Process for heavy oil upgrading utilizing hydrogen and water

Patent metadata

Field	Value
Publication number	US-11286429-B2
Application number	US-202016911827-A
Country	US
Kind code	B2
Filing date	Jun 25, 2020
Priority date	Jun 25, 2020
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

A process for upgrading heavy oil is provided, which integrates thermal cracking, hydrogenolysis, and catalytic aquathermolysis. A catalytic hydrogen-aquathermolysis reactor receives a heavy oil feed, water and hydrogen. In addition catalytic materials and a viscosity reducing agent are introduced. The catalytic hydrogen-aquathermolysis reactor is operated at conditions effective to produce an upgraded heavy oil product.

First claim

The invention claimed is:

1. A process for upgrading heavy oil integrating thermal cracking, hydrogenolysis, and catalytic aquathermolysis, the process comprising:
charging to a catalytic hydrogen-aquathermolysis reactor
heavy oil feed,
water in a quantity of about 1 to about 20 weight percent relative to the mass of the heavy oil feed,
hydrogen in a quantity of about 1 to about 1000 normalized cubic meters of hydrogen to cubic meters of heavy oil feed,
viscosity reducing agent in a quantity of 10 to about 40 weight percent relative to the mass of the heavy oil feed, and
catalytic materials in a quantity of about 100 to 20,000 parts per million active catalyst particles on a weight basis relative to the mass of the heavy oil feed;

operating the catalytic hydrogen-aquathermolysis reactor at a hydrogen pressure of no more than about 60 bars of hydrogen partial pressure, a temperature of at least about 400° C. and a liquid hourly space velocity on a fresh feed basis relative to the reactor volume of at least 0.1 h −1 , discharging from the catalytic hydrogen-aquathermolysis reactor a mixed gas and liquid reactor effluents, passing the mixed gas and liquid reactor effluents to a vapor-liquid separator to separate light effluents from upgraded heavy oil effluents, wherein the upgraded heavy oil effluents have a stability P-Value of at least about 1.2.

2. The process as in claim 1 wherein the heavy oil feed comprises vacuum residue, atmospheric residue or a combination of vacuum residue and atmospheric residue.

3. The process of claim 2 wherein the heavy oil feed further comprises effluent from one or more of a downstream fractionator unit, a solvent deasphalting unit, a delayed coking unit, a gasification unit, or a catalytic hydroprocessing unit.

4. The process as in claim 1 , further comprising:
prior to charging to the reactor, mixing the heavy oil feed, catalytic particles and viscosity reducing agent to produce a first mixture at a temperature of 40-80° C. at a pressure the range of about 1-30 bars;
pre-heating the first mixture to a reaction temperature in the range of from about 400° C. to 500° C.;
mixing the pre-heated first mixture with hydrogen and water to provide a second mixture, and

charging the second mixture to the reactor.

5. The process as in claim 4 , wherein production and pre-heating of the first mixture occurs in the absence of added hydrogen.

6. The process as in claim 4 , wherein catalytic material is provided in the form of particles that decompose during the pre-heating step to form active catalyst particles.

7. The process as in claim 4 , wherein catalytic material is provided in the form of catalytic metals precursors that form active catalyst particles during the pre-heating step.

8. The process as in claim 1 , further comprising:
prior to charging to the reactor, mixing the heavy oil feed, catalytic particles and viscosity reducing agent to produce a first mixture at a temperature of at most 100° C.;
pre-heating the first mixture to a temperature below a reaction temperature;
mixing the pre-heated first mixture with hydrogen and water to provide a second mixture, and
charging the second mixture to the reactor, wherein the second mixture is heated to the reaction temperature in the range of from about 400° C. to 500° C. in the reactor.

9. The process as in claim 8 , wherein production and pre-heating of the first mixture occurs in the absence of added hydrogen.

10. The process as in claim 8 , wherein catalytic material is provided in the form of particles that decompose during the pre-heating step to form active catalyst particles.

