separating the fourth catalytic cracked product into dry gas, liquefied gas, gasoline, cycle oil and slurry oil,
(3-10) subjecting the slurry oil obtained in any step of the upgrading process and/or an externally supplied slurry oil to the step (1), step (2), and/or step (3), or
(3-11) subjecting the liquefied gas obtained in any step of the upgrading process to the step (3) or step (3-1).

### Claim 9 (depends on 8)

The upgrading process according to claim 8, wherein the step (3-2) or step (3-8) is carried out in the presence of a hydrogenation catalyst under the following conditions: a hydrogen partial pressure between 5.0 MPa and 20.0 MPa, a reaction temperature between 330° C. and 450° C., a volumetric space velocity of the feedstock oil between 0.1 h−1 and 3.0 h−1, and a volume ratio of hydrogen to feedstock oil between 300 and 3000;
or alternatively, the step (3-3) is carried out in the presence of a hydrocracking catalyst under the following conditions: a hydrogen partial pressure between 10.0 MPa and 20.0 MPa, a reaction temperature between 310° C. and 420° C., a volumetric space velocity of the upgraded oil between 0.3 h−1 and 1.2 h−1, and a volume ratio of hydrogen to the upgraded oil between 600 and 1500;
or alternatively, the step (3-4), step (3-5), step (3-6) or step (3-9) is carried out in the presence of a cracking catalyst under the following conditions: a reaction temperature between 450° C. and 650° C., a reaction pressure between 0.15 MPa and 0.4 MPa, a reaction time between 0.1 seconds and 10 seconds, a weight ratio of cracking catalyst to feedstock oil between 3 and 30, and a weight ratio of steam to feedstock oil between 0.05 and 0.6;
or alternatively, the step (3-7) is carried out in the presence of a hydrogenation catalyst under the following conditions: a hydrogen partial pressure between 7.0 MPa and 15.0 MPa, a reaction pressure between 8 MPa and 12 MPa, a reaction temperature between 340° C. and 400° C.; a volumetric space velocity of the atmospheric gas oil between 0.6 h−1 and 1.5 h−1, and a volume ratio of hydrogen to the atmospheric gas oil between 500 and 800.

### Claim 10 (depends on 1)

The upgrading process according to claim 1, wherein the conversion reaction is carried out in the presence of a conversion catalyst under the following conditions: a hydrogen partial pressure between 10.0 MPa and 25.0 MPa, a reaction temperature between 380° C. and 470° C., a volumetric space velocity of the upgrading feedstock between 0.01 h−1 and 2.0 h−1, and a volume ratio of hydrogen to the upgrading feedstock between 500 and 5000.

### Claim 11 (depends on 1)

The upgrading process according to claim 1, wherein the pitch has a softening point of less than 150° C.

### Claim 12 (depends on 1)

The upgrading process according to claim 1, wherein the low-quality oil is one or more selected from the group consisting of inferior oils, deoiled asphalt, heavy oil, extra heavy oil, coal-derived oil, shale oil, and petrochemical waste oil, and wherein the heavy oil is one or more selected from the group consisting of topped crude oil, heavy oil derived from oil sands bitumen, and heavy oil having an initial boiling point of greater than 350° C., the coal-derived oil is one or more selected from the group consisting of coal liquefied oil produced by coal liquefaction and coal tar produced by coal pyrolysis, or the petrochemical waste oil is one or more selected from the group consisting of petrochemical waste oil sludge, petrochemical oil residue, and refined products thereof.

### Claim 13 (depends on 1)

The upgrading process according to claim 1, wherein the first processed product has an initial boiling point of greater than or equal to 330° C., or the first processed product further comprises a light component having a boiling point or a boiling range of less than or equal to 350° C., or the first processed product further comprises a heavy component having a boiling point or a boiling range of greater than 500° C.

### Claim 14 (depends on 1)

The upgrading process according to claim 1, wherein in step (2), one or more second processed products are obtained in addition to the first processed product, and wherein the second processed product or any component thereof has a final boiling point of less than or equal to 350° C.

### Claim 15 (depends on 1)

The upgrading process according to claim 1, further comprising:
(4) subjecting all or a part of the pitch to step (1).

### Claim 16

An upgrading system, comprising a conversion reactor, a conversion product processing unit, a first control unit, and an extraction column, wherein the conversion product processing unit comprises a flash tank, a fractionation column, or a distillation column,
wherein the conversion reactor is configured to conduct a conversion reaction of a low-quality oil in the presence of hydrogen and discharge a conversion product,
the conversion product processing unit is configured to process the conversion products and discharge a first processed product,
the first control unit comprises a first pressure control device and/or a first temperature control device and is configured to control the operating conditions of the conversion product processing unit such that the first processed product comprises from 20 wt % to 60 wt % of a component having a boiling point or a boiling range between 350° C. and 524° C., and
the extraction column is configured to conduct an extraction separation of the first processed product and discharge an upgraded oil and a pitch.

### Claim 17 (depends on 16)

The upgrading system according to claim 16, wherein the conversion product processing unit further comprises a first conversion product separation unit, and a second conversion product separation unit,
the first conversion product separation unit comprises a pressure distillation column and is configured to separate the conversion product and discharge a gas component and a liquid component, and
the second conversion product separation unit comprises a flash tank and/or an atmospheric distillation column is configured to separate the liquid component and discharge a second separated product and a first separated product.

### Claim 18 (depends on 17)

The upgrading system according to claim 17, further comprising a a second control unit and a third control unit, wherein the second control unit comprises a second pressure control device and is configured to control the operating pressure of the first conversion product separation unit, the third control unit comprises a third pressure control device and is configured to control the operating pressure of the second conversion product separation unit, so that the operating pressure of the first conversion product separation unit is greater than the operating pressure of the second conversion product separation unit,
wherein the third control unit is configured to control the operating conditions of the second conversion product separation unit so that the first separated product is the first processed product and the second separated product or any component thereof has a final boiling point of less than or equal to 350° C.

### Claim 19 (depends on 17)

The upgrading system according to claim 17, further comprising one or more of the following reactors:
a first hydrogenation reactor configured to conduct a hydrotreating on the upgraded oil and discharge a hydrotreated upgraded oil,
a second hydrogenation reactor configured to conduct hydrocracking of the upgraded oil and separate a resulting hydrocracked product into dry gas, liquefied gas, aviation kerosene, diesel oil, and hydrogenated tail oil,
a first catalytic cracking reactor configured to conduct catalytic cracking of the hydrotreated upgraded oil and separate a resulting first catalytic cracked product into dry gas, liquefied gas, gasoline, cycle oil, and slurry oil,
a second catalytic cracking reactor configured to conduct catalytic cracking of a mixture comprising the hydrotreated upgraded oil and an atmospheric gas oil, and separate a resulting second catalytic cracked product into dry gas, liquefied gas, gasoline, cycle oil, and slurry oil,
a third catalytic cracking reactor configured to conduct catalytic cracking of a mixture comprising the hydrotreated upgraded oil and the second separated product, and separate a resulting third catalytic cracked product into dry gas, liquefied gas, gasoline, cycle oil and slurry oil,
a third hydrogenation reactor configured to hydrotreating on an atmospheric gas oil and discharge a diesel oil,
a fourth hydrogenation reactor configured to hydrotreating a mixture comprising a cycle oil obtained in the upgrading system and the upgraded oil and discharge a hydrotreated oil,
a fourth catalytic cracking reactor configured to conduct catalytic cracking of a mixture comprising the hydrotreated oil and the second separated product, and separate a resulting fourth catalytic cracked product into dry gas, liquefied gas, gasoline, cycle oil and slurry oil,
a slurry oil transport pump configured to transport a slurry oil obtained in the upgrading system and/or an externally supplied slurry oil to the conversion reactor, the conversion product processing unit, and/or the extraction column, and
a liquefied gas transport pipe configured to transport the liquefied gas obtained in the upgrading system to the extraction column.

### Claim 20 (depends on 16)

The upgrading system according to claim 16, wherein the extraction column is configured to contact the first processed product with a solvent and discharge the upgraded oil and the pitch.