Supercritical reactor systems and processes for petroleum upgrading

• US 10,543,468 B2
• Filed: 03/03/2017
• Issued: 01/28/2020
• Est. Priority Date: 12/15/2015
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: Choi, Ki-Hyouk, Alabdulhadi, Abdullah T., Al-Abdullah, Mohammad A.
• Primary Examiner(s): Singh, Prem C
• Assistant Examiner(s): Doyle, Brandi M
• Application Number:
  US15/448,961
• Publication Number:
  US 20170175006A1
• Time in Patent Office: 1,061 Days
• CPC Class Codes: B01J 3/008 Processes carried out under supercritical conditions
• CPC Class Codes: B01J 3/02 Feed or outlet devices therefor
• CPC Class Codes: C10G 11/10 with stationary catalyst bed
• CPC Class Codes: C10G 2300/70 Catalyst aspects
• CPC Class Codes: C10G 2300/703 Activation
• CPC Class Codes: C10G 2300/805 Water
• CPC Class Codes: C10G 2300/807 Steam
• CPC Class Codes: C10G 31/08 by treating with water
• CPC Class Codes: C10G 49/18 in the presence of hydrogen-generating compounds, e.g. ammonia, water, hydrogen sulfide
• CPC Class Codes: C10G 51/026 only catalytic cracking steps
• CPC Class Codes: C10G 65/02 plural serial stages only
• CPC Class Codes: C10G 65/10 including only cracking steps
• CPC Class Codes: C10G 65/12 including cracking steps and other hydrotreatment steps
• CPC Class Codes: C10G 75/00 Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general C10G7/10, C10G9/16 take precedence
• CPC Class Codes: C10G 75/04 by addition of antifouling agents
• CPC Class Codes: Y02P 20/54 using solvents, e.g. supercritical solvents or ionic liquids

Abstract

Provided herein are supercritical upgrading reactors and reactor systems for upgrading a petroleum-based composition by using one or more supercritical upgrading reactors and one or more supercritical standby reactors that alternate functions such that the supercritical upgrading reactor is converted to a supercritical standby reactor and the supercritical standby reactor is converted to a supercritical upgrading reactor. The supercritical upgrading reactor upgrades a combined feed stream while a supercritical standby reactor delivers a cleaning fluid into the supercritical standby reactor. The supercritical reactors may have one or more catalyst layers and one or more purging fluid inlets, and the catalyst layers may have differing void volume ratios.

Claims

1. A process for upgrading a petroleum-based composition comprising:

combining a supercritical water stream with a pressurized, heated petroleum-based composition in a mixing device to create a combined feed stream,

introducing the combined feed stream into an upgrading reactor system comprising one or more supercritical upgrading reactors and one or more supercritical standby reactors,

where the supercritical upgrading reactor and the supercritical standby reactor both operate at a temperature greater than a critical temperature of water and a pressure greater than a critical pressure of water,

where the supercritical upgrading reactor and the supercritical standby reactor both comprise at least one catalyst layer,

where the supercritical upgrading reactor, the supercritical standby reactor, or both comprise a first catalyst layer and a second catalyst layer, where the first catalyst layer comprises a heterogeneous porous metal containing catalyst having a first void volume ratio and the second catalyst layer comprises a heterogeneous porous metal containing catalyst having a second void volume ratio, where the second void volume ratio is less than the first void volume ratio, and

upgrading the combined feed stream in the supercritical upgrading reactor to produce an upgraded product;

cleaning the supercritical standby reactor by passing a cleaning fluid into the supercritical standby reactor, while the upgrading step is being performed in the supercritical upgrading reactor; and

alternating functions of the supercritical upgrading reactor and the supercritical standby reactor, such that the supercritical upgrading reactor is converted to a supercritical standby reactor undergoing a cleaning operation by the delivery of the cleaning fluid, while the supercritical standby reactor is converted to a supercritical upgrading reactor that upgrades the combined feed stream.

2. The process of claim 1, where the at least one catalyst layer comprises a heterogeneous porous metal containing catalyst.

3. The process of claim 2, where the heterogeneous porous metal containing catalyst includes one or more components selected from the group consisting of transition metals and precious metals.

4. The process of claim 1, further comprising one or more pressure sensors upstream and downstream of the supercritical upgrading reactor, the supercritical standby reactor, or both.

5. The process of claim 4, where the one or more pressure sensors trigger shutting down the combined feed stream from the supercritical upgrading reactor and commencing a cleaning operation.

6. The process of claim 4, where the one or more pressure sensors trigger an alert when the pressure of at least one supercritical upgrading reactor or supercritical standby reactor has deviated from an operating pressure by from 1% to 10%.

7. The process of claim 1, where the cleaning fluid comprises supercritical water, oil, or both.

8. The process of claim 1, where the cleaning fluid comprises between 0.1 weight percent (wt %) and 2.0 wt % O₂.

9. The process of claim 1, where the supercritical upgrading reactor, the supercritical standby reactor, or both comprise one or more purging fluid inlets.

10. The process of claim 9, where the one or more purging fluid inlets inject a purging fluid into the supercritical upgrading reactor, supercritical standby reactor, or both, in response to one or more pressure sensors.