11. The process as in claim 8 , wherein catalytic material is provided in the form of catalytic metals precursors that form active catalyst particles during the pre-heating step.

12. The process as in claim 1 , further comprising:
prior to charging to the reactor, mixing the heavy oil feed, catalytic particles and viscosity reducing agent to produce a first mixture at a temperature of at most 100° C.;
pre-heating the first mixture to a temperature below a reaction temperature;
mixing the pre-heated first mixture with hydrogen and water to provide a second mixture,
pre-heating the second mixture to a reaction temperature in the range of from about 400° C. to 500° C. upstream of the reactor; and
charging the pre-heated second mixture to the reactor.

13. The process as in claim 12 , wherein production and pre-heating of the first mixture occurs in the absence of added hydrogen.

14. The process as in claim 13 , wherein during the step of pre-heating the first mixture catalytic material is converted to active catalyst particles.

15. The process as in claim 14 , wherein catalytic material is provided in the form of catalyst particles that decompose during the first pre-heating step to form active catalyst particles.

16. The process as in claim 14 , wherein catalytic material is provided in the form of catalytic metals precursors that form active catalyst particles during the first pre-heating step.

17. The process as in claim 1 , wherein catalytic material is provided in the form of active catalyst particles.

18. The process as in claim 1 , further comprising recycling at least a portion of the light effluents back to the reactor.

19. The process as in claim 1 , wherein the reactor operates at a hydrogen partial pressure (bar) of 5-60;
a temperature (° C.) of 400-500; and
a liquid hourly space velocity (h −1 ), on a fresh feed basis relative to the catalysts, in the range of 0.1-20.

20. The process as in claim 1 , further comprising passing the upgraded heavy oil effluents to a separation zone to recover hydrocarbon products and bottoms, and optionally recycling bottoms to the reactor.

21. The process as in claim 20 , further comprising
passing bottoms and C3 to C8 light paraffins at a solvent-to-bottoms ratio (weight to weight) is in the range of about 2:1-10:1 to a solvent deasphalting unit to separate a deasphalted oil phase and an asphalt phase,
recovering deasphalted upgraded oil as the deasphalted oil phase;
discharging as the asphalt phase asphalt and catalyst particles; and
optionally recycling all or a portion of the asphalt phase including catalyst particles to the catalytic hydrogen-aquathermolysis reactor.

22. The process as in claim 20 , comprising
mixing bottoms with paraffinic solvent and an effective quantity of solid adsorbent material, at a temperature and pressure that are below the critical pressure and temperature of the solvent to promote solvent-flocculation of solid asphaltenes, and for a time sufficient to adsorb on the solid adsorbent material sulfur-containing and nitrogen-containing polynuclear aromatic molecules that are contained in the upgraded heavy oil effluents, to form a mixture;
passing the mixture to a first separation vessel;
separating a solid phase comprising asphaltenes and solid adsorbent material from a liquid phase comprising deasphalted oil and paraffinic solvent;
passing the solid phase to a filtration vessel with an aromatic and/or polar solvent to desorb the adsorbed contaminants and to recover regenerated solid adsorbent material; and
passing the liquid phase to a second separation vessel to separate deasphalted oil and paraffinic solvent, and optionally recycling at least a portion of the separated paraffinic solvent to the step of mixing bottoms with paraffinic solvent and an effective quantity of solid adsorbent material.

Assignees

• Saudi Arabian Oil Co

Inventors

• Fathi Mazin M
• Koseoglu Omer Refa

Classifications

• C10G45/16

  suspended in the oil, e.g. slurries · CPC title

• C10G21/14

  Hydrocarbons · CPC title

• C10G2300/4012

  Pressure · CPC title

• C10G67/14 Primary

  including at least two different refining steps in the absence of hydrogen · CPC title

• C10G47/02

  characterised by the catalyst used · CPC